CN100524931C - Thin film lithium battery - Google Patents
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- CN100524931C CN100524931C CNB2006800016817A CN200680001681A CN100524931C CN 100524931 C CN100524931 C CN 100524931C CN B2006800016817 A CNB2006800016817 A CN B2006800016817A CN 200680001681 A CN200680001681 A CN 200680001681A CN 100524931 C CN100524931 C CN 100524931C
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Abstract
Disclosed is a thin film lithium battery which realizes a high yield by solving various problems caused by generation of pinholes in a solid electrolyte layer. Specifically disclosed is a thin film lithium battery wherein a positive electrode layer (20), a negative electrode layer (50), a solid electrolyte layer (40) arranged between the electrode layers, and a collector (10) electrically connected to one or both of the positive electrode layer (20) and the negative electrode layer (50) are arranged in layers. When the lamination of the layers in this battery is viewed in plan, the positive electrode layer (20) and the negative electrode layer (50) are arranged not to overlap each other. By having such a structure, even when a pinhole is formed in the solid electrolyte layer (40), the electrode layers (20, 50) are prevented from being short-circuited by the pinhole.
Description
Technical field
The present invention relates to film lithium cell.Particularly, the present invention relates to a kind of film lithium cell, described film lithium cell can be realized the increase of productive rate, and is accompanied by the area increase and increase capacity and current density.
Background technology
Among all-solid-state battery, film lithium cell is mainly as the baby battery with several very low capacities to tens microamperes hours and be studied and develop.Its structure is a stepped construction, and wherein, for example positive electrode layer, solid electrolyte layer, positive electrode layer are formed on the metal forming in proper order or are formed at being used as on the metallic film of collector electrode of forming on the ceramic bases of being made by aluminium oxide and so on.As the method that forms above-mentioned layer, for example use, vapour deposition process, for example sputtering method, and oxide and lithium metal are used separately as solid electrolyte layer and positive electrode layer (for example, seeing patent documentation 1 to 5 and non-patent literature 1 and 2).
In addition, for the increase capacity, studied the electrolytical all solid lithium rechargeable battery of use powder solid.This battery has stepped construction usually, and wherein positive electrode layer, solid electrolyte layer and positive electrode layer order are stacked mutually.As positive electrode, the mixture that use is made of powder solid electrolyte, powder active positive electrode material and the main powder conductive auxiliary agent that is formed by carbon, and, except lithium metal foil, also used with lithium and formed for example aluminium of alloy or the metal of indium as negative electrode.As solid electrolyte, used the sulfide sill that has than high ion-conductivity in many situations.Because it is do not use organic electrolyte solution,, highly stable in addition and not 100 ℃ or higher high-temperature district decreased performance (for example, seeing patent documentation 6 to 8) so all-solid-state battery is outstanding in the secure context performance
Patent documentation 1: TOHKEMY communique No.2004-235155
Patent documentation 2: TOHKEMY communique No.2004-179158
Patent documentation 3: TOHKEMY communique No.2004-127743
Patent documentation 4: the flat 10-83838 of TOHKEMY communique No.
Patent documentation 5: the flat 4-231346 of TOHKEMY communique No.
Patent documentation 6: TOHKEMY communique No.2004-95243
Patent documentation 7: TOHKEMY communique No.2003-68361
Patent documentation 8: the flat 6-54687 of TOHKEMY communique No.
Non-patent literature 1:Electrochemistry Communication 6, (2004), pp.417-421
Non-patent literature 2:Solid State Ionics 69 (1994), pp.357-368
Summary of the invention
The problem to be solved in the present invention
Yet, according to above-mentioned hull cell, in all structures, because positive electrode layer and positive electrode layer are arranged overlappedly, and owing to the dissimilar materials of the layer below pasting when forming solid electrolyte layer is easy to form pin hole in solid electrolyte layer, so the shortcoming of short circuit between the negative electrodes layer, can occur.As a result, reduced the productive rate of hull cell.In addition, in such hull cell, when attempting to increase capacity, even if only in solid electrolyte layer, form a pin hole by the area that increases electrode layer and solid electrolyte layer, also can short circuit occur between the negative electrodes layer, battery can not be worked at all as a result.In addition, for fear of the formation of pin hole, because the clean room that need have high cleanliness must carry out a large amount of plant investments to its installation.
