CN1830102A

CN1830102A - Secondary cell electrode and fabrication method, and secondary cell, complex cell, and vehicle

Info

Publication number: CN1830102A
Application number: CNA2004800216937A
Authority: CN
Inventors: 长山森; 斋藤崇实; 岛村修
Original assignee: Nissan Motor Co Ltd
Current assignee: Nissan Motor Co Ltd
Priority date: 2003-07-31
Filing date: 2004-07-27
Publication date: 2006-09-06
Anticipated expiration: 2024-07-27
Also published as: JP4055671B2; JP2005050755A; CN100463254C

Abstract

In a nonaqueous electrolyte cell-oriented electrode (10), an electrode active material layer (12) formed on a collector (1) has a density gradient developed with a gradient of a varied concentration of a solid along a thickness from a surface of the electrode active material layer (12) toward the collector (1), and in a gel electrolyte cell-oriented electrode (30), an electrode active material layer (32) formed on a collector (1) has a density gradient developed with (a) gradient(s) of (a) varied concentration(s) of one or both of an electrolyte salt and a film forming material along a thickness from a surface of the electrode active material layer (32) toward the collector (1).

Description

Electrode for secondary battery and manufacture method, and secondary cell, composite battery, and vehicle

Technical field

The present invention relates to a kind of electrode for secondary battery, and relate in particular to nonaqueous electrolyte electrode and gel electrolyte electrode, and then relate to the manufacture method of above-mentioned electrode, and use the secondary cell of described electrode for secondary battery, the composite battery of the described secondary cell of use, and the vehicle that uses described secondary cell or composite battery.

Background technology

Under the background of environmental protection ascendant trend, seen recent years further developing motor vehicle (EV), motor vehicle driven by mixed power (HEV) and fuel cell-powered car (FCV), and development is used for the battery of its CD-ROM drive motor.

For the object of high output of needs and high-energy-density, for example be used to drive the motor of EV, HEV or FCV, to handle large-sized simple battery and be actually difficulty, typical measure is to use the composite battery of being made up of a plurality of series-connected cells.For using this composite battery, Japanese patent application discloses 2003-151526 number and has advised a kind of thin laminated cell.

Summary of the invention

This laminated cell has and uses coating machine etc. that electrode active material is coated on collector electrode or the metal forming and the plus or minus polarizing electrode that forms, thereby solid material or electrolyte components concentration on three-dimensional are even.

As hereinafter described, such laminated cell will be exhausted by the Li ion can under big current rate in the charge or discharge unfavorable trend, this just causes for example battery performance reduction of charge or discharge capacity.

Consider that these aspects have invented the present invention.Therefore, an object of the present invention is to provide a kind of in addition under big current rate also workable electrode for secondary battery and manufacture method thereof, and the vehicle of a kind of secondary cell, composite battery and use secondary cell.

The inventor has been found that and adopts the electrolyte that changes to form in the typing (patterning) in electrode active material layers, uses its electrode active material layers the diffusion of the Li ion of dielectric substrate supply to be had the electrode of low resistance.

In order to realize described purpose, first aspect of the present invention provides a kind of electrode for secondary battery that comprises the electrode active material layers with density gradient.

Another aspect of the present invention provides a kind of manufacture method, and it comprises makes the electrode for secondary battery that comprises the electrode active material layers with density gradient.

Another aspect of the present invention provides a kind of secondary cell that comprises described electrode for secondary battery.

Another aspect of the present invention provides a kind of composite battery that comprises a plurality of secondary cells connected to one another.

Another aspect of the present invention provide a kind of comprise a plurality of by described manufacture method make and composite battery secondary cell connected to one another.

Another aspect of the present invention provides a kind of vehicle that comprises described secondary cell.

Another aspect of the present invention provides a kind of vehicle that comprises the secondary cell of making by described manufacture method.

In conjunction with the accompanying drawings, of the present invention other will become obvious with further feature, advantage and interests from following specification.

Description of drawings

Fig. 1 is the profile of the electrode of typical rechargeable nonaqueous electrolytic battery.

Fig. 2 is the profile of the electrode of the rechargeable nonaqueous electrolytic battery of first embodiment according to the present invention.

Fig. 3 is the profile according to the electrode of the rechargeable nonaqueous electrolytic battery of first embodiment modification.

Fig. 4 is the profile of the electrode of the gel electrolyte secondary battery of second embodiment according to the present invention.

Fig. 5 is the profile according to the electrode of the gel electrolyte secondary battery of second embodiment modification.

Fig. 6 is the block diagram of secondary cell manufacturing installation.

Fig. 7 is the control flow chart of battery manufacturing installation.

Fig. 8 is the plane graph of electrode for secondary battery.

Fig. 9 is the perspective view of secondary cell.

Figure 10 A is to use the plane graph of the composite battery of described secondary cell.

Figure 10 B is the cutaway view along Figure 10 A line B-B.

Figure 10 C is the cutaway view along Figure 10 A line C-C.

Figure 11 is to use the perspective view of the battery module of composite battery.

Figure 12 is to use the end view of the vehicle of described battery module.

Embodiment

With reference to accompanying drawing in detail, the preferred embodiment of the invention as best mode will be described in detail below.Components identical or part are represented by identical Reference numeral.

This specification is made up of four parts.

First's embodiment brief introduction

The details of second portion embodiment

The third part specific embodiment

The 4th part is replenished

In order to ensure understanding, the commentary of duplication similarity, note or a part are described, with the concrete meaning of pointing out that it relates to.

First's embodiment brief introduction

This part comprises:

1.1 the typical structure of electrode

1.2 the first embodiment brief introduction

1.3 the second embodiment brief introduction

1.4 make and install

1.1 the typical structure of electrode

Fig. 1 has represented the electrode of typical rechargeable nonaqueous electrolytic battery SC by constructed profile.

In secondary cell SC, (this paper is called " current collector " to a slice charge-trapping utmost point, or abbreviation work " collector electrode ") 1 has coating in the above to form the active material layer 2 of electrode, and active material layer has the film like dielectric substrate 3 that forms in the above again.

(this paper is referred to as " electrode active material " as equally distributed electro-chemical activity compound to apply active material layer 2 on electrode zone, or abbreviation work " active material ") the electrode definition system of 4 particles, the spaces of using pentalyte (this paper is called " electrolyte ") 5 to fill therebetween.

Suppose that secondary cell SC is a lithium ion battery, dielectric substrate 3 comprises the Li ion 6 that can be used as the positive carrier diffusion motion.

Collector electrode 1 has the free electron 7 as the charge carriers conduction.

The speed of entire electrode reaction depends on 2 pairs of resistances from Li ion 6 diffusions of dielectric substrate 3 supplies of electrode active material layers.

For instance, in the discharge process of secondary cell SC, the Li ion 6 in the electrolyte 5 of electrode active material layers 2 is rapidly absorbed in the particle of electrode active material 4.

The reduction of Li ion 6 concentration in the electrolyte 5 of gained electrode active material layers 2 replenishes by the diffusion of Li ion 6 from dielectric substrate 3.

Similarly, according to the variation of the Li ion concentration of electrode active material layers 2, Li ion 6 returns and enters dielectric substrate 3 to outdiffusion.Simultaneously, the electronics 7 of collector electrode 1 conducts by the electrochemistry electric conducting material, thereby has promoted electrode reaction.

The diffusion of Li ion 6 is slowly with respect to the conduction of electronics 7.Under the high speed charge or discharge, Li ion 6 trends towards exhausting, and along with moving to the depths, this trend increases, and the ionic mobility that causes in the depths diffusion reduces.

On the other hand, the conductivity of Li ion 6 increases along with the increase of Li ion 6 concentration, but reduces along with the excessive increase of Li ion concentration, and this is accompanied by the increase of electrolyte viscosity, thereby has limited the diffusion of Li ion 6.

Once more, under the high speed charge or discharge, Li ion 6 trends towards exhausting, and along with moving to the depths, this trend increases, and the ionic mobility that is caused by diffusion in the depths reduces.

In the electrode SC of the uniform electrode active material layers 2 of three-dimensional, under the high speed charge or discharge, in this floor 2 diffusion of Li ion 6 be unable to catch up with near or the thickness of the bottom of extending near collector electrode 1 upside or degree of depth district in the variation of Li ion concentration, cause occurring overvoltage, thereby enough charge or discharge capacity can not be provided, and this is a problem.

A kind of effective solution as this problem, the inventor has invented and provides a kind of electrode for secondary battery with electrode active material layers, described material layer has continuous or stepping concentration of component gradient, thereby is uneven on three-dimensional.

1.2 first embodiment brief introduction

As first embodiment of the present invention, electrode for secondary battery preferably includes the electrode (nonaqueous electrolyte cell-oriented electrode) that is suitable for nonaqueous electrolyte, wherein form electrode active material layers on collector electrode, its density gradient is along with along the solid concentration of the increase of the thickness from the electrode active material layers surface to collector electrode and develop.

Fig. 2 has represented electrode according to the rechargeable nonaqueous electrolytic battery 10 of first embodiment by constructed profile.

In secondary cell 10, a slice electric charge collector electrode 1 has coating in the above to form the active material layer 12 of electrode, and this active material layer has the film like dielectric substrate 3 that forms in the above again.

On electrode zone, apply the electrode definition system of active material layer 12, use liquid electrolyte 15 to fill therebetween along the stepping space of depth direction as the particle of non-" evenly three-dimensional " distribution of solid active material 14.

Solid active material 14 has the concentration of equal variation, and following density gradient is provided in active material layer 12:

Among near first degree of depth district 12a electrode active material layers 12 upper surfaces, the concentration of solid active material 14a is less among the electrolyte 15a.

Among second degree of depth district 12b below first degree of depth district 12a, the concentration of solid active material 14b is medium among the electrolyte 15b.

Below second degree of depth district 12b and among near the 3rd degree of depth district 12c the collector electrode 1, the concentration of solid active material 14c is bigger among the electrolyte 15c.

First degree of depth district 12a comprises the electrolyte 15 of more volume, and wherein Li ion 6 can spread and Li ion 6 is had the diffusional resistance of reduction.

The 3rd degree of depth district 12c comprises more substantial solid material 14, for example electrode active material, electric conducting material and binding agent, and have the contact resistance of reduction with collector electrode 1, this just allows the increase of electronics 7 mobilities.

As a result, the trend that Li ion 6 diffuses in the 3rd degree of depth district 12c increases, and electronics 7 increases from the trend that collector electrode 1 moves, thereby makes electrode 10 stand the high speed charge or discharge.

Noting preferably can be along the degree of depth of electrode active material 12, perhaps even change the concentration of solid active material 15 continuously or step by step in each degree of

depth district

12a, 12b, 12c or a plurality of degree of depth district.At any degree of depth place, the concentration of solid material can be got rid of its bidimensional gradient well.

Fig. 3 has represented the electrode of the rechargeable nonaqueous electrolytic battery 20 revised according to first embodiment by constructed profile.

This battery 20 is different with first embodiment 10, because having as coating, electrode active material layers 22 piles up and first, second and the 3rd degree of depth district 22a, 22b, 22c stacked together,

external boundary

8,8 with the continuous extension that forms with dielectric substrate 3 and collector electrode 1, and same

inner boundary

9,9 of extending.

Among near first degree of depth district 22a electrode active material layers 22 upper surfaces, the concentration of solid active material 24a is less among the electrolyte 25a.

Among second degree of depth district 22b below first degree of depth district 22a, the concentration of solid active material 24b is medium among the electrolyte 25b.

Below second degree of depth district 22b and among near the 3rd degree of depth district 22c the collector electrode 1, the concentration of solid active material 24c is bigger among the electrolyte 25c.

Stacked degree of depth district 22a, 22b, 22c can make the concentration of the solid material 25 in the electrolyte 25 prepare in related coatings (22a, 22b, 22c) evenly.

According to first embodiment, can be preferably by stacked a plurality of because the different thin layers with different densities of solid material concentration provide electrode active material layers.

Solid concentration is the concentration of electrode active material preferably.

Solid concentration is the concentration of electrode active material, electric conducting material and binding agent preferably.

The electrode active material preferred thickness is in the scope of 1-100 micron.

When described electrode for secondary battery comprises the electrode that is suitable for nonaqueous electrolyte, its manufacture method preferably includes: (a) change the amount that will be added with the solid material of forming electrode active material layers, thereby prepare multiple owing to the different electrode slurrys with different densities of solid material concentration; And (b) apply collector electrodes with a series of multiple electrode slurrys, the concentration that makes solid material from the surface of electrode active material layers to the increase of collector electrode order, thereby stacked a plurality of density and the different thin layer of solid material concentration.

The thickness that described thin layer applies in step (b) is preferably in the scope of 1-100 micron.

In step (b), described electrode slurry preferably is coated on the collector electrode by ink ejecting method.

Described ink ejecting method preferably uses piezoelectric system.

According to the secondary cell of first embodiment bipolar cell preferably.

1.3 the brief introduction of second embodiment

As second embodiment of the present invention, electrode for secondary battery preferably includes the electrode that is suitable for gel electrolyte, wherein the electrode active material layers on the collector electrode have along from the surface of electrode active material layers to collector electrode thickness, the density gradient that develops along with the change in concentration of component (perhaps electrolytic salt or filmogen, or its combination).

Fig. 4 has represented electrode according to the gel electrolyte secondary battery 30 of second embodiment by constructed profile.

In secondary cell 30, a slice electric charge collector electrode 1 has coating in the above to form the active material layer 32 of electrode, and this active material layer has the film like dielectric substrate 3 that forms in the above again.

On electrode zone, apply the electrode definition system of active material layer 32, use the liquid electrolyte 35 filling spaces therebetween of non-" evenly three-dimensional " preparation as the three-dimensional equally distributed particle of solid active material 34.

Electrolyte 35 has the gradient concentration of equal variation, and the density gradient of active material layer 32 is provided, and is as follows:

Near first degree of depth district 32a that is arranged in electrode active material layers 32 upper surfaces has less concentration with respect to the electrolytic salt of the intergranular electrolyte 34a that is filled in solid active material 35a.

Second degree of depth district 32b that is arranged in first degree of depth district 32a below has medium concentration with respect to the above-mentioned electrolytic salt that is filled in the intergranular electrolyte 34b of solid active material 35b.

Near the 3rd degree of depth district 32c of electrode active material layers 32 bottoms that is arranged in second degree of depth district 32b below and the extension of collector electrode 1 upper surface has bigger concentration with respect to the above-mentioned electrolytic salt that is filled in the intergranular electrolyte 34c of solid active material 35c.

As a result, the trend that Li ion 6 diffuses in the 3rd degree of depth district 32c increases, and even also can be not depleted under the high speed charge or discharge.

In addition, along the potential gradient that the concentration gradient owing to electrolytic salt causes, Li ion 6 and electronics 7 are accelerated, and the trend of diffusion from dielectric substrate 3 increases.

On the contrary, the concentration of electrolytic salt is along the degree of depth from the upper surface of electrode active material layers 32 to collector electrode 1 and reduce.In the case, the Li ion among first degree of depth district 32a is enrichment, and trends towards therefrom discharging.In addition, because concentration gradient, the diffusion tendency of Li ion increases.

Therefore, secondary cell 30 is suitable for dealing with the high speed charge or discharge.

Noting preferably can be along the degree of depth of electrode active material 32, perhaps even change the concentration gradient of electrolytic salt continuously or step by step in each degree of

depth district

32a, 32b, 32c or a plurality of district.At any degree of depth place, the concentration of electrolytic salt can be got rid of its bidimensional gradient well.

Preferably provide electrode active material layers by the different thin layer of stacked multilayer electrolyte salinity.

Fig. 5 has represented the electrode of the gel electrolyte secondary battery 40 revised according to second embodiment by constructed profile.

This battery 40 is different with second embodiment 30, because having as coating, electrode active material layers 42 piles up and first, second and the 3rd degree of

depth district

42a, 42b, 42c stacked together, itself and dielectric substrate 3 and collector electrode 1 form the external boundary 8 that extends continuously, 8, and same

inner boundary

9,9 of extending.The whole system of the three-dimensional equally distributed solid active material granule of Reference numeral 45 expressions.

Near first degree of depth district 42a that is arranged in electrode active material layers 42 upper surfaces has less concentration with respect to the electrolytic salt of the intergranular electrolyte 44a that is filled in solid active material 45a.

Second degree of depth district 42b that is arranged in first degree of depth district 42a below has medium concentration with respect to the above-mentioned electrolytic salt that is filled in the intergranular electrolyte 44b of solid active material 45b.

Near the 3rd degree of depth district 42c of electrode active material layers 42 bottoms that is arranged in second degree of depth district 42b below and the extension of collector electrode 1 upper surface has bigger concentration with respect to the above-mentioned electrolytic salt that is filled in the intergranular electrolyte 44c of solid active material 45c.

Stacked degree of

depth district

42a, 42b, 42c can make the electrolytic salinity in the electrolyte 44 prepare in related coatings (42a, 42b, 42c) evenly.

According to per two embodiments, when described electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, its manufacture method preferably includes: (a) change the amount that will be added with the electrolytic salt of forming electrode active material layers, thereby prepare multiple owing to the different electrode slurrys with different densities of electrolytic salinity; And (b) with a series of multiple electrode slurrys coating collector electrodes, thereby stacked a plurality of density and the different thin layer of electrolytic salinity, make electrode active material layers have along with from the surface of electrode active material layers to the concentration gradient of collector electrode electrolytic salt and the density gradient that develops.

Perhaps, when described electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, its manufacture method preferably includes: (a) change the amount that will be added with the film forming raw material of forming electrode active material layers, thereby prepare the different electrode slurrys with different densities of multiple concentration owing to the film forming raw material; And (b) with a series of multiple electrode slurrys coating collector electrodes, thereby stacked a plurality of density and the different thin layer of film forming material concentration, make electrode active material layers have along with from the surface of electrode active material layers to the concentration gradient of collector electrode film forming raw material and the density gradient that develops.

Perhaps, when described electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, its manufacture method preferably includes: (a) change will be added with the electrolytic salt of composition electrode active material layers and the amount of film forming raw material, thereby prepares the multiple different electrode slurrys with different densities of concentration owing to electrolytic salt and film forming raw material; And (b) with a series of multiple electrode slurrys coating collector electrodes, thereby the thin layer that stacked a plurality of density and electrolytic salt are different with the film forming material concentration, make electrode active material layers have along with from the surface of electrode active material layers to the concentration gradient of collector electrode electrolytic salt and film forming raw material and the density gradient that develops.

Described ink ejecting method preferably uses piezoelectric system.

According to the secondary cell of second embodiment lithium rechargeable battery preferably.

Described secondary cell is bipolar cell preferably.

Described secondary cell preferably includes: the positive pole that comprises first collector electrode and be suitable for anodal active material layer, and the described density gradient that is suitable for anodal active material layer is along with developing along the concentration gradient of the electrolytic salt that increases to the thickness of first collector electrode from the surface that is suitable for anodal active material layer; The negative pole that comprises second collector electrode and be suitable for the active material layer of negative pole, the density gradient of the described active material layer that is suitable for negative pole is along with developing along the concentration gradient of the electrolytic salt that reduces to the thickness of second collector electrode from the surface of the active material layer that is suitable for negative pole; And dielectric substrate.

On the contrary, described secondary cell preferably includes: the positive pole that comprises first collector electrode and be suitable for anodal active material layer, and the described density gradient that is suitable for anodal active material layer is along with developing along the concentration gradient of the electrolytic salt that reduces to the thickness of first collector electrode from the surface that is suitable for anodal active material layer; The negative pole that comprises second collector electrode and be suitable for the active material layer of negative pole, the density gradient of the described active material layer that is suitable for negative pole is along with developing along the concentration gradient of the electrolytic salt that increases to the thickness of second collector electrode from the surface of the active material layer that is suitable for negative pole; And dielectric substrate.

The active material layer that is suitable for negative pole preferably has the density gradient that develops along with along the concentration gradient of the filmogen that increases to the thickness of second collector electrode from the surface of the active material layer that is suitable for negative pole.

Described secondary cell preferably comprises density gradient along with the active material layer that is suitable for negative pole that develops along the concentration gradient of the filmogen that increases to the thickness of second collector electrode from the surface of the active material layer that is suitable for negative pole.

1.4 make and install

Fig. 6 has represented the battery electrode manufacturing installation CF of electrode for secondary battery according to an embodiment of the invention by block diagram.

Battery electrode manufacturing installation CF is equipped with: as the controller 100 of the computer that has been equipped with necessary peripheral hardware, it comprises multi-purpose interface 102, interactive display 104 and storage necessary program and memory of data; Ink-jet system comprises one group of

nozzle

108a, 108b ... (general designation 108) and one group of

print cartridge

109a, 109b ... (general designation 109), and corollary equipment comprise drying heater 112 and the carrier 150 that is used for carrying collector electrode 110.

The whole manufacturing installation CF of controller 100 controls, and have and be used for handling four-dimensional data, thereby the seasonal effect in time series of drawing ink P injection pattern (pattern) is drawn arithmetic unit 101, wherein selected one is indicated on the display 104, all be stored in the memory 106, and neededly send the local control of ink-jet system and corollary equipment to order, thus on controller 110 the current ink-jetting pattern of exploitation.

Nozzle sets 108 can be but be not limited to one of piezoelectric system, hot system and bubble jet (trade mark) system.

In piezoelectric system, the piezoelectric element that is placed on ink accumulator chamber bottom is out of shape by electricity, thereby sprays ink droplet from relevant injection nozzle 108.

In hot system and bubble spraying system, the heating element heating ink causes evaporation and is accompanied by steam explosion that its energy makes ink droplet ejection from relevant injection nozzle 108.Heat is wanting different on the area heated with the bubble spraying system, but is identical on the principle.

Print cartridge group 109 is divided into a few height groups (as 109a, 109b by the kind of the active material of processing ...), and one to one with nozzle 108 (108a, 108b ...) connect.Print cartridge group 109 can be equipped with the stirring module 109c that stirs ink, and the heater 109d of heating ink.

Heater 112 is used for drying and is deposited on active material on the collector electrode 110.After deposit of ink, collector electrode 110 moves in the drying oven that heater 112 wherein has been installed under the situation by carrier 150 carryings.

Manufacturing installation CF has a large amount of different types of inks, and according to the purpose polarity of each electrode, and the purpose concentration of solid material in the electrode active material layers relevant thickness district or electrolytic salt is selected suitable a kind of.

For instance, prepare in the ink group of straight polarity electrode being used for, any ink all comprises the component of this electrode active material layers, and the kind of the ratio of component by ink changes.

Equally, prepare in the ink group of negative polarity electrode being used for, any ink all comprises the component of this electrode active material layers, and the kind of the ratio of component by ink changes.

Fig. 7 has represented to make the series of steps of electrode for secondary battery.

In step S1, the deposited picture of preparation necessary amount in computer 100.

In step S2, deposited picture is stored in the memory 106.

In step S3, use for current manufacturing, from memory 106, read corresponding pattern.

In step S4, handle the pattern of reading by drawing arithmetic unit 101, thereby deposit active material in the drawing a design on collector electrode 110.

In step S5, collector electrode 110 is sent in the drying oven, wherein by heater 112 heating and the dry active material layer that deposits.

Making electrode for secondary battery as forming positive electrode layer on collector electrode 110 1 sides and on opposite side, forming in the situation of bipolar electrode of positive electrode layer, repeat the step twice of described order, once be used for forming positive electrode layer, another time is used for forming positive electrode layer.

Fig. 8 with plan representation as the electrode for secondary battery of the bipolar electrode of making by the step that repeats described order.

Size is formed electrode layers 111 of active material of injection certain volume on collector electrode 100 1 sides less than the shade plane domain of collector electrode 110.

Bipolar electrode has positive pole and the negative pole that forms in collector electrode 110 both sides.The electrode layer 111 of supposing Fig. 8 is anodal, forms positive electrode layer so on opposing face.

Fig. 9 has represented the perspective view of simple secondary cell 120.

These secondary cell 120 inside have the cell device of being made up of according to described method manufacturing and the electrode for secondary battery (can be bipolar electrode) that stacks layer by layer with intermediate electrolyte a plurality of.Described cell device is installed in by in the film formed planar housings 122 of a pair of bubble-tight polymer-metal composite laminate.Inner positive terminal 124 that is connected with cell device and negative pole end 126 extend by the edge of shell 122, are used for outside the connection thereby expose.

This secondary cell can series, parallel, perhaps connection in series-parallel, and be encapsulated as composite battery or battery component.

Figure 10 A to 10C has shown the composite battery 200 that is encapsulated in the rectangle elongation shell 202.This composite battery 200 is equipped with a plurality of secondary cells 120 that series, parallel or connection in series-parallel connect in shell 202, and has pair of lead wires end 204, its any be connected with the positive terminal 124 of outmost secondary cell 120, and another is connected with the negative pole end 126 of another outmost secondary cell 120, and reach the outside of shell 204, be used for being connected with corollary apparatus is outside.

This composite battery can series, parallel or connection in series-parallel, and piles up and be assembled into battery module 300.

Figure 11 is the perspective view of battery module 300.

Battery module 300 is equipped with that a plurality of series, parallel or connection in series-parallel connect piles up composite battery 200, and be connected end plate 302 by the fixing electricity of screw 304 and be assembled together.Protect battery module 300 not to be subjected to external impact by the elastomeric material that is applied on the outer surface that space neutralization comprises basal surface.

The quantity of the composite battery 200 of the quantity of the secondary cell 120 of composition composite battery 200 and composition battery module 300, and their connection is decided according to desired volume and power.The secondary cell that making stability increases is used for composite battery, and the secondary cell that stability further increases is used for battery module.At composite battery, and in the battery module, used secondary cell is whole to be kept stable and the durability increase, thereby avoids worsening the adverse effect that causes by any secondary cell.

This composite battery or battery module can perform well in the vehicle.

Figure 12 has represented wherein to install the typical vehicle 400 of composite battery 200 and battery module 300 combinations with end view.

The composite battery 200 and the battery module 300 that are installed in the vehicle 400 make the electrology characteristic of for example specified supply power and required performance, for example the power division of vehicle 400 and driving coupling.The secondary cell that composite battery 200 and battery module 300 have even also can meet the power supply service and have the height durability after long-time the use.In addition, they are configured to make it to show stable performance for the continuous shaking in vehicle 400, and can be owing to resonance shows tangible deterioration.

The details of second portion embodiment

The details of the nonaqueous electrolyte electrode of first embodiment has been contained according to the present invention in this part, and according to the present invention the details of the gel electrolyte electrode of second embodiment.

2.1 the details of first embodiment (nonaqueous electrolyte electrode)

2.1.1 the structure of nonaqueous electrolyte electrode

2.1.1a nonaqueous electrolyte electrode

Electrode active material layers is preferably but not limited to being configured to have a plurality of laminated thin retes that solid concentration differs from one another.

Described structure allows to form electrode active material layers, and its concentration gradient makes solid concentration increase along the thickness from laminar surface to collector electrode.

The quantity of laminated thin rete can be two-layer or more than, preferably three layers or more than, perhaps more preferably five layers or more than.

Term in the solid concentration " solid " means the solid electrode material, for example may be included in electrode active material, electric conducting material or binding agent in the electrode active material layers.

Suitably select this solid, form the concentration gradient that the thickness solid concentration along the electrode active material layers surface to collector electrode increases.

For instance, under this concentration gradient, can reduce the diffusional resistance of Li ion, even also allow effective electrode reaction takes place under the high speed charge or discharge, this is an advantage.

For more favourable effect, also can be under this concentration gradient distribution electrode active material, electric conducting material and binding agent, thereby reduce contact resistance between collector electrode and the electrode.

Polarity is that the thickness of electrode preferred electrode active material layer of plus or minus is in the scope of 1-100 micron, more preferably in the scope of 5-50 micron.

The preferred thickness range of electrode active material layers does not comprise the very thickness range below 1 micron of difficulty of formation concentration gradient, and the ions diffusion distance may can not guarantee the high scope of exporting more than 100 microns too greatly.