In addition, in using the electrolytical all-solid-state battery of powder solid, must exert pressure so that reduce interface resistance between the powder grain to entire cell, and the result be difficult to form usually can commercial button and card-shape battery.
The present invention considers said circumstances and conceives, and a target of the present invention is to provide the film lithium cell that can realize high yield by the variety of issue that is produced that forms that solves by pin hole in solid electrolyte layer.
In addition, another target of the present invention provides and can realize along with area increases and the film lithium cell of increase capacity and current density.
The approach of dealing with problems
Arranged stacked by design negative electrodes layer can realize above-mentioned target of the present invention.
The membrane according to the invention lithium battery comprises: positive electrode layer; Positive electrode layer; The solid electrolyte layer that provides betwixt; With mutual stacked at least one collector electrode, described at least one collector electrode is electrically connected at least one positive electrode layer and positive electrode layer.When the stacked direction of described layer is seen, positive electrode layer and positive electrode layer are arranged in not overlapped position.
Usually, in the solid electrolyte layer that forms layer shape, pin hole is easy to form on thickness direction.In the present invention, because positive electrode layer and positive electrode layer are arranged not overlappedly,, thereby can keep the function of battery so even if form pin hole in solid electrolyte layer, two electrode layers can the short circuit significantly by this pin hole yet.
In addition, the electrolytical all-solid-state battery of powder solid is different with using, according to the present invention, because hull cell uses the height adhesion between the layer to form by thin film technique, reduce the interface resistance between solid electrolyte layer and the active material simultaneously so can realize the increase of the area of battery and capacity.Particularly, in the present invention, owing to formed hull cell, so also can easily form Coin-shaped battery and card-type battery.
In addition, according to the present invention, owing to can form the all-solid-state battery that does not use organic electrolyte solution, so can solve by the caused inconvenience of the use of organic electrolyte solution.As above-mentioned inconvenience, for example, can point out to leak caused safety problem by electrolyte solution; The caused heat resistance problem of volatilization by organic electrolyte solution under the temperature of the boiling point that in hot environment, surpasses organic electrolyte solution; In low temperature environment,, the ionic conductivity of organic electrolyte solution causes the decline of cell reaction, the frozen problem of organic electrolyte solution because significantly descending.
In battery according to the present invention, arrange an electrode layer and another electrode layer, make it not overlapped, in addition, solid electrolyte layer is provided between two electrode layers.In this stage, as the stepped construction of layer, mentioned an electrode layer wherein directly be formed on the metal collector situation and wherein an electrode layer directly be formed on the dielectric base or directly be not formed at the situation that collector electrode is provided on the dielectric base betwixt.
In above-mentioned last situation, collector electrode is made of metal, a described electrode layer directly forms on this collector electrode of part and electric insulation layer is not provided betwixt, and electric insulation layer does not form thereon on the surface of other part of collector electrode of a described electrode layer and forms.In addition, on a described electrode layer and electric insulation layer, form solid electrolyte layer, and another electrode layer with on the described electrode layer position overlapped not forming at dielectric substrate.
According to this structure, another electrode is provided in described electrode layer top, and solid electrolyte layer is folded between it but not overlapping with a described electrode layer.In addition, another electrode layer is in the face of being electrically connected to the collector electrode of a described electrode layer; But, between another electrode layer and collector electrode, provide electric insulation layer.Thereby, even if in solid electrolyte layer, there is pin hole, also can suppress the short circuit between another electrode layer and the collector electrode.
Below, in above-mentioned back one situation, collector electrode forms in the SI semi-insulation substrate, thereby forms a described electrode layer covering set electrode subsequently, or a described electrode layer directly is formed in the SI semi-insulation substrate.Then, solid electrolyte layer is formed on a described electrode layer and the dielectric base, and on this dielectric substrate, another electrode layer be formed at not with a described electrode layer position overlapped on.