Collector electrode typically or in general is, and the clad metal material of clad metal material, SUS and the aluminium of clad metal material, copper and the aluminium of aluminium foil, SUS (stainless steel) paper tinsel, nickel and aluminium is preferably perhaps wanted the combination of these metals of plating for instance.

In addition, collector electrode can be the metal of its surface with the aluminium covering, perhaps can be a pair of coherent metal forming when environment needs.

When using compound collector electrode, the material of its positive polarity collector electrode is for example aluminium, aluminium alloy, SUS preferably, the perhaps conducting metal of titanium, and aluminium is most preferred.

The material of negative polarity collector electrode is the conducting metal of copper, nickel, silver or SUS for example preferably, and nickel and SUS are most preferred.

In compound collector electrode, positive polarity and negative polarity collector electrode are direct each other well, perhaps connect by the conduction intermediate layer of being made up of the third material.

The thickness of the positive polarity of compound collector electrode and negative polarity collector electrode is for instance in the typical range of about 1-100 micron.

For collector electrode (comprising compound collector electrode), be preferred from the thickness range of the about 1-100 micron of angle of making thin battery.

2.1.1b be used for anodal electrode

In order to be used for positive pole, (this paper is called sometimes that " positive electrode layer ") comprises positive electrode active materials and necessary additive, comprises electric conducting material, the binding agent that is used for strengthening electronic conductivity, lithium salts and the electrolyte that is used for strengthening ionic conductivity to be suitable for anodal electrode active material layers.

Positive electrode active materials is lithium-compound transition metal oxide preferably, and it is the composite oxides of transition metal and lithium.

More particularly, positive electrode active materials one of following material preferably: LiCoO for example ₂Li-Co composite oxides family, for example LiNiO ₂Li-Ni composite oxides family, for example LiMn ₂O ₄Li-Mn composite oxides family, and LiFeO for example ₂Li-Fe composite oxides family, perhaps their other transition metals of any usefulness replace the material of its transition metal.

These lithium-transition metal composite oxides are being excellent aspect reactive and the cycle life, and cost is lower.

Therefore, they are advantageously used in the electrode of the battery that excellent output performance can be provided.

Positive electrode active materials is one of following material preferably: the phosphate of lithium and transition metal or sulfate, for example LiFePO ₄Transition metal oxide or sulfide, for example V ₂O ₅, MnO ₂, TiS ₂, MoS ₂And MoO ₃And other available compound, for example PbO ₂, AgO and NiOOH.

The particle diameter of positive electrode active materials preferably drops in the scope of 0.1-50 micron, perhaps more preferably in the scope of 0.1-20 micron.

Preferred particle size range does not comprise the scope below 0.1 micron of making difficulty and required charge or discharge characteristic can not being provided, and the scope more than 50 microns that is difficult to grind to form positive electrode active materials.

Electric conducting material is acetylene black, carbon black, graphite etc. preferably.

The particle diameter of electric conducting material preferably drops in the scope of 0.1-50 micron, perhaps more preferably in the scope of 1-30 micron.

The preferable particle size scope of electric conducting material does not comprise the scope below 0.1 micron that increases the electric conducting material amount for necessary electronic conduction needs, and the scope more than 50 microns that is difficult to grind to form positive electrode active materials.

Binding agent can be but be not limited to polyvinylidene fluoride (PVDF), SBR, polyimides etc.

Lithium salts can be but be not limited to one of following material: BETI (lithium two (to the PVF sulfimide)), Li (C ₂F ₅SO ₂) ₂N, LiBF ₄, LiPF ₆, LiN (SO ₂CF ₃) ₂, LiN (SO ₂C ₂F ₅) ₂And LiBOB (double oxide lithium borate), perhaps one of its mixture.

Electrolyte is the nonaqueous electrolyte that the concentration gradient of necessity can be provided.The total solids electrolyte that nonaqueous electrolyte preferably is made up of the support salt of electrolyte high polymer and for example lithium salts is perhaps by the electrolyte high polymer with remain on the high coagel electrolyte that electrolyte solution is wherein formed.

When electrolyte was nonaqueous phase, positive electrode layer preferably comprised nonaqueous electrolyte.

Fill at nonaqueous electrolyte under the situation of positive electrode active materials intergranular space, the ion transfer in the positive electrode layer is steady, and this just makes entire cell have the output of enhancing.

If electrolyte is high coagel or has barrier film with the electrolyte solution that soaks that under the situation of the particle that makes known binding agent bonding positive electrode active materials, positive electrode layer can not contain electrolyte.

Total solids electrolyte high polymer can be but be not limited to polyethylene glycol oxide (PEO), PPOX (PPO) and copolymer thereof.These polyalkylene oxides can dissolve lithium salts, for example BETI, LiBF well ₄, LiPF ₆, LiN (SO ₂CF ₃) ₂And LiN (SO ₂C ₂F ₅) ₂

They form crosslinked structure, thereby show excellent mechanical strength.

According to the present embodiment, in the negative or positive electrode active material layer, comprise solid polymeric electrolyte at least.

But,, preferably in both, all comprise in order to increase the performance of bipolar cell.

The high polymer gel electrolyte can be comprise electrolyte solution be suitable for the electrolytical ionic conduction high polymer of total solids, perhaps in its skeleton, maintain the main polymer (host polymer) of the non-conducting lithium ion of similar electrolyte solution.

The electrolyte solution that comprises in the high polymer gel electrolyte (electrolytic salt and plasticizer) can be the typical electrolyte solutions that is used for lithium ion battery, and can be but be not limited to the electrolyte solution that comprises at least a lithium salts (electrolyte support salt), described lithium salts is selected from inorganic anion salt, for example LiBOB (double oxide lithium borate), LiPF ₆, LiBF ₄, LiClO ₄, LiAsF ₆, LiTaF ₆, LiAlCl ₄And Li ₂B ₁₀Cl ₁₀, and organic anion salt, for example LiCF ₃SO ₃, Li (CF ₃SO ₂) ₂N and Li (C ₂F ₅SO ₂) ₂N, in the organic solvent (plasticizer) of for example aprotic solvent, use the aprotic solvent of at least a or two or more mixing, described aprotic solvent is selected from for example cyclic carbonate of propene carbonate (PC) and ethylene carbonate (EC), dimethyl carbonate for example, the linear carbonate of methyl ethyl carbonate and diethyl carbonate, oxolane for example, the 2-methyltetrahydrofuran, 1, the 4-dioxane, 1,2-dimethoxy-ethane and 1, the ether of 2-dibutoxy ethane, the lactone of gamma-butyrolacton for example, the for example nitrile of acrylonitrile, for example ester of methyl propionate, for example acid amides of dimethyl formamide, methyl acetate, and methyl formate.

The main polymer of the non-conducting lithium ion that comprises in the high polymer gel electrolyte can be but be not limited to the monomer that forms gelatin polymer, for example polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polyacrylonitrile (PAN), perhaps polymethyl methacrylate (PMMA).

Note PAN, PMMA etc. just exemplarily as the main polymer of the non-conducting lithium ion that comprises in the high polymer gel electrolyte,, and can belong to and be used for electrolytical ionic conduction high polymer group although they have an ionic conduction.

The high polymer in the high polymer gel electrolyte and the ratio of electrolyte solution can be from 2:98 to 90 according to purpose etc.: 10 mass ratioes.

Therefore, can also seal effectively, prevent to ooze out electrolyte from the periphery of electrode active material layers by insulating barrier or insulated part are provided.

Therefore, the high polymer in definite high polymer gel electrolyte and the mass ratio of electrolyte solution under the situation of more preferably considering battery performance.

For the positive electrode layer that comprises positive electrode active materials, electric conducting material, binding agent, nonaqueous electrolyte (main polymer, electrolyte solution etc.), lithium salts etc., the conductivity that can consider the purpose (paying the utmost attention to output, energy etc.) of battery and Li ion is determined the ratio of these components.

For instance, if the ratio of nonaqueous electrolyte less than the required ratio of positive electrode layer, then the conduction resistance of Li ion and diffusional resistance become big, make battery performance reduce.

On the contrary, if the ratio of nonaqueous electrolyte greater than the required ratio of positive electrode layer, then the energy density of battery reduces.

Consider that these factors determine the amount of nonaqueous electrolyte, thereby satisfy described purpose.

Omitted as mentioned above explanation herein about positive electrode layer thickness.

Positive electrode layer has as mentioned above the preferred thickness of (consulting the 2.1.1a part).

2.1.1c be used for the electrode of negative pole

In order to be used for negative pole, (this paper is called sometimes that " positive electrode layer ") comprises negative active core-shell material and necessary additive, comprises electric conducting material, the binding agent that is used for strengthening electronic conductivity, lithium salts and the electrolyte that is used for strengthening ionic conductivity to be suitable for the electrode active material layers of negative pole.These additives are similar to the material of positive electrode layer (consulting the 2.1.1b part).

Negative active core-shell material preferably for example natural or one of the various graphite of synthetic graphite (for example fiber graphite, crystalline flake graphite and globular graphite), various lithium alloys etc.

More particularly, negative active core-shell material is one of carbon, graphite and lithium-transition metal composite oxide preferably, and carbon and lithium-transition metal composite oxide are preferred.

Lithium-transition metal composite oxide and carbon are being excellent aspect reactive and the cycle life, and cost is lower.

Lithium-transition metal composite oxide can be Li for example for instance ₄Ti ₅O ₁₂Lithium-titanium composite oxide.

Carbon can be graphite, hard carbon or soft carbon for instance.

2.1.2 the manufacturing of nonaqueous electrolyte electrode

2.1.2a manufacture method

First embodiment according to the present invention, make the nonaqueous electrolyte electrode by the following method, described method comprises: change will be added the amount with the solid material of forming electrode active material layers, thereby prepares the step (a) of the multiple density electrode slurry different with solid material concentration; And apply collector electrode with multiple electrode slurry, and make that the concentration from the surface of electrode active material layers to the collector electrode solid material increases in proper order, thus the step (b) of the different thin layer of stacked a plurality of solid material concentration.

This method can provide the nonaqueous electrolyte according to first embodiment, and the thin layer that wherein stacked a plurality of density are different with solid material concentration makes it to have the concentration gradient that increases to collector electrode solid material concentration from the electrode active material surface.

2.1.2b the manufacturing of straight polarity electrode

Be suitable for anodal electrode in order to make, in the step (a) of described method (consulting the 2.1.2a part), prepare multiple electrode slurry respectively as the corresponding solution that comprises positive electrode active materials (this paper is called for short " anode sizing agent ", perhaps is called for short " positive electrode ink " in the present embodiment sometimes).

Described slurry can comprise as required electric conducting material, binding agent, as the non-aqueous solution electrolysis raw material be suitable for electrolytical high polymer, electrolyte is supported salt, initator, solvent etc.

For instance, anode sizing agent can be supported the additive of salt by add electric conducting material for example, binding agent and electrolyte in the solvent that comprises positive electrode active materials, and waits and stirring gained solution prepares in order evenly to mix.

Equally, prepare the multiple for example slurry of the solid material of positive electrode active materials, electric conducting material and binding agent that has, change the amount of its interpolation as required, thereby required concentration gradient is provided.

Positive electrode active materials, electric conducting material, binding agent, be suitable for electrolytical high polymer and electrolyte and support the explanation of salt with reference to the front.

For the viscosity control of anode sizing agent, can select appropriate solvent according to the kind of slurry, for example positive N-methyl-2-2-pyrrolidone N-(NMP) or positive pyrrolidones.

Preferably use identical solvent for various anode sizing agents.

Consider the thickness of positive electrode layer, the particle diameter that positive electrode active materials can be set is below 50 microns, preferably in the scope of 0.1-50 micron, perhaps more preferably in the scope of 1-20 micron.

According to the method for wanting polymeric compounds and polymerization to use, for example thermal polymerization, photopolymerization, radiation polymerization or electron beam polymerization are suitably selected initator.

For instance, initator can be but be not limited to as light trigger benzyl dimethyl ketal (benzyldimetilketarl) or as the azodiisobutyronitrile of thermal initiator.

Support salt and conductive auxiliary agent for positive electrode active materials, electrolyte, can be according to its additions of control such as purpose of battery.

The addition of initator depend on be used for nonaqueous electrolyte be suitable for the crosslinkable number of functional groups of electrolytical polymer.

Typically, its addition is in the scope with respect to the about 0.01-1% of mass ratio that is suitable for electrolytical polymer.

In the step (b) in described manufacture method (consulting the 2.1.2a part), " applying collector electrode with multiple anode sizing agent " can be preferably by a kind of carrying out in silk screen printing, spraying method, electrostatic coating method and the ink ejecting method.

Ink ejecting method is that the drop with anode sizing agent is coated to the method on the collector electrode from ink nozzle, can make the target area of collector electrode be coated with the slurry that is covered with required homogeneous film thickness, thereby makes the pattern coating of anode sizing agent with optimum.This is preferred.

Mean with " optimum pattern " coating anode sizing agent in coating by ink ejecting method anode sizing agent is coated on the collector electrode, the concentration of solid material is increased in proper order.

Ink ejecting method uses the known ink system (drop-on-demand system) that drips as required.

Described optimum system choosing is a piezo-electric type, and wherein ceraminator is out of shape along with the voltage that applies on it, thereby discharges liquid.

In piezo type, the electrode material that comprises in the anode sizing agent (being positive electrode ink) is excellent aspect thermal stability, and it is variable making the quantity of ink that must apply.

The piezo-electric type ink gun is suitable for the liquid of carrying various viscosity higher, in effective conveying scope of viscosity 10Pas (100cp), and the accuracy that it has reliable stability and is better than other type.

Typical piezo-electric type ink gun is equipped with at head and stores the print cartridge of positive electrode ink and the ink guide member that is communicated with print cartridge by ink channel.

This ink gun has a plurality of nozzles that come its lower part, the array of piezoelectric elements of face portion disposed thereon, and the drive pressure electric device carries the driver of liquid in the print cartridge, thus ink-jet from relevant nozzle.

This ink gun structure is exemplary, rather than restrictive.

Can use commercially available ink gun well.

It is difficult that the metal forming that applies positive electrode ink is sent in the ink-jet printer.This paper tinsel can paste on the high-quality paper, sends in the ink-jet printer again.

The ink guide member that plastics are made may be partly dissolved by the solvent of positive electrode ink.

The ink guide member is metal preferably.

The viscosity of anode sizing agent is preferably placed under 25 ℃ in the scope of 0.1-100cP, more preferably in the scope of 0.5-10cP, perhaps more more preferably in the scope of 1-3cP.

Preferred range of viscosities can not comprise the scope below the 0.1cP of the control amount of liquid difficulty as the ink of ink-jet time of positive electrode ink wherein, and positive electrode ink scope that surpasses 100cP by the nozzle difficulty as the ink of ink-jet time the wherein.

Can measure viscosity well by L type viscosimeter, rotation viscometer etc.

During as the ink of ink-jet, the anode sizing agent that is coated on the collector electrode has line, fritter or thin spot at the anode sizing agent that uses high viscosity.

In the case, preferably use heater heats anode sizing agent that print cartridge provides to suitable viscosity.

Low-viscosity anode sizing agent can make positive electrode active materials be deposited in the print cartridge, can be by stirrings well such as rotating vanes.

Method by ink-jet system coating anode sizing agent can be preferably but is not limited to one of following method: provide the liquid of an ink gun and a plurality of nozzle of small diameter of independent control to carry behavior, thereby with the pattern of optimum drop is sprayed to the lip-deep method of collector electrode (1); And provide a plurality of ink guns and independent its liquid of control to carry behavior, thereby drop is sprayed to the lip-deep method of collector electrode (2) with the pattern of optimum.

These methods can form required optimum pattern at short notice.

In described method (1) and (2), " independent controlling liquid conveying behavior " is connected, passes through software including, but not limited to the ink-jet printer that will use ink gun with commercially available computer etc. for instance, for example the required pattern of Power Points (Microsoft) or Auto CAD (AutoDesk company) preparation is also therefrom read, and uses from the electrical signal of this software and carry out control.

In method (1), " with optimum pattern drop is sprayed on the collector electrode surface " and preferably include following steps: independent control nozzle of small diameter liquid is separately carried behavior, thereby a kind of anode sizing agent is sprayed on the collector electrode surface, form thin layer, repeat to spray the less anode sizing agent of another kind of solid material concentration then, each formation thin film layer, thereby the different anode sizing agent coating of stacked multilayer concentration, thus realize required concentration gradient.

In method (2), " drop is sprayed on the collector electrode surface " and preferably include following steps: independent each ink gun of control with optimum pattern, thereby the mixing drop of the various anode sizing agents that solid material concentration is different sprays on the collector electrode surface, thus stacked multi-layer thin rete with desired concn gradient.

Consider the thickness of positive electrode layer, the granular size of the anode sizing agent drop that preferred setting will be carried from ink gun is in the scope of 1-500pl, perhaps more preferably in the scope of 1-100pl.

The film thickness that applies is preferably in the scope of 1-100 micron, and perhaps more preferably in the scope of 5-50 micron, in order to realize the anode active material layer of desired thickness, described thickness can be regulated.

The scope below 1 micron that the battery capacity wherein of not comprising preferred thickness range extremely reduces, and wherein the diffusion length that prolongs in electrode of Li ion can cause that resistance becomes the big scope more than 100 microns.

Stacked multi-layer thin rete can be distinguished suitably and to determine its thickness in anode active material layer, thereby realizes required electrode characteristic, and needs not be impartial.

The anode sizing agent of coating is typically can be in atmosphere dry, preferably under vacuum atmosphere 20-200 ℃ temperature range inner drying 1 minute to 8 hours, perhaps more preferably 80-150 ℃ temperature range inner drying 3 minutes to 1 hour.

These conditions are not restrictive, thereby can come to determine drying condition by rights according to the quantity of solvent in the anode sizing agent of coating for instance.

If the anode sizing agent that uses does not contain nonaqueous electrolyte (being suitable for the high polymer or the high polymer gel electrolyte of all solid state electrolyte), dry anode sizing agent can soak with the electrolyte slurry that the following describes.

Preferably by but be not limited to and be configured to supply a spot of applicator (applicator) or coating machine (coater) soaks.

Method according to the electrolyte high polymer that comprises in the suitably definite polymerization anode sizing agent of used initator, and for instance when using light trigger, even can in atmosphere, carry out, but it is preferred in the inert atmosphere of for example argon gas or nitrogen, perhaps more preferably in vacuum atmosphere, in 0-150 ℃ temperature range, preferred again in 20-40 ℃ temperature range, in 1 minute to 8 hours scope, more preferably in 5 minutes to 1 hour scope, shine with ultraviolet ray.

According to the present embodiment, can make straight polarity electrode according to other mode.

For instance, use is suitable for electrolytical high polymer and initially prepares anode sizing agent to the initator that wherein adds.

Preferably apply the step of multiple anode sizing agent by order, can well multilayer anode sizing agent coat layer be stacked on the substrate, for example on dielectric substrate (dielectric film) or the barrier film with the electrolyte immersion, stacked from the sort of beginning of solid material concentration minimum, thus realize required concentration gradient.

Then, as the available method of another kind, can make straight polarity electrode in conjunction with collector electrode on the lamination of the anode sizing agent coating of drying and polymerization.

2.1.2c the manufacturing of negative polarity electrode

In order to make the electrode that is suitable for negative pole, in the step (a) of described method (consulting the 2.1.2a part), prepare multiple electrode slurry respectively as the corresponding solution that comprises negative active core-shell material (this paper is called for short " cathode size ", perhaps is called for short " negative electrode ink " in the present embodiment sometimes).

For negative active core-shell material, electric conducting material, binding agent and be suitable for electrolytical high polymer, electrolyte and support salt, initator, solvent etc., the amount of its kind and interpolation is with reference to the explanation of front.

The particle diameter that negative active core-shell material preferably is set is below 50 microns, and more preferably in the scope of 0.1-20 micron, this particle is dispersed in the anode active material layer.

In the step (b) in described manufacture method (consulting the 2.1.2a part), " applying collector electrode with multiple cathode size " can be preferably by carrying out with the anode sizing agent similar methods.

Attention is preferably made negative polarity electrode and straight polarity electrode, thereby is avoided moisture is included in the electrode in first embodiment under-20 ℃ dew point and following temperature.

2.1.3 the application of nonaqueous electrolyte electrode

2.1.3a nonaqueous electrolyte battery

First embodiment provides the various nonaqueous electrolyte electrodes that can bear the high speed charge or discharge, uses the nonaqueous electrolyte battery that they can the obtained performance excellence.

For the positive pole and the negative polarity electrode of nonaqueous electrolyte battery, with reference to the explanation of front.

Nonaqueous electrolyte battery has dielectric substrate, and arbitrary layer can be to have the high polymer that is suitable for all solid state electrolyte or the non-aqueous electrolyte layer of high polymer gel electrolyte.

In order to form this dielectric substrate, prepare suitable electrolyte slurry (being called " electrolyte ink " in the present embodiment sometimes), it comprises and is suitable for electrolytical high polymer and lithium salts, and initator, solvent etc.Can suitably prepare these components, thereby obtain required non-aqueous electrolyte layer.

By but be not limited to from being used for the mixture polymerization single polymerization monomer of electrolytical high polymer and lithium salts, form the high polymer that is suitable for all solid state electrolyte as the compound of polymer and lithium salts.

Can form the high polymer that is suitable for all solid state electrolyte by the high polymer that soaks gel electrolyte to barrier film or be suitable for all solid state electrolyte.

Be suitable for electrolytical high polymer, lithium salts, initator and solvent to above-mentioned similar.

By but be not limited to use and comprise the electrolyte solution that is suitable for electrolytical high polymer and come polymerization single polymerization monomer, form gelatin polymer, can form the high polymer gel electrolyte.

Be suitable for electrolytical high polymer and electrolyte solution, with and ratio to above-mentioned similar.

But it is impartial that the amount of the electrolyte solution that comprises in the high polymer gel electrolyte preferably keeps basically, perhaps reduces towards periphery from central authorities according to the mode that tilts.

The former makes as an advantage and reacts in wideer zone.The latter has the sealing of increase for the electrolyte solution of the high polymer that is suitable for all solid state electrolyte in the periphery as an advantage.

The thickness of non-aqueous electrolyte layer is more little, and it has good more performance aspect the reduction internal resistance.

The thickness of non-aqueous electrolyte layer can drop in the scope of 0.1-100 micron, and is perhaps preferred in the scope of 5-20 micron.

The make a comment or criticism thickness of the non-aqueous electrolyte layer between the utmost point and the negative pole of described thickness.

Therefore, in some dielectric substrate manufacture methods, can for example form non-aqueous electrolyte layer by in conjunction with the identical or different dielectric film of thickness by being pasted together.

Even in the case, the thickness of non-aqueous electrolyte layer refers to by in conjunction with the film formed thickness of electrolyte.

According to the nonaqueous electrolyte battery of the present embodiment can by but be not limited to following steps manufacturing: on collector electrode, form anode active material layer with described method; By stacked non-aqueous electrolyte layer of ink-jet system and anolyte layer, thereby provide lamination in the above; Between collector electrode etc., keep described lamination; And, make simple positive pole and negative polarity contact conductor reach the battery outside with battery case sealing gained lamination.

Non-aqueous electrolyte layer, positive pole and negative pole all have nonaqueous electrolyte separately as required, and they can be identical or different.

Electrolyte slurry preferably by but be not limited to and use the piezo-electric type ink-jet system to apply, this allows to form extremely thin non-aqueous electrolyte layer.

The viscosity of electrolyte slurry can be similar to anode sizing agent.

The gravel size decision of the dielectric substrate of coating is a bit larger tham the part that forms electrode.

The electrolyte slurry of coating can be according to the dry and polymerization with the anode sizing agent similar methods.

The polymeric electrolyte slurry can be according to being used for forming negative active core-shell material with described method similar methods, thereby required concentration gradient is provided.

For will applying the non-aqueous electrolyte layer of different cathode sizes as thin layer in the above, preferred lamination is from having the cathode size of low solid concentration, and behind the repetition lamination of multi-layer thin rete, is the cathode size with higher solids concentrations at last.

So the lamination of preparation can remain between the independent collector electrode etc., and with the battery case sealing, makes anodal and the negative polarity contact conductor reaches outside the battery.

External impact when battery case can be configured to prevent to use or ecological deterioration.

For instance, can fuse the shell of making by laminated material, perhaps be arranged in the encapsulated member that the opening part close thermal fuses, make the lead end of anodal and negative pole to stretch out from fusing partly along peripheral heat with stacked high-polymer membrane and metal forming.

The quantity that lead-in wire elongates part can be one or more for each lead end.

Except described material, the material of battery case can also be plastics, metal, rubber etc. for instance, perhaps their combination.Structure can also be membranaceous, plane or box-shaped.

Battery case can be equipped with the connector that is used for connecting its battery that is connected with collector electrode the inner and its battery outer end that is connected with lead end, thereby therefrom takes out electric current.

According to the present embodiment, gel electrolyte battery can be lithium rechargeable battery, sodium ion secondary battery, potassium ion secondary cell, magnesium ion secondary cell, perhaps calcium ion secondary cell.

From practical standpoint, lithium rechargeable battery is preferred.

Use can be divided into according to configuration or structure according to the nonaqueous electrolyte battery of the electrode of the present embodiment, but is not limited to (flat board) roll extrusion battery (rolled cell), (cylinder) laminated cell, perhaps any known form or other type.

As advantage, nonaqueous electrolyte battery does not have leak of liquid, and does not have the liquid problem of short-circuit, thereby has reliability, the constructional simplicity of height, and excellent output characteristic.

Use lithium-compound transition metal oxide can improve the output characteristic of nonaqueous electrolyte battery as positive electrode active materials, as advantage, described composite oxides are lower cost materials of reactive and cycle life excellence.

By using the simple seal technology by for example thermo-compressed that (plane) of guaranteeing long-term reliability laminated construction can be provided, nonaqueous electrolyte battery has advantage aspect cost and the machinability.

2.1.3b bipolar cell

Electricity connects (electrode structure) angle internally, can be divided into bipolar cell (type of internal series-connection) or non-bipolar cell (inner type in parallel) according to the nonaqueous electrolyte of the present embodiment.

Bipolar cell has higher voltage as simple battery (simplex cell), and allows the battery of manufacturing capacity and output characteristic excellence.

Nonaqueous electrolyte battery according to the present embodiment preferably manufactures bipolar lithium rechargeable battery (this paper is called for short " bipolar cell " sometimes).

2.1.3c composite battery

According to the present embodiment, use a plurality of nonaqueous electrolyte batteries, a plurality of bipolar cells of perhaps preferred use form composite battery.

In other words, can connection in series-parallel connect two or more bipolar cells according to the present embodiment, composite battery is provided, and as high power capacity, high output battery or battery component, this allows with lower cost processing intent relevant various battery capacities and output demand.

2.1.3d vehicle

According to the present embodiment, nonaqueous electrolyte battery has various advantages, and is preferably applied in the vehicle, and particularly conduct is to the driving power of the vehicle of energy and output density demand harshness, for example motor vehicle or motor vehicle driven by mixed power.Can be provided in the motor vehicle or the motor vehicle driven by mixed power of fuel consumption and rideability aspect excellence.

This motor vehicle or motor vehicle driven by mixed power preferably have one group of composite battery, and it is installed in as driving power but is not limited to vehicle middle seat below, between the passenger or luggage compartment stay favourable wide space.

The composite battery group can be installed under the vehicle floor, perhaps between luggage compartment, engine, in roof space, bonnet (bonnet hood) etc.

Battery pack requires to preferably include composite battery, bipolar cell or its combination according to purpose.

Battery pack bipolar and/or composite battery can be preferably mounted at but be not limited in motor vehicle or the motor vehicle driven by mixed power.