In this external this structure, another electrode is provided in described electrode layer top, and solid electrolyte layer is folded in therebetween but not overlapping with a described electrode layer and collector electrode.In addition, although the surface of another electrode layer face solid electrolyte layer, dielectric base is provided in the back of solid electrolyte layer.Thereby, even if in solid electrolyte layer, there is pin hole, also can suppress the short circuit between another electrode layer and the described electrode layer (collector electrode).As dielectric base of the present invention, for example can use pottery such as aluminium oxide or SiO2, or the plastics of polyethylene terephthalate (PET) for example.
In addition, in battery of the present invention, positive electrode layer and positive electrode layer are not preferably arranged at grade.
Positive electrode layer and positive electrode layer are formed at the situation on the same level therein, when having the conduction dissimilar materials in the plane, and can short circuit at two electrode layers of some situations.Thereby, when positive electrode layer and positive electrode layer are not arranged on the identical surface, can suppress by the caused short circuit of the interfacial conductive of dissimilar materials.In order on different planes, to form two electrode layers, can mention wherein solid electrolyte layer and electric insulation layer and all be formed on the plane or only have solid electrolyte layer to be formed at method on the plane, provide a dielectric substrate on the described plane so as to form another electrode layer and a described electrode layer between step.
In addition, in battery of the present invention, preferred solid electrolyte layer is by in the face of first dielectric substrate of positive electrode layer with in the face of second dielectric substrate of positive electrode layer forms, thereby and forms that first dielectric substrate and second dielectric substrate are different to have different compositions.
By said structure, can reduce between solid electrolyte layer and the positive electrode layer and at least one interface resistance between solid electrolyte layer and the positive electrode layer.Thereby, can realize the improvement of battery performance, for example increase battery capacity.
For first (the second) dielectric substrate, the preferred use with positive electrode layer (positive electrode layer) has 10,000 Ω cm
2The material of following interface resistance.Interface resistance more preferably is 5,000 Ω cm
2Below, more preferably be 1,000 Ω cm
2Below, more preferably be 500 Ω cm
2Below.In addition, for first dielectric substrate, with solid electrolyte layer wherein is to compare with the situation that one deck of the second dielectric substrate same material forms by using, preferred use can reduce and positive electrode layer between the material of interface resistance, and for second dielectric substrate, be to use the situation that forms with one deck of the first dielectric substrate same material to compare with solid electrolyte layer wherein, can preferably use reduce and positive electrode layer between the material of interface resistance.By selecting material as mentioned above, can reduce interface resistance between solid electrolyte layer and the positive electrode layer or the interface resistance between solid electrolyte layer and the positive electrode layer.Particularly, for example, Li-P-S-N can be proposed, Li-P-S-O can be introduced as second dielectric substrate as first dielectric substrate.The thickness of first dielectric substrate can be not and the consistency of thickness of second dielectric substrate.
In addition, between first dielectric substrate and second dielectric substrate, can also provide the layer of the intermediate electrolyte with different components.For the intermediate electrolyte layer, can preferably use electrolyte with relative high ion-conductivity.In addition, this intermediate electrolyte layer can be formed by one or more layers itself.
After this, the structure of unitary part of the present invention will be described in detail.
(positive electrode layer material)
Positive electrode layer is formed by the active material that comprises occlusion and release lithium ion.Particularly, can preferably use from by lithium cobalt oxide (LiCoO
2), lithiated nickel dioxide (LiNiO
2), lithia magnesium (LiMn
2O
4) and olivine-type iron lithium phosphate (LiFePO
4) or the group formed of its mixture in the oxide selected.In addition, positive electrode layer can also preferably be formed by the sulfide of selecting from the group of being made up of for example sulphur (S), lithium sulfide, titanium sulfide or its mixture.