2.2 the details of second embodiment (gel electrolyte electrode)

2.2.1 the structure of gel electrolyte electrode

2.2.1a gel electrolyte electrode

Electrode active material layers with described concentration gradient preferably has, but is not limited to the structure of the laminated thin rete that a plurality of density and electrolytic salinity differ from one another.The quantity of laminated thin rete can be two-layer or more than, and preferably three layers or more than.When the quantity of laminated thin rete is less than when two-layer, when increasing ion concentration, can implement to discharge fast for instance, but the reduction of the capacity normal speed under.On the contrary, when ion concentration reduced, the capacity under the normal speed increased, but the repid discharge difficulty.

The electrolytic salt that uses in this second embodiment can be, but be not limited to one of following material: BETI (lithium two (perfluoroethylene sulfimide)), i.e. Li (C ₂F ₅SO ₂) ₂N, LiBF ₄, LiPF ₆, LiN (SO ₂CF ₃) ₂, LiN (SO ₂C ₂F ₅) ₂And LiBOB (double oxide lithium borate), perhaps one of its mixture.

The composition of electrode will illustrate below.

In addition, collector electrode can be the metal that its surface covers with aluminium, and perhaps needing according to environment can be a pair of coherent metal forming.

2.2.1b be used for anodal electrode

In order to be used for positive pole, (this paper is called sometimes that " positive electrode layer ") comprises positive electrode active materials and is used for strengthening the electrolytic salt of ionic conductivity to be suitable for anodal electrode active material layers; And necessary additive, comprise electric conducting material, the binding agent that is used for strengthening electronic conductivity, lithium salts and the electrolyte that is used for strengthening ionic conductivity.

The particle diameter of positive electrode active materials preferably drops in the scope of 0.1-50 micron, perhaps more preferably in the scope of 1-20 micron.

For the explanation of electrolytic salt with reference to the front.

In using the situation of barrier film as dielectric substrate that adopts gel electrolyte or electrolyte solution dipping, positive electrode layer need not comprise electrolyte, but need comprise the known binding agent of positive electrode active materials particle adhered to one another.

Electrolyte preferably is used for strengthening the gel electrolyte of Li ionic conductivity.The gel electrolyte that typically comprises electrolyte solution in all solid state high polymeric polyelectrolyte of ionic conduction can be additional electrolyte with the similar electrolyte solution in electrolyte high polymer (main polymer) skeleton that remains on the non-conducting lithium ion.

The electrolyte solution that comprises in the gel electrolyte (electrolytic salt and plasticizer) can be the typical electrolyte solutions that is used for lithium ion battery, and can be, but be not limited to the electrolyte solution that comprises at least a following electrolytic salt, described electrolytic salt is selected from inorganic anion salt, for example LiBOB (double oxide lithium borate), LiPF ₆, LiBF ₄, LiClO ₄, LiAsF ₆, LiTaF ₆, LiAlCl ₄And Li ₂B ₁₀Cl ₁₀, and organic anion salt, for example LiCF ₃SO ₃, Li (CF ₃SO ₂) ₂N and Li (C ₂F ₅SO ₂) ₂N, in the organic solvent (plasticizer) of for example aprotic solvent, use the aprotic solvent of at least a or two or more mixing, described aprotic solvent is selected from for example cyclic carbonate of propene carbonate (PC) and ethylene carbonate (EC), dimethyl carbonate for example, the linear carbonate of methyl ethyl carbonate and diethyl carbonate, oxolane for example, the 2-methyltetrahydrofuran, 1, the 4-dioxane, 1,2-dimethoxy-ethane and 1, the ether of 2-dibutoxy ethane, for example lactone of gamma-butyrolacton, the nitrile of acrylonitrile for example, the for example ester of methyl propionate, for example acid amides of dimethyl formamide, methyl acetate, and methyl formate.

The main polymer of the non-conducting lithium ion that comprises in the gel electrolyte can be but be not limited to the monomer that forms gelatin polymer, for example polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polyacrylonitrile (PAN), perhaps polymethyl methacrylate (PMMA).

The high polymer in the high polymer gel electrolyte and the ratio of electrolyte solution according to purpose etc. can be from 2: 98 to 90: 10 mass ratio.

Therefore, the high polymer in definite gel electrolyte and the mass ratio of electrolyte solution under the situation of more preferably considering battery performance.

2.2.1c be used for the electrode of negative pole

In order to be used for negative pole, (this paper is called sometimes that " positive electrode layer ") comprises negative active core-shell material and is used for increasing the electrolytic salt of ionic conductivity to be suitable for the electrode active material layers of negative pole, and necessary additive, comprise the electric conducting material, binding agent, the electrolyte that are used for strengthening electronic conductivity, and be used for film forming filmogen.Except negative active core-shell material and filmogen, other additive is similar to positive electrode layer (consulting the 2.2.1b part).

More particularly, positive electrode active materials is one of carbon, graphite and lithium-transition metal composite oxide preferably, and carbon and lithium-transition metal composite oxide are preferred.

Carbon can be graphite, hard carbon or soft carbon for instance.

Filmogen means by form catabolite film (solid electrolyte interface: the various additives SEI film) at negative terminal surface reduction decomposition gel electrolyte.The required feature of film to be formed approaches, thereby has higher ionic conductivity, and limit electrolysis matter is infiltrated in the electrode.

Therefore, described film forming raw material can be a succinyl oxide, 1,6-dioxy spiral shell [4,4] nonane-2, and 7-diketone, 1,4-dioxy spiral shell [4,5] decane-2-ketone etc. are any; Can be the carbonic ester of vinylene carbonate for example in addition; Trifluoro polypropylene carbonate alkene ester; Carbonic acid catechu phenolic ester; The cyclic ethers of 12-crown-4-ether for example; The acid anhydrides of glutaric anhydride for example; The cyclic ketones of cyclopentanone, cyclohexanone for example; For example 1,3-N-morpholinopropanesulfonic acid lactone, 1, the sultone of 4-butyl sultone; The sulfur-containing compound that comprises thiocarbonate; And the nitrogen-containing compound that comprises acid imide.

The film forming raw material preferably include have-OS (=O) ₂-the sulfur-containing compound of sultone, and its concrete example comprises 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, 2,3-dimethyl butyrate sultones, 2-ethyoxyl pentafluoropropane-1,2-sultone, dimethyl suflfate, dithyl sulfate, sulfonic acid second methyl esters.Adopt this film forming raw material that lithium-sulphur compound is mixed in the film of negative terminal surface, increased the conductivity of ion in film, and made ion transfer steady.

The electrode that the electrode of the present embodiment can be in the electrode active material layers on collector electrode, density gradient develops along with the concentration gradient from the electrode active material layers surface to the collector electrode filmogen.In addition, filmogen is a reason of disturbing the Li ions diffusion under the high speed charge or discharge.Therefore, the concentration that is designed to filmogen when the active material layer that is suitable for negative pole is along from the surface that is suitable for anode active material layer to the thickness of collector electrode and when increasing, can reduce the concentration of the lip-deep filmogen that is suitable for anode active material layer, the Li ion is steadily spread.

Compare with the electrode with the filmogen that forms under uniform high concentration, the Li ion steadily spreads in the electrode with filmogen concentration gradient.In addition, compare with the electrode with the filmogen that forms under uniform low concentration, in the electrode with filmogen concentration gradient, the stability of negative pole increases.

The electrode of the present embodiment is preferably in the electrode active material of collector electrode, preferably have the concentration gradient of electrolytic salt and filmogen along surface to the thickness of collector electrode, thereby under the high speed charge or discharge, show more excellent effect from electrode active material layers.Suitably determine the concentration gradient of electrolytic salt and filmogen, obtain required electrode.

Polarity is that the thickness of preferred its electrode active material layers of the electrode of plus or minus is in the 1-100 micrometer range, more preferably in the scope of 5-50 micron.

The preferred thickness of electrode active material layers does not comprise wherein the very scope below 1 micron of difficulty formation concentration gradient, and wherein the ions diffusion distance can not guarantee the high scope of exporting more than 100 microns too greatly.

2.2.2 the manufacturing of gel electrolyte electrode

2.2.2a manufacture method

According to second embodiment, make the gel electrolyte electrode by the following method, described method comprises: change will be added the amount with the electrolytic salt of forming electrode active material layers, thereby prepares the step (a) of the multiple density electrode slurry different with electrolytic salinity; And apply collector electrodes with a series of multiple electrode slurrys, make electrode active material layers density gradient along with from the surface of electrode active material layers to the concentration gradient of collector electrode electrolytic salt and develop, thereby the step (b) of stacked a plurality of density thin layer different with electrolytic salinity.

This method can provide the gel electrolyte according to second embodiment, and the different thin layer of wherein stacked a plurality of electrolytic salinities makes it to have electrolytic salt has concentration gradient from the electrode active material surface to collector electrode concentration gradient.

2.2.2b the manufacturing of straight polarity electrode

In order to make the electrode that is suitable for positive polarity, in the step (a) of described method (consulting the 2.2.2a part), prepare multiple electrode slurry respectively as the corresponding solution that comprises positive electrode active materials (this paper is called for short " anode sizing agent ", perhaps is called for short " positive electrode ink " in the present embodiment sometimes).Described slurry can comprise electric conducting material, binding agent as required, be suitable for electrolytical high polymer, initator etc. as the gel electrolyte raw material.

For instance, anode sizing agent can be by adding for example additive of electric conducting material and binding agent in the solvent that comprises positive electrode active materials, and wait and stirring gained solution prepares in order evenly to mix.

Equally, prepare multiple slurry, change the amount of its interpolation as required, thereby required concentration gradient is provided with solvent or electrolytic salt.

Positive electrode active materials, electric conducting material, binding agent, electrolyte high polymer and electrolytic salt are with reference to the explanation of front.

Consider to grind to form anode active material layer, the particle diameter that positive electrode active materials can be set is below 50 microns, preferably in the scope of 0.1-50 micron, perhaps more preferably in the scope of 1-20 micron.

For instance, initator can be but be not limited to as the benzyl dimethyl ketal of light trigger or as the azodiisobutyronitrile of thermal initiator.

For positive electrode active materials, electrolytic salt, binding agent and electrolyte high polymer, can be according to its additions of control such as purpose of battery.

The addition of initator depends on and is being used for the crosslinkable number of functional groups of electrolyte high polymer of gel electrolyte.

In the step (b) in described manufacture method (consulting the 2.2.2a part), " applying collector electrode with multiple anode sizing agent " can be preferably by a kind of carrying out in silk screen printing, spraying method, electrostatic coating method and the ink ejecting method.

Ink ejecting method is to use anode sizing agent to be coated to method on the collector electrode as ink-jet ink and with the drop of anode sizing agent from ink nozzle, can make the target area of collector electrode be coated with the slurry that is covered with required homogeneous film thickness, thereby make the pattern coating of anode sizing agent with optimum.This is preferred.

Mean with " optimum pattern " coating anode sizing agent in coating by ink ejecting method anode sizing agent is coated on the collector electrode, make electrolytic salt have required concentration gradient.

Described optimum system choosing is a piezo-electric type, and wherein ceraminator is out of shape along with the voltage that applies on it and discharges liquid.

The piezo-electric type ink gun is suitable for the liquid of carrying various viscosity higher, in effective conveying scope of 10Pas (100cp), and the accuracy that it has reliable stability and is better than other type.

Typical piezo-electric type ink gun is equipped with the print cartridge that stores positive electrode ink at head, and the ink guide member that is communicated with print cartridge by ink channel.

This ink gun has a plurality of nozzles that come its lower part, the array of piezoelectric elements that is placed on its upper part, and the drive pressure electric device carries the driver of liquid in the print cartridge, thus ink-jet from relevant nozzle.

This ink gun structure is exemplary, rather than restrictive.

Can use commercially available ink gun well.

The ink guide member is metal preferably.

The viscosity of anode sizing agent preferably drops under 25 ℃ in the scope of 0.1-100cP, more preferably in the scope of 0.5-10cP, perhaps more more preferably in the scope of 1-3cP.

Can measure viscosity well by L type viscosimeter, rotation viscometer etc.

These methods can form required optimum pattern at short notice.

In method (1), " with optimum pattern drop is sprayed on the collector electrode surface " and preferably include following steps: independent control nozzle of small diameter liquid is separately carried behavior, thereby various anode sizing agents are sprayed on the collector electrode surface, form thin layer, repeat to spray the less anode sizing agent of another kind of electrolytic salinity then, each formation thin film layer, thus the different anode sizing agent coating of stacked multilayer concentration realizes required concentration gradient.Carry and the different anode sizing agent drop of mixed electrolyte salinity, thereby form thin layer.In addition, described method can comprise according to the different thin layer of the stacked multilayer electrolyte salinity of suitable mode, obtain required concentration gradient.

In method (2), " drop is sprayed on the collector electrode surface " for instance and preferably includes following steps: independent each ink gun of control with optimum pattern, thereby spraying is carried and the drop of the multiple anode sizing agent that the electrolytic salinity of mixing is different, thereby forms thin layer.In addition, described method can comprise according to the different multi-layer thin rete of the stacked electrolytic salinity of suitable mode, obtain required concentration gradient.

Consider the thickness of thin layer, the granular size of the anode sizing agent drop that preferred setting will be carried from ink gun is in the scope of 1-500pl, perhaps more preferably in the scope of 1-100pl.

The film thickness that is coated with and applies is preferably in the scope of 1-100 micron, and perhaps more preferably in the scope of 5-50 micron, in order to realize the anode active material layer of desired thickness, described thickness can be regulated.

The thickness of stacked multi-layer thin rete can be distinguished suitably and to determine in anode active material layer, thereby realizes required electrode characteristic, and needs not be impartial.

The anode sizing agent of coating is typically can be in atmosphere dry well, preferably under vacuum atmosphere 20-200 ℃ temperature range inner drying 1 minute to 8 hours, perhaps more preferably 80-150 ℃ temperature range inner drying 3 minutes to 1 hour.

These conditions are not restrictive, thereby come to determine drying condition by rights according to the quantity of solvent in the anode sizing agent of coating for instance.

Method according to the electrolyte high polymer that comprises in the suitably definite polymerization anode sizing agent of used initator, and for instance when using light trigger, even can in atmosphere, carry out, but preferred inert atmosphere at for example argon gas or nitrogen, perhaps more preferably in vacuum atmosphere in 0-150 ℃ temperature range, preferred again in 20-40 ℃ temperature range, in 1 minute to 8 hours scope, more preferably in 5 minutes to 1 hour scope, shine with ultraviolet ray.