(forming the method for positive electrode layer)
As the method that forms positive electrode layer, can use wet method and dry method.As wet method, gel sol method, colloid method and casting can be proposed.As dry method, the vapour deposition process such as vapour deposition method, ion implantation, sputtering method or laser ablation method for example can be proposed.
(positive electrode layer material)
Positive electrode layer is also formed by the active material that comprises occlusion and release lithium ion.For example as positive electrode layer, the preferred use from by the lithium metal with can form selected a kind of material the group of the metal of alloy or its mixture or its alloy composition with it.As the metal that can form alloy with lithium, can be preferably selected at least a from the group of forming by aluminium (Al), silicon (Si), tin (Sn), bismuth (Bi) and indium (In) (after this being called " alloy material ").
The positive electrode layer that comprises above-mentioned material can have by himself as the function of collector electrode and because its occlusion and to discharge the ability of lithium ion high and by preferred.Particularly, silicon (Si) is compared the ability with high occlusion and release lithium ion and can be increased energy density with graphite (blacklead).
In addition, because the alloy phase with lithium metal is as positive electrode layer, effect can be obtained wherein can to reduce, and the increase of the resistance of initial charge stage alloy material in first circulation can be suppressed at the transfer resistance of the alloy material of alloying and the lithium ion on the interface between the lithium ion conducting solid electrolyte layer with lithium metal.
In addition, when the metallic element of alloy material is used for positive electrode layer, in the circulation of first charging and discharging, exists and compare the problem that discharge capacity is significantly little with charging capacity; But, when having used the positive electrode layer material that passes through alloy lithium Metal and Alloy material and obtain in advance, can suppress this irreversible capacity extremely low.Thereby, need not add the active positive electrode material of extra quantity corresponding to irreversible capacity, and thereby can improve the capacity density of hull cell.
(structure of positive electrode layer)
Positive electrode layer is not being formed collector electrode, and positive electrode layer (negative electrode active material) self can have the function as collector electrode.In this situation, owing to omit the collector electrode of positive electrode layer thereby be preferred.Particularly, have pattern, and pattern is formed by the district of a plurality of divisions thereby be preferably formed positive electrode layer.In this stage, the district of independent division preferably is connected to the wire portion of collection of energy by melting end.In the district that divides, when the collector electrode short circuit of a district's (positive electrode layer) that divides and positive electrode layer, the melting end fusing between the district of the division of wire portion and short circuit, and thereby can guarantee the safety of battery.For example, the district of independent division forms island shape respectively, and the main lead-in wire (wire portion) that is used for collection of energy is connected to independent island by ligament (melting end).By said structure, increase even if unexpected electric current in one of island, occurs by short circuit and so on, corresponding ligament also can melt, and makes the island of short circuit and the conduction between the main lead-in wire get clogged, and thereby avoids short-circuit condition continuous.
Preferred melting end has little cross section by forming with the wire portion identical materials with the district that divides and comparing with wire portion with the district of division.By said structure, can produce the fusing that causes by short circuit current reliably.Usually, thereby, district, wire portion and the melting end divided have the basic thickness that equates mutually, so the width of melting end can form forr a short time than the width of district that divides and wire portion because forming by pattern-forming.When the positive electrode layer material by having low-melting metal when forming, can improve above-mentioned so-called insurance effect (fuse effect), and, when prior formation has the alloy phase of lithium metal, can further improve this effect in the situation of alloy-based material.
(material of solid electrolyte layer)
Preferred solid electrolyte layer is a lithium ion conductor, and (20 ℃) lithium-ion-conducting of solid electrolyte layer is for being 10
-5More than the S/cm, and the lithium ion mobility is more than 0.999.Particularly, the preferred lithium ionic conductivity 10
-4More than the S/cm, and the lithium ion mobility is more than 0.9999.As the material of solid electrolyte layer, preferred sulfide sill, and solid electrolyte layer is preferably by Li, P with S forms and can comprise oxygen.
(forming the method for positive electrode layer and solid electrolyte layer)
As the method that forms positive electrode layer and solid electrolyte layer, preferred vapour deposition process.As vapour deposition process, for example PVD (physical vapor is synthetic) method and CVD (chemical gaseous phase is synthetic) method can be proposed.Particularly, for example as the PVD method, can propose for example vacuum vapour deposition, sputtering method, ion plating method or laser ablation method, and, can propose hot CVD method or plasma CVD method as the CVD method.
(collector electrode)
On the other hand, collector electrode preferably uses metal forming.For example, selected a kind of material from the group of being made up of copper (Cu), nickel (Ni), iron (Fe), chromium (Cr) and composition thereof can be proposed as the negative electrode collector material.Because these metals do not form intermetallic compound with lithium (Li), so can avoid forming the inconvenience of intermetallic compound with lithium.As above-mentioned inconvenience, for example, because the decline of the collection of energy that is caused by the charging and the structural deterioration of the expansion of discharge operation and the positive electrode layer that contraction causes and positive electrode layer are easy to the inconvenience of dropping from collector electrode owing to the bonding deterioration with the collector electrode that pastes positive electrode layer.As the concrete example of positive electrode collector electrode, selected a kind of material from the group of being made up of aluminium (Al), nickel (Ni) and its alloy and stainless steel can be proposed.
These collector electrodes can form by PVD method or CVD method.Particularly, thus when forming collector electrode and have predetermined pattern,, can easily form collector electrode with predetermined pattern by using suitable mask.
Advantage
By film lithium cell of the present invention, can obtain down column effect.
(1) make it not overlapped owing to arrange positive electrode layer and positive electrode layer, so even if produce pin hole in solid electrolyte layer, two electrode layers can not pass through this pin hole and short circuit significantly yet, and the result, can keep the function as battery.
(2) in addition, can suppress decline, and the result can realize high yield owing to the caused productive rate of pin hole that in solid electrolyte layer, exists.Particularly, in the method for not using electrolyte solution, can form all solid-state thin-film lithium battery with outstanding fail safe, thermal endurance and cryogenic property.Thereby, by increasing area, can realize the increase of capacity and current density, and the result, can obtain to have the lithium rechargeable batteries of high battery capacity and outstanding charge-discharge cycles performance.
Description of drawings
Fig. 1 is the longitdinal cross-section diagram according to the battery of example 1 of the present invention.
Fig. 2 is the longitdinal cross-section diagram according to the battery of example 2 of the present invention.
Fig. 3 is the longitdinal cross-section diagram according to the battery of example 3 of the present invention.
Fig. 4 is the longitdinal cross-section diagram according to the battery of example 4 of the present invention.
Fig. 5 is the longitdinal cross-section diagram according to the battery of example 5 of the present invention.
Fig. 6 is the longitdinal cross-section diagram according to the battery of example 6 of the present invention.
Fig. 7 is the longitdinal cross-section diagram according to the battery of example 7 of the present invention.
Fig. 8 is the schematic diagram that the pattern of employed mask when forming positive electrode layer is shown.
Fig. 9 is the schematic diagram that the pattern of employed mask when forming positive electrode layer is shown.
Reference number
10,11 collector electrodes
20 positive electrode layers
30 electric insulation layers
40 solid electrolyte layers
40L first dielectric substrate
40U second dielectric substrate
50 positive electrode layer
60 dielectric base
70 masks
71 comb electrode holes
The 71A fairlead
71B pectination perforation
80 masks
81,82 comb electrode holes
81A, 82A fairlead
82B, 82B pectination perforation
83 main fairleads
84 lead fixed holes
85 ligament holes
Embodiment
After this, embodiment of the present invention will be described.
Example 1
Fig. 1 is the longitdinal cross-section diagram according to battery of the present invention.This battery has positive electrode layer 20 and the electric insulation layer 30 on the collector electrode of being made by metal forming 10, and solid electrolyte layer 40 is formed on above-mentioned two- layer 20 and 30, and in addition, positive electrode layer 50 is formed on this dielectric substrate 40.