In addition, preferably apply the step of multiple anode sizing agent by order, can well multilayer anode sizing agent coat layer be stacked on the substrate, for example on dielectric substrate or the barrier film with the electrolyte immersion, the sort of beginning that is adjusted to predetermined value from electrolytic salinity is stacked, thereby realizes required concentration gradient.

2.2.2c the manufacturing of negative polarity electrode

In order to make the electrode that is suitable for negative polarity, in the step (a) of described method (consulting the 2.2.2a part), prepare multiple electrode slurry respectively as the corresponding solution that comprises negative active core-shell material (this paper is called for short " cathode size ", perhaps is called for short " negative electrode ink " in the present embodiment sometimes).Described slurry can comprise electric conducting material, binding agent, the electrolyte high polymer as the gel electrolyte raw material, initator, film forming raw material etc. as required.

For negative active core-shell material, electric conducting material, binding agent, electrolyte high polymer, electrolytic salt, initator, solvent, film forming raw material etc. are with reference to the explanation of front.

The particle diameter that negative active core-shell material preferably is set is below 50 microns, and perhaps more preferably in the scope of 0.1-20 micron, this particle is dispersed in the anode active material layer.

In the step (b) in described manufacture method (consulting the 2.2.2a part), " applying collector electrode with multiple cathode size " can be preferably by carrying out with the anode sizing agent similar methods.

Aforementioned production method is to form electrode, makes electrolytic salt have required concentration gradient.But the present embodiment is not limited to this, and the formation of electrode can make filmogen have required concentration gradient.This method comprises: (a) change the amount of the film forming raw material that constitutes electrode active material layers, thereby prepare multiple density and the different electrode slurry of film forming material concentration; And (b) electrode coated slurry to collector electrode, the density gradient that makes electrode active material along with along from the surface of electrode active material layers to the concentration gradient of the film forming raw material of the thickness of collector electrode and develop, thereby stacked a plurality of density and the different thin layer of film forming material concentration.

As another kind of method, form electrode, make electrolytic salt and filmogen have required concentration gradient respectively.That is, this method comprises: (a) change the electrolytic salt of formation electrode active material layers and the amount of film forming raw material, thereby prepare multiple density and the electrolytic salinity electrode slurry different with the film forming material concentration; And (b) electrode coated slurry to collector electrode, the density gradient that makes electrode active material is along with along developing from the surface of electrode active material layers to the concentration gradient of the electrolytic salt of the thickness of collector electrode and film forming raw material, thus the different respectively thin layer of stacked a plurality of density and electrolytic salinity and film forming material concentration.

2.2.3 the application of gel electrolyte electrode

2.2.3a gel electrolyte battery

Second embodiment provides the various gel electrolyte electrodes that can bear the high speed charge or discharge, uses the gel electrolyte battery that they can the obtained performance excellence.

For instance, when battery comprises: positive pole, it comprises collector electrode and is suitable for anodal active material layer, just has along from being suitable for the electrolytic salinity gradient that anodal dielectric substrate surface increases to the thickness of collector electrode thereby make; Negative pole, it comprises collector electrode and be suitable for the active material layer of negative pole, thereby makes negative pole have the electrolytic salinity gradient that reduces to the thickness of collector electrode along from the dielectric substrate surface that is suitable for negative pole; And during dielectric substrate, can provide the battery that is exclusively used in high rate discharge.

In the constant conventional batteries of electrolytic salinity, the Li ion may exhaust in the positive pole under high rate discharge in electrode.In addition, when the concentration of electrolytic salt in the negative pole kept even, the Li ionic conductivity may reduce.But the negative pole in the present embodiment battery comprises the electrolytic salt with above-mentioned concentration gradient, makes negative pole discharge the Li ion easily.In addition, positive pole comprises the electrolytic salt with finite concentration gradient, makes the electrolytic salinity that is suitable for anodal active material layer high near collector electrode.This facilitates the diffusion of Li ion, and comprises a large amount of electrolytic salts near the active material layer that being suitable for positive pole collector electrode, thereby has avoided exhausting of Li ion, thereby has avoided superpotential generation.

In the battery of at a high speed charging, set up with discharge under the opposite concentration gradient of electrode (positive pole and negative pole) be enough.That is, it is had by setting battery: positive pole, it comprises collector electrode and is suitable for anodal active material layer, just has along from being suitable for the electrolytic salinity gradient that anodal dielectric substrate surface reduces to the thickness of collector electrode thereby make; Negative pole, it comprises collector electrode and be suitable for the active material layer of negative pole, thereby makes the electrolytic salinity gradient that negative pole has to be increased to the thickness of collector electrode along from the dielectric substrate surface that is suitable for negative pole; And dielectric substrate, can provide to be exclusively used in charging, for example Zai Sheng battery at a high speed.Herein, term " regeneration " means following situation: use brake in the motor vehicle driven by mixed power of the motor that uses starting and accelerating vehicle, thereby according to the mode opposite with discharge, by the kinetic energy rotation motor of vehicle, thereby make battery charge.

The above-mentioned battery combination that is exclusively used in high rate discharge and the at a high speed charging bigger electric current that can discharge at short notice and charge, and this for instance battery is suitable for using in motor vehicle driven by mixed power.

In addition, in the battery of the present embodiment, the active material layer that is suitable for negative pole have the concentration that makes filmogen along from the dielectric substrate surface that is suitable for negative pole to the thickness of collector electrode and the concentration gradient that increases, thereby can increase the Li ionic conductivity.Because filmogen is the reason that reduces the Li ionic conductivity,, thereby make battery be exclusively used in high rate discharge and charging so described concentration gradient reduces the concentration of filmogen.The concentration gradient that more preferably in the negative pole of the above-mentioned battery that is exclusively used in high rate discharge or charges at a high speed, comprises described filmogen.This just can provide the battery that is exclusively used in the high speed charge or discharge.

Described battery has the dielectric substrate that preferably comprises gel electrolyte.

In order to form this dielectric substrate, prepare suitable electrolyte slurry (being called " electrolyte ink " in the present embodiment sometimes), it comprises electrolyte high polymer and electrolytic salt, and initator, solvent etc.Can suitably prepare these components, thereby obtain required high polymeric polyelectrolyte layer.

Electrolyte high polymer and electrolytic salt are to above-mentioned similar.

By but be not limited to and use the electrolyte solution comprise the electrolyte high polymer to come polymerization single polymerization monomer, form gel electrolyte.

Electrolyte high polymer and electrolyte solution, and their ratio is to above-mentioned similar.

But it is impartial that the amount of the electrolyte solution that comprises in the gel electrolyte preferably keeps basically therein, perhaps reduces towards periphery from central authorities according to the mode that tilts.

The former allows to react in wideer zone as an advantage.The latter has the sealing of increase in the periphery for the electrolyte solution of all solid state high polymeric polyelectrolyte part as an advantage.

The thickness of gel electrolyte layer is more little, and it has good more performance aspect the reduction internal resistance.

The thickness of dielectric substrate can drop in the scope of 0.1-100 micron, preferably in the scope of 1-20 micron, perhaps more preferably in the scope of 5-20 micron.

The thickness of the dielectric substrate that provides between positive pole and negative pole is provided described thickness.

Therefore, in some dielectric substrate manufacture methods, can for example by being pasted together, perhaps applying these films and form dielectric substrate by in conjunction with the identical or different multilayer electrolyte membrane of thickness by ink ejecting method.Even in the case, the thickness of dielectric substrate refers to by in conjunction with the film formed thickness of electrolyte.

Gel electrolyte battery according to the present embodiment can pass through, but is not limited to following steps manufacturing: form anode active material layer with described method on collector electrode; By stacked dielectric substrate of ink-jet system and anolyte layer, thereby provide lamination in the above; Between collector electrode etc., keep described lamination; And, make positive pole and negative polarity contact conductor only reach the battery outside with battery case sealing gained lamination.

Gel electrolyte layer, positive pole and negative pole all have its gel electrolyte as required, and they can be identical or different.

Electrolyte slurry preferably passes through, and uses the piezo-electric type ink-jet system to apply but be not limited to, and this just allows to form extremely thin high polymeric polyelectrolyte layer.

The viscosity of electrolyte slurry can be similar to above-mentioned anode sizing agent.

The electrolyte slurry of coating can be according to the dry and polymerization with above-mentioned anode sizing agent similar methods.

According to the ink ejecting method similar, use the polymeric electrolyte slurry to form negative active core-shell material, thereby required concentration gradient is provided to described method.

So the lamination of preparation can remain between the independent collector electrode etc., and with the battery case sealing, makes anodal and the negative polarity contact conductor only reaches outside the battery.

From practical standpoint, lithium rechargeable battery is preferred.

Use can be divided into according to configuration or structure according to the gel electrolyte battery of the electrode of the present embodiment, but is not limited to (flat board) roll extrusion battery, (cylinder) laminated cell, perhaps any known form or other type.

As advantage, gel electrolyte battery does not have leak of liquid, and does not have the liquid problem of short-circuit, thereby has reliability, the constructional simplicity of height, and excellent output characteristic.

Use lithium-compound transition metal oxide can improve the output characteristic of gel electrolyte battery as positive electrode active materials, as advantage, described composite oxides are lower cost materials of reactive and cycle life excellence.

By using the simple seal technology by for example thermo-compressed that (plane) of guaranteeing long-term reliability laminated construction can be provided, gel electrolyte battery has advantage aspect cost and the machinability.

2.2.3b bipolar cell

Electricity connects (electrode structure) angle internally, can be divided into bipolar cell (type of internal series-connection) or non-bipolar cell (inner type in parallel) according to the gel electrolyte of the present embodiment.

Bipolar cell has higher voltage as simple battery, and allows the battery of manufacturing capacity and output characteristic excellence.

Gel electrolyte battery according to the present embodiment preferably manufactures excellent bipolar lithium rechargeable battery (this paper is called for short " bipolar cell " sometimes).

2.2.3c composite battery

According to the present embodiment, use a plurality of gel electrolyte batteries, a plurality of bipolar cells of perhaps preferred use form composite battery.

2.2.3d vehicle

According to the present embodiment, gel electrolyte battery has various advantages, and is preferably applied in the vehicle, and particularly conduct is to the driving power of the vehicle needs harshness of energy and output density, for example motor vehicle or motor vehicle driven by mixed power.For instance, provide motor vehicle or the motor vehicle driven by mixed power that can be provided in fuel consumption and rideability aspect excellence.

The composite battery group can be installed under the vehicle floor, perhaps between luggage compartment, engine, in roof space, bonnet etc.

Battery pack bipolar and/or composite battery can be preferably mounted at, but is not limited in motor vehicle or the motor vehicle driven by mixed power.

Third part

This part is contained

3.1 the embodiment of first embodiment

3.2 the embodiment of second embodiment

3.1 the embodiment of first embodiment

First embodiment illustrates as follows.

3.1.1 embodiment-1

3.1.1a the preparation of positive electrode ink

Mix a certain amount of (90 gram weight) spinel structure LiMn ₂O ₄(particle diameter: average 0.6 micron) is as positive electrode active materials, a certain amount of (5 gram weight) acetylene black is as electric conducting material, and a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, and in described mixture, mix a certain amount of (300 gram weight) acrylonitrile as solvent, thereby prepare a kind of slurry as positive electrode ink-1.Positive electrode ink-1 has the viscosity of 3cP under 25 ℃ temperature.

Next, according to amount blended anode active material, electric conducting material and the binding agent identical with positive electrode ink-1, and in described mixture, mix a certain amount of (500 gram weight) acrylonitrile as solvent, thus prepare solid concentration than the rarer another kind of slurry of positive electrode ink-1 as positive electrode ink-2.Positive electrode ink-2 has the viscosity of 2cP under 25 ℃ temperature.

In addition, according to amount blended anode active material, electric conducting material and the binding agent identical with positive electrode ink-1, and in described mixture, mix a certain amount of (900 gram weight) acrylonitrile as solvent, thus prepare solid concentration than rarer another slurry of positive electrode ink-2 as positive electrode ink-3.Positive electrode ink-3 has the viscosity of 1cP under 25 ℃ temperature.

3.1.1b the preparation of negative electrode ink

The graphite (particle diameter: average 0.7 micron) that mixes a certain amount of (90 gram weight) pulverizing is as negative active core-shell material, a certain amount of (5 gram weight) acetylene black is as electric conducting material, and a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, and in described mixture, mix a certain amount of (300 gram weight) acrylonitrile as solvent, thereby prepare a kind of slurry as negative electrode ink-1.Negative electrode ink-1 has the viscosity of 3cP under 25 ℃ temperature.

Next, mix negative active core-shell material, electric conducting material and binding agent according to the amount identical with negative electrode ink-1, and in described mixture, mix a certain amount of (500 gram weight) acrylonitrile as solvent, thus prepare solid concentration than the rarer another kind of slurry of negative electrode ink-1 as negative electrode ink-2.Negative electrode ink-2 has the viscosity of 2cP under 25 ℃ temperature.

In addition, mix negative active core-shell material, electric conducting material and binding agent according to the amount identical with negative electrode ink-1, and in described mixture, mix a certain amount of (900 gram weight) acrylonitrile as solvent, thus prepare solid concentration than rarer another slurry of negative electrode ink-2 as negative electrode ink-3.Negative electrode ink-3 has the viscosity of 1cP under 25 ℃ temperature.

3.1.1c the preparation of electrolyte ink

Prepare a certain amount of (160 gram weight) macromonomer between polyethylene glycol oxide and PPOX as and positive electrode ink preparation in identical electrolytic polymer, a certain amount of (80 gram weight) LiBETI as electrolytic salt, and a certain amount of (electrolytic polymer quality 0.1%) benzyl dimethyl ketal is as the photochemical polymerization initator, acrylonitrile as solvent a certain amount of to wherein adding (760 gram weight), and fully stir described mixture, thereby prepare slurry as electrolyte ink.This ink has the viscosity of 2cP.