In this battery, collector electrode 10 is most preferably made by selected metal from the group of being made up of aluminium (Al), nickel (Ni), iron (Fe) and stainless steel.Thereby being formed at, positive electrode layer 20 has predetermined pattern on the segment set electrode surface.Do not form thereon on the other parts on collector electrode surface of positive electrode layer, form electric insulation layer 30.Because positive electrode layer 20 is thicker than electric insulation layer 30, so the surface of positive electrode layer 20 is outstanding from electric insulation layer 30.In addition, form solid electrolyte layer 40 so that cover positive electrode layer 20 and electric insulation layer 30.Be that solid electrolyte layer 40 contacts with the upper surface of positive electrode layer 20 and contacts with the lower surface of positive electrode layer 50, and the part solid electrolyte layer 40 that is provided on the positive electrode layer 20 only is in outstanding state.On the other hand, positive electrode layer 50 is formed at not on the position with the overlapping solid electrolyte layer 40 of positive electrode layer 20.Positive electrode layer 50 also forms to such an extent that have a predetermined pattern.For example, thus when forming positive electrode layer 20 and positive electrode layer 50 and have pectination, can wholely increase the magnitude of current that allows by battery.
In said structure, when positive electrode layer 20 is formed on the collector electrode 10, make the oxidized formation of the part metal oxide layer that will form the collector electrode surface outside the positive electrode layer 20 on it thereby collector electrode 10 is exposed to air atmosphere, and this metal oxide layer is preferably used as electric insulation layer 30.In addition, after forming positive electrode layer 20, use the mask that has corresponding to the pattern of positive electrode layer 20, electric insulation layer 30, for example metal oxide layer or organic polymer layers are on the part on the collector electrode surface outside can formation positive electrode layer 20 formed thereon.
By having the battery of this structure, because positive electrode layer 20 is arranged in different positions with positive electrode layer 50 and makes at its thickness direction not overlapped, even if, also can avoid two electrode layer short circuits so in being provided in two solid electrolyte layers between the electrode layer, form pin hole.In addition, although in the face of the positive electrode layer 50 of collector electrode is electrically connected positive electrode layer 20, electric insulation layer 30 is formed between collector electrode 10 and the solid electrolyte layer 40, and solid electrolyte layer 40 is positioned at below the positive electrode layer 50.Thereby, even if form pin hole in the solid electrolyte layer below positive electrode layer 40, also can be suppressed at the short circuit between positive electrode layer 50 and the collector electrode 10.
Example 2
Fig. 2 is the longitdinal cross-section diagram according to battery of the present invention, and its structure is different with the structure of example 1.Except the place-exchange of the position of positive electrode layer 20 and positive electrode layer 50, the basic structure of this example and example 1 are roughly the same.Promptly the battery of this example has positive electrode layer 50 and the electric insulation layer 30 on the collector electrode of being made by metal forming 11, and solid electrolyte layer 40 is formed on described two layers 50 and 30, and in addition, positive electrode layer 20 is formed on the dielectric substrate 40.
In this battery, owing to collector electrode 11 contacts with positive electrode layer 50, so most preferably use selected metal from the group of forming by copper (Cu), nickel (Ni), iron (Fe) and stainless steel.In addition, in this structure, although not shown, the positive electrode collector electrode is formed at positive electrode side.This positive electrode collector electrode only be formed on the positive electrode layer and the zone that does not form positive electrode 20 not formed thereon in.Thereby, even if form pin hole in the solid electrolyte layer 40 on positive electrode layer 40, also can avoid positive electrode layer 50 and the short circuit of positive electrode collector electrode.
Structure by this example, because positive electrode layer 20 also is arranged in different positions with positive electrode layer 50 and makes on its thickness direction not overlapped, identical with the situation of example 1, even if in being provided in two solid electrolyte layers 40 between the electrode layer, form pin hole, also can avoid two electrode layer short circuits.In addition, owing to electric insulation layer 30 is formed between positive electrode layer 20 and the collector electrode 11, so, also can suppress the short circuit between positive electrode layer 20 and the collector electrode 11 even if form pin hole in the solid electrolyte layer below positive electrode layer 40.
Example 3
Fig. 3 is the longitdinal cross-section diagram according to the battery of use dielectric base of the present invention.In this example, have pattern thereby be formed on the dielectric base 60 by the collector electrode that metal forming is made, positive electrode layer 20 is formed on the collector electrode overlapping, and forms solid electrolyte layer 40 so that cover dielectric base 60 and positive electrode layer 20.Subsequently, positive electrode layer 50 is formed on the dielectric substrate 40 not and positive electrode layer 20 position overlapped.
In this battery, as dielectric base 60, the preferred sheet material of making by for example pottery or organic polymer of using.In the position that collector electrode 10 and positive electrode layer 20 are provided, form solid electrolyte layer 40 and make outstanding from other position.In addition, although clearly do not illustrate in Fig. 3, the surface of the collector electrode 10 under being positioned at below the positive electrode layer 20 is partly exposed, and by this part that is exposed, can carry out collection of energy.
Structure by this example, because positive electrode layer 20 also is arranged in different positions with positive electrode layer 50 and makes on its thickness direction not overlapped, identical with the situation of example 1, even if in being provided in two solid electrolyte layers 40 between the electrode layer, form pin hole, also can avoid two electrode layer short circuits.In addition, although solid electrolyte layer 40 is positioned at below the positive electrode layer 50, dielectric base 60 is positioned at below this dielectric substrate 40, and positive electrode layer 50 is arranged not overlappingly with the collector electrode 10 that is positioned at below the positive electrode layer 20; Thereby, even if having pin hole in the solid electrolyte layer below positive electrode layer 40, also can avoid positive electrode layer 50 and collector electrode 10 short circuits.In addition, in this example, because positive electrode layer 50 itself also plays the positive electrode layer collector electrode, thus need not the positive electrode layer collector electrode, and thereby can simplify the structure of battery.
Example 4
Fig. 4 is the longitdinal cross-section diagram according to battery of the present invention, and the position of positive electrode layer wherein shown in Figure 3 and the position of positive electrode layer are exchanged mutually.In this battery, have pattern thereby be formed on the dielectric base 60 by the collector electrode 11 that metal forming forms, positive electrode layer 50 is formed on this collector electrode to overlap, and in addition, forms solid electrolyte layer 40 so that cover dielectric base 60 and positive electrode layer 50.Subsequently, positive electrode layer 20 is formed on this dielectric substrate not and positive electrode layer 50 position overlapped.In addition, in this example, collector electrode 10 is formed on the upper surface of positive electrode layer 20.This collector electrode 10 only is formed on the upper surface of positive electrode layer 20 and is not formed on other position.
In this structure, make not overlapped on its thickness direction because positive electrode layer 20 also is arranged in different positions with positive electrode layer 50, even if, also can avoid two electrode layer short circuits so in being provided in two solid electrolyte layers 40 between the electrode layer, form pin hole.In addition, although solid electrolyte layer 40 is positioned at below the positive electrode layer 20, because dielectric base 60 is provided in below this dielectric substrate 40, and positive electrode layer 20 is arranged not overlappingly with the collector electrode 11 that is positioned at below the positive electrode layer 50, even if, also can avoid positive electrode layer 20 and collector electrode 11 short circuits so have pin hole in the solid electrolyte layer 40 below positive electrode layer.
Example 5
Fig. 5 is the longitdinal cross-section diagram according to battery of the present invention, and wherein positive electrode layer directly is formed on the dielectric base.In this example, thereby positive electrode layer 50 is formed at and has predetermined pattern in the SI semi-insulation substrate 60, and forms solid electrolyte layer 40 so that cover the other parts of positive electrode layer 50 and dielectric base 60.Subsequently, positive electrode layer 20 and collector electrode 10 are formed on the solid electrolyte layer 40 not and positive electrode layer 50 position overlapped in order.This collector electrode