3.1.1d the manufacturing of secondary cell

By using the ink-jet printer be purchased according to the methods below, use prepared positive electrode ink-1 to positive electrode ink-3 and negative electrode ink-1 to negative electrode ink-3, make anodal and negative pole (corresponding to the electrode among Fig. 2 or Fig. 3).

The problem that the plastic components of the ink leader of appearance formation ink-jet printer is dissolved by the solvent acrylonitrile when using similar ink.Therefore, replace plastic components, and directly to metal parts, supply ink from print cartridge with metal parts.In addition, precipitate because of ink viscosity reduces, use rotating vane to stir print cartridge always for fear of active material.

With computer that is purchased and software control ink-jet printer.In order to make positive pole, use positive electrode ink-1 to positive electrode ink-3.By ink-jet printer, print these inks according to the pattern that computer is described.Directly send into the difficulty of printer for fear of metal forming and non-aqueous solution electrolysis plasma membrane, these electrod assemblies are adhered on the high-quality paper of A4 size, are provided in the printer then and print.

Positive electrode ink-1 to positive electrode ink-3 is introduced in the ink-jet printer according to described method improvement, thereby on the stainless steel foil collector electrode (corresponding to the collector electrode of Fig. 2 or Fig. 3) of 20 micron thickness, print print pattern from computer drawing, thus form by collector electrode and the anode active material layer that forms in the above (corresponding to the positive electrode active materials 12 of Fig. 2 or Fig. 3 22) positive electrode layer formed (corresponding to the combination of 1+22 among the combination of 1+12 among Fig. 2 or Fig. 3).

More particularly, on collector electrode, print the positive thin layer-1 of 5 micron thickness (corresponding to the district 12c of Fig. 2 or the coating 22c of Fig. 3) by using positive electrode ink-1.Then, by using just thin layer-2 (corresponding to the district 12b of Fig. 2 or the coating 22b of Fig. 3) of positive electrode ink-2 prints 5 micron thickness on positive thin layer-1 another floor.In addition, by using just thin layer-3 (corresponding to the district 12a of Fig. 2 or the coating 22a of Fig. 3) of positive electrode ink-3 prints 5 micron thickness on positive thin layer-2 another floor again.For the solvent of the positive thin layer of dry each printing, described thin layer in vacuum drying chamber under 60 ℃ temperature dry 2 hours.

To positive thin layer-3, flood electrolyte ink to positive thin layer-1, under the condition of finding time, use ultraviolet irradiation 20 minutes, thereby make nonaqueous electrolyte be retained in positive thin layer-1 to positive thin layer-3.

Print by the cubic graph case, form the active material layer of positive electrode layer, the solid concentration gradient that its density gradient increases along with the thickness along the anode active material layer surface to collector electrode and developing.

Next, electrolyte ink is introduced in the improved ink-jet printer, thereby on positive electrode layer, printed, make it to be coated in the active material layer top, slightly outstanding in its edge.The positive electrode layer of dielectric substrate with printing like this in vacuum drying chamber under 60 ℃ temperature dry 2 hours, thereby dry solvent, and under the condition of finding time, use ultraviolet irradiation 20 minutes, thereby the polyeletrolyte polymer forms non-aqueous electrolyte layer (corresponding to the layer 3 among Fig. 2 or Fig. 3) on the active material layer of positive electrode layer.Non-aqueous electrolyte layer is uniform rather than irregular.

Then, negative electrode ink-1 to negative electrode ink-3 is introduced in the improved ink-jet printer, thereby on above-mentioned non-aqueous electrolyte layer, print the print pattern that it is drawn from computer, thereby form anode active material layer (corresponding to 22 among the layer 12 among Fig. 2 or Fig. 3) in the above.

More particularly, on non-aqueous electrolyte layer, print the negative pole thin layer-3 of 5 micron thickness (corresponding to the district 12a of Fig. 2 or the coating 22a of Fig. 3) by using negative electrode ink-3.Then, on negative pole thin layer-3, print another floor negative pole thin layer-2 of 5 micron thickness (corresponding to the district 12b of Fig. 2 or the coating 22b of Fig. 3) by using negative electrode ink-2.In addition, on negative pole thin layer-2, print another floor negative pole thin layer-1 again of 5 micron thickness (corresponding to the district 12c of Fig. 2 or the coating 22c of Fig. 3) by using negative electrode ink-1.For the solvent of the negative pole thin layer of dry each printing, described thin layer in vacuum drying chamber under 60 ℃ temperature dry 2 hours.

Negative pole thin layer-1 to drying floods electrolyte ink to negative pole thin layer-3, use ultraviolet irradiation 20 minutes under the condition of finding time, thereby make nonaqueous electrolyte be retained in negative pole thin layer-1 to negative pole thin layer-3.

Print by the cubic graph case, form the active material layer of positive electrode layer, its density gradient develops along with the solid concentration gradient that increases along the thickness from the basal surface of anode active material layer to its upper surface.

The upper surface of anode active material layer is coated with collector electrode.The lamination of gained positive electrode layer, non-aqueous electrolyte layer, positive electrode layer and collector electrode has the sandwich structure between the stainless steel foil that is clipped in collected current, encapsulation total and seal with the aluminium lamination laminate materials that will be molded, only make positive pole and negative wire be exposed to the outside, thereby rechargeable nonaqueous electrolytic battery is provided.

3.1.2 comparing embodiment-1

3.1.2a the formation of positive electrode layer

Mix a certain amount of (90 gram weight) spinel structure LiMn ₂O ₄(particle diameter: average 0.6 micron) is as positive electrode active materials, a certain amount of (5 gram weight) acetylene black is as electric conducting material, a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, and a certain amount of (100 gram weight) acrylonitrile is as solvent, thereby prepares anode sizing agent.Described slurry is applied to a side of the stainless steel foil (20 micron thickness) as collector electrode.Then, the dry slurry that applies under about 110 ℃ temperature, thus form the positive electrode layer of 15 micron thickness.

3.1.2b the formation of positive electrode layer

The graphite (particle diameter: average 0.6 micron) that mixes a certain amount of (90 gram weight) pulverizing is as negative active core-shell material, a certain amount of (5 gram weight) acetylene black is as electric conducting material, a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, and a certain amount of (100 gram weight) acrylonitrile is as solvent, thereby prepares cathode size.Described slurry is applied on the above-mentioned stainless steel foil side opposite with anodal layer.Then, the dry slurry that applies under about 110 ℃ temperature, thus form the positive electrode layer of 15 micron thickness.

3.1.2c the formation of dielectric substrate

Prepare a certain amount of (160 gram weight) macromonomer between polyethylene glycol oxide and PPOX as with embodiment 1 in identical electrolytic polymer, a certain amount of (240 gram weight) N-methyl pyrrolidone as solvent, the 0.1M LiBETI of a certain amount of (80 gram weight) is as electrolytic salt, and a certain amount of (electrolytic polymer quality 0.1%) benzyl dimethyl ketal is as the photochemical polymerization initator, thus preparation pregel solution.Described solution impregnation is gone in non-woven fibre (100 micron thickness) sheet that PP makes, and accepts thermal polymerization in inert atmosphere under 90 ℃ temperature, thereby forms the barrier film that wherein remains with gel electrolyte.

3.1.2d the manufacturing of secondary cell

Above-mentioned pregel solution is impregnated in anodal and the positive electrode layer, and accepts thermal polymerization in inert atmosphere under 90 ℃ temperature, thereby forms the dielectric substrate that wherein remains with gel electrolyte.

Stacked these dielectric substrates make the gel electrolyte diaphragm clip betwixt.Then, encapsulate whole lamination and with the sealing of the aluminium lamination laminate materials of the formation battery case that will be molded, only make anodal and negative wire is exposed to the outside, thereby gel electrolyte secondary battery is provided.

3.1.2e estimate

The secondary cell of making in embodiment-1 and the comparing embodiment-1 is put into thermostatic chamber, and its temperature remains under 25 ℃, uses the charge-discharge device to carry out the discharge performance test.

In the discharge performance test, its discharge capacity in measuring high rate discharge, thereby determine that its discharge rate is { before (discharge capacity/theoretical capacity under 10CA) * 100%}, reaching the described secondary cell of constant current charge under the constant voltage of fully charged state (4.2V), and to the level 2.5V that reduces, it the results are shown in table-1 with the current rate constant-current discharge of 20CA.

The theoretical capacity of secondary cell is determined based on the amount of the positive electrode active materials of the theoretical capacity of the positive electrode active materials that uses and coating.

Table 1

	Embodiment-1	Comparing embodiment-1
	Embodiment-1	Comparing embodiment-1	Discharge rate under the high rate discharge, %	84	53

As shown in table 1, the discharge rate of embodiment-1 is 84%, and the discharge rate of comparing embodiment-1 is 53%, thereby the former secondary cell is more superior.

3.2 the embodiment of second embodiment

Second embodiment illustrates as follows.

3.2.1 embodiment-2

3.2.1a the preparation of positive electrode ink

Mix a certain amount of (90 gram weight) spinel structure LiMn ₂O ₄(particle diameter: average 0.6 micron) is as positive electrode active materials, a certain amount of (5 gram weight) acetylene black is as electric conducting material, a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, a certain amount of (40 gram weight) LiBETI is as electrolytic salt, a certain amount of (40 gram weight) discloses the macromonomer of synthetic oxirane of 2002-110239 disclosed method and expoxy propane as electrolytic polymer according to Japanese patent application, and a certain amount of (electrolytic polymer quality 0.1%) benzyl dimethyl ketal is as the photochemical polymerization initator, and in described mixture, mix a certain amount of (820 gram weight) acrylonitrile as solvent, thereby prepare a kind of slurry as positive electrode ink-4.Positive electrode ink-4 has the viscosity of 3cP under 25 ℃ temperature.

Next, the positive electrode active materials as positive electrode ink-4, electric conducting material, binding agent, electrolytic polymer and photochemical polymerization initator with a certain amount of (30 gram weight) as the LiBETI mixing same amount of electrolytic salt, and in described mixture, mix a certain amount of (830 gram weight) acrylonitrile as solvent, thus prepare electrolytic salinity than the rarer another kind of slurry of positive electrode ink-4 as positive electrode ink-5.Positive electrode ink-5 has the viscosity of 3cP under 25 ℃ temperature.

In addition, the positive electrode active materials as positive electrode ink-4, electric conducting material, binding agent, electrolytic polymer and photochemical polymerization initator with a certain amount of (20 gram weight) as the LiBETI mixing same amount of electrolytic salt, and in described mixture, mix a certain amount of (840 gram weight) acrylonitrile as solvent, thus prepare electrolytic salinity than rarer another slurry of positive electrode ink-5 as positive electrode ink-6.Positive electrode ink-6 has the viscosity of 3cP under 25 ℃ temperature.

3.2.1b the preparation of negative electrode ink

The graphite (particle diameter: average 0.6 micron) that mixes a certain amount of (90 gram weight) pulverizing is as negative active core-shell material, a certain amount of (5 gram weight) acetylene black is as electric conducting material, a certain amount of (5 gram weight) polyvinylidene fluoride is as binding agent, a certain amount of (40 gram weight) LiBETI is as electrolytic salt, a certain amount of (40 gram weight) macromonomer between polyethylene glycol oxide and PPOX as to positive electrode ink preparation in used similar electrolytic polymer, and a certain amount of (electrolytic polymer quality 0.1%) benzyl dimethyl ketal is as the photochemical polymerization initator, and in described mixture, mix a certain amount of (820 gram weight) acrylonitrile as solvent, thereby prepare a kind of slurry as negative electrode ink-4.Negative electrode ink 14 has the viscosity of 3cP under 25 ℃ temperature.

Next, the negative active core-shell material as negative electrode ink-4, electric conducting material, binding agent, electrolytic polymer and photochemical polymerization initator with a certain amount of (30 gram weight) as the LiBETI mixing same amount of electrolytic salt, and in described mixture, mix a certain amount of (830 gram weight) acrylonitrile as solvent, thus prepare electrolytic salinity than the rarer another kind of slurry of negative electrode ink-4 as negative electrode ink-5.Negative electrode ink-5 has the viscosity of 3cP under 25 ℃ temperature.

In addition, the negative active core-shell material as negative electrode ink-4, electric conducting material, binding agent, electrolytic polymer and photochemical polymerization initator with a certain amount of (20 gram weight) as the LiBETI mixing same amount of electrolytic salt, and in described mixture, mix a certain amount of (840 gram weight) acrylonitrile as solvent, thus prepare electrolytic salinity than rarer another slurry of negative electrode ink-5 as negative electrode ink-6.Negative electrode ink-6 has the viscosity of 3cP under 25 ℃ temperature.

3.2.1c the preparation of electrolyte ink

3.2.1d the manufacturing of secondary cell

By according to the methods below, use the ink-jet printer that is purchased, use prepared positive electrode ink-, 4 to positive electrode ink-6 and negative electrode ink-4 to negative electrode ink-6, make anodal and negative pole (corresponding to the electrode among Fig. 4 or Fig. 5).

As mentioned above, the problem that the plastic components of the ink leader of appearance formation ink-jet printer is dissolved by the solvent acrylonitrile when using similar ink.Therefore, replace plastic components, and directly to metal parts, supply ink from print cartridge with metal parts.In addition, precipitate because of ink viscosity reduces, use rotating vane to stir print cartridge always for fear of active material.

With computer that is purchased and software control ink-jet printer.In order to make positive pole, use positive electrode ink-4 to positive electrode ink-6.By ink-jet printer, print these inks according to the pattern that computer is described.Directly send into the difficulty of printer for fear of metal forming and non-aqueous solution electrolysis plasma membrane, these electrod assemblies are adhered on the high-quality paper of A4 size, are provided in the printer then and print.

Positive electrode ink-4 to positive electrode ink-6 is introduced in the ink-jet printer according to described method improvement, thereby on the stainless steel foil collector electrode (corresponding to the collector electrode 1 of Fig. 4 or Fig. 5) of 20 micron thickness, print print pattern from computer drawing, thus form by collector electrode and the anode active material layer that forms in the above (corresponding to the positive electrode active materials 32 of Fig. 4 or Fig. 5 42) positive electrode layer formed (corresponding to the combination of 1+42 among the combination of 1+32 among Fig. 4 or Fig. 5).

More particularly, on collector electrode, print the positive thin layer-4 of 5 micron thickness (corresponding to the district 32c of Fig. 4 or the coating 42c of Fig. 5) by using positive electrode ink-4.Then, by using just thin layer-5 (corresponding to the district 32b of Fig. 4 or the coating 42b of Fig. 5) of positive electrode ink-5 prints 5 micron thickness on positive thin layer-4 another floor.In addition, by using just thin layer-6 (corresponding to the district 32a of Fig. 4 or the coating 42a of Fig. 5) of positive electrode ink-6 prints 5 micron thickness on positive thin layer-5 another floor.For the solvent of the positive thin layer of dry each printing, described thin layer in vacuum drying chamber under 60 ℃ temperature dry 2 hours.

To positive thin layer-6, flood electrolyte ink to positive thin layer-4, under the condition of finding time, use ultraviolet irradiation 20 minutes, thereby make gel electrolyte be retained in positive thin layer-4 to positive thin layer-6.Print by the cubic graph case, form the active material layer of positive electrode layer, the electrolytical concentration gradient that its density gradient increases along with the thickness along the anode active material layer surface to collector electrode and developing.

Next, electrolyte ink is introduced in the improved ink-jet printer, thereby on positive electrode layer, printed, make it to be coated in the active material layer top, slightly outstanding in its edge.The positive electrode layer of dielectric substrate with printing like this in vacuum drying chamber under 60 ℃ temperature dry 2 hours, thereby dry solvent, and under the condition of finding time, use ultraviolet irradiation 20 minutes, thereby the polyeletrolyte polymer forms gel electrolyte layer (corresponding to the layer 3 among Fig. 4 or Fig. 5) on the active material layer of positive electrode layer.Gel electrolyte layer is uniform rather than irregular.

Then, negative electrode ink-4 to negative electrode ink-6 is introduced in the improved ink-jet printer, thereby on above-mentioned gel electrolyte layer, printed the print pattern that it is drawn from computer, thereby form anode active material layer in the above.

More particularly, on gel electrolyte layer, print the negative pole thin layer-4 of 5 micron thickness by using negative electrode ink-4.Then, on negative pole thin layer-4, print another layer negative pole thin layer-5 of 5 micron thickness by using negative electrode ink-5.In addition, on negative pole thin layer-5, print the another layer negative pole thin layer-6 of 5 micron thickness by using negative electrode ink-6.For the solvent of the negative pole thin layer of dry each printing, described thin layer in vacuum drying chamber under 60 ℃ temperature dry 2 hours.

Under the condition of finding time with ultraviolet irradiation negative pole thin layer-4 to negative pole thin layer-620 minute, thereby make gel electrolyte be retained in negative pole thin layer-4 to negative pole thin layer-6.Print by the cubic graph case, form the active material layer of positive electrode layer, its density gradient develops along with the electrolytical concentration gradient that increases along the thickness from the basal surface of anode active material layer to its upper surface.

The upper surface of anode active material layer is coated with collector electrode.The lamination of gained positive electrode layer, gel electrolyte layer, positive electrode layer and collector electrode has the sandwich structure between the stainless steel foil that is clipped in collected current, encapsulation total and seal with the aluminium lamination laminate materials that will be molded, only make positive pole and negative wire be exposed to the outside, thereby gel electrolyte secondary battery is provided.

3.2.2 comparing embodiment-2

3.2.2a the formation of positive electrode layer

3.2.2b the formation of positive electrode layer

3.2.2c the formation of gel electrolyte layer

3.2.2d the manufacturing of secondary cell

3.2.2e estimate

The secondary cell of making in embodiment-2 and the comparing embodiment-2 is put into thermostatic chamber, and its temperature remains under 25 ℃, uses the charge-discharge device to carry out the discharge performance test.

In the discharge performance test, its discharge capacity in measuring high rate discharge, thereby determine that its discharge rate is { before (discharge capacity/theoretical capacity under 20CA) * 100%}, reaching under the constant voltage of fully charged state (4.2V), the described secondary cell of constant current charge, and to the level 2.5V that reduces, it the results are shown in table-2 with the current rate constant-current discharge of 20CA.

Table 2

	Embodiment-2	Comparing embodiment-2
	Embodiment-2	Comparing embodiment-2	Discharge rate under the high rate discharge, %	21	12

As shown in table 2, the discharge rate of embodiment-2 is 21%, and the discharge rate of comparing embodiment-2 is 12%, thereby the former secondary cell is more superior.

The 4th part is replenished

" density gradient " of noting electrode active material layers is the statement of general designation, and variation or the gradient intentionally that comprise concentration in this layer, perhaps one or more parts or component (solid for example, electrolyte and/or film forming raw material) a plurality of variation or gradients of having a mind to coexistence, and the technical staff can provide extremely important or important basically configuration, wherein said density is strict or strictly keep constant basically on the thickness direction of this layer at least, allow having a mind to set of variations branch ratio provides the concentration of component of variation, for example is used for the diffusional resistance of motion particle of Change Example such as ion.

The Japanese patent application of submitting in Japan on July 31st, 2003 2003-283974 number, and the full content of the Japanese patent application of submitting in Japan on July 31st, 2003 2003-283975 number is incorporated herein for referencial use.

Although with reference to embodiments more of the present invention the present invention has been described above, the present invention is not limited to described embodiment.Under instruction of the present invention, those skilled in the art can make embodiment and revising and change.Scope of the present invention defines with reference to following claim.

Industrial applicability

The present invention particularly is applicable to the nonaqueous electrolyte electrode of rapid charge or discharge and configuration, manufacturing and the commercial Application of gel electrolyte electrode and has widely application for the industrial circle of secondary cell.

Claims

1. an electrode for secondary battery comprises the electrode active material layers with density gradient.

2. electrode for secondary battery as claimed in claim 1, it comprises the electrode that is suitable for nonaqueous electrolyte battery that electrode active material layers wherein forms on collector electrode, the density gradient of this electrode active material layers forms along with the solid concentration gradient that increases along the thickness from the electrode active material layers surface to collector electrode.

3. electrode for secondary battery as claimed in claim 2, wherein said electrode active material layers comprise the different laminated thin rete of a plurality of solid concentrations.

4. electrode for secondary battery as claimed in claim 2, wherein said solid concentration are the concentration of electrode active material.

5. electrode for secondary battery as claimed in claim 2, wherein said solid concentration comprises the concentration of electrode active material, electric conducting material and binding agent.

6. electrode for secondary battery as claimed in claim 2, the thickness of wherein said electrode active material layers is in the scope of 1-100 micron.

7. electrode for secondary battery as claimed in claim 1, it comprises the electrode that is suitable for gel electrolyte battery that electrode active material layers wherein forms on collector electrode, the density gradient of this electrode active material layers is along with along the concentration gradient of the electrolytic salt of the thickness from the electrode active material layers surface to collector electrode and form.

8. electrode for secondary battery as claimed in claim 7, wherein said electrode active material layers comprise the different laminated thin rete of a plurality of electrolytic salinities.

9. electrode for secondary battery as claimed in claim 1, it comprises the electrode that is suitable for gel electrolyte battery that electrode active material layers wherein forms on collector electrode, the density gradient of this electrode active material layers is along with along the concentration gradient of the filmogen of the thickness from the electrode active material layers surface to collector electrode and form.

10. electrode for secondary battery as claimed in claim 9, wherein said electrode active material layers comprise the different laminated thin rete of a plurality of filmogen concentration.

11. electrode for secondary battery as claimed in claim 1, it comprises the electrode that is suitable for gel electrolyte battery that electrode active material layers wherein forms on collector electrode, the density gradient of this electrode active material layers is along with along the concentration gradient of the electrolytic salt of the thickness from the electrode active material layers surface to collector electrode and filmogen and form.

12. electrode for secondary battery as claimed in claim 9, wherein said electrode active material layers comprise a plurality of electrolytic salinities laminated thin rete different with filmogen concentration.

13. electrode for secondary battery as claimed in claim 1, the thickness of wherein said electrode active material layers is in the scope of 1-100 micron.

14. a manufacture method, it comprises makes the electrode for secondary battery that comprises the electrode active material layers with density gradient.

15. as the manufacture method of claim 14, wherein said electrode for secondary battery comprises the electrode that is suitable for nonaqueous electrolyte, described method comprises:

(a) change the amount that will be added, thereby prepare the different electrode slurry of multiple solid material concentration with the solid material of forming electrode active material layers; And

(b) apply collector electrode with multiple electrode slurry, make density gradient along with from the surface of electrode active material layers to collector electrode and the concentration gradient of the solid material that order increases and forming, thereby the different thin layer of stacked a plurality of solid concentration.

16. as the manufacture method of claim 15, wherein in described step (b), the thickness that described thin layer applies is in the scope of 1-100 micron.

17., wherein in described step (b), described electrode slurry is coated on the collector electrode by ink ejecting method as the manufacture method of claim 15.

18. as the manufacture method of claim 17, wherein said ink ejecting method uses piezoelectric system.

19. as the manufacture method of claim 14, wherein said electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, described method comprises:

(a) change the amount that will be added, thereby prepare the different electrode slurry of multiple electrolytic salinity with the electrolytic salt of forming electrode active material layers; And

(b) apply collector electrode with multiple electrode slurry, make density gradient along with forming from the surface of electrode active material layers to the concentration gradient of the electrolytic salt of collector electrode, thus the different thin layer of stacked a plurality of electrolytic salinity.

20. as the manufacture method of claim 14, wherein said electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, described method comprises:

(a) change the amount that will be added, thereby prepare the different electrode slurry of multiple film forming material concentration with the film forming raw material of forming electrode active material layers; And

(b) apply collector electrode with multiple electrode slurry, make density gradient along with forming from the surface of electrode active material layers to the concentration gradient of the film forming raw material of collector electrode, thus the different thin layer of stacked a plurality of film forming material concentrations.

21. as the manufacture method of claim 14, wherein said electrode for secondary battery comprises the electrode that is suitable for gel electrolyte, described method comprises:

(a) change will be added with the electrolytic salt of composition electrode active material layers and the amount of film forming raw material, thereby prepares the multiple electrolytic salt electrode slurry different with the film forming material concentration; And

(b) apply collector electrode with multiple electrode slurry, make density gradient along with forming from the surface of electrode active material layers to the concentration gradient of the electrolytic salt of collector electrode and film forming raw material, thus stacked a plurality of electrolytic salt thin layer different with the film forming material concentration.

22. as the manufacture method of claim 19, wherein in described step (b), the thickness that described thin layer applies is in the scope of 1-100 micron.

23. as the manufacture method of claim 20, wherein in described step (b), the thickness that described thin layer applies is in the scope of 1-100 micron.

24. as the manufacture method of claim 21, wherein in described step (b), the thickness that described thin layer applies is in the scope of 1-100 micron.

25., wherein in described step (b), described electrode slurry is coated on the collector electrode by ink ejecting method as the manufacture method of claim 19.

26., wherein in described step (b), described electrode slurry is coated on the collector electrode by ink ejecting method as the manufacture method of claim 20.

27., wherein in described step (b), described electrode slurry is coated on the collector electrode by ink ejecting method as the manufacture method of claim 21.

28. as the manufacture method of claim 25, wherein said ink ejecting method uses piezoelectric system.

29. as the manufacture method of claim 26, wherein said ink ejecting method uses piezoelectric system.

30. as the manufacture method of claim 27, wherein said ink ejecting method uses piezoelectric system.

31. secondary cell that comprises the electrode for secondary battery of claim 1.

32. as the secondary cell of claim 31, wherein said secondary cell is a lithium rechargeable battery.

33. as the secondary cell of claim 31, wherein said secondary cell is a bipolar cell.

34. the secondary cell as claim 31 comprises:

The positive pole that comprises first collector electrode and be suitable for anodal active material layer, this is suitable for anodal active material layer has along with the concentration gradient along the electrolytic salt that increases to the thickness of first collector electrode from the surface that is suitable for anodal active material layer;

The negative pole that comprises second collector electrode and be suitable for the active material layer of negative pole, this active material layer that is suitable for negative pole have along with along from the surface of the active material layer that is suitable for negative pole to the thickness of second collector electrode and the concentration gradient of the electrolytic salt that reduces; And

Dielectric substrate.

35. as the secondary cell of claim 31, it comprises:

The positive pole that comprises first collector electrode and be suitable for anodal active material layer, this is suitable for anodal active material layer has along with the concentration gradient along the electrolytic salt that reduces to the thickness of first collector electrode from the surface that is suitable for anodal active material layer;

The negative pole that comprises second collector electrode and be suitable for the active material layer of negative pole, this active material layer that is suitable for negative pole have along with along from the surface of the active material layer that is suitable for negative pole to the thickness of second collector electrode and the concentration gradient of the electrolytic salt that increases; And

Dielectric substrate.

36. as the secondary cell of claim 34, the wherein said active material layer that is suitable for negative pole have along from the surface of the active material layer that is suitable for negative pole to the thickness of second collector electrode and the concentration gradient of the filmogen that increases.

37. as the secondary cell of claim 35, the wherein said active material layer that is suitable for negative pole have along from the surface of the active material layer that is suitable for negative pole to the thickness of second collector electrode and the concentration gradient of the filmogen that increases.

38. secondary cell as claim 31, wherein said electrode active material layers comprises the active material layer that is suitable for negative pole, this active material layer that is suitable for negative pole have along from the surface of the active material layer that is suitable for negative pole to the thickness of second collector electrode and the concentration gradient of the filmogen that increases.

39. as the secondary cell of claim 31, wherein said density gradient forms along with the active material layer component concentrations gradient of described electrode for secondary battery.

40. a composite battery comprises a plurality of secondary cells according to claim 1 connected to one another.

41. a composite battery comprises a plurality of secondary cells of making according to the manufacture method of claim 14 connected to one another.

42. one kind comprises the vehicle according to the secondary cell of claim 1.

43. vehicle that comprises the secondary cell of making according to the manufacture method of claim 14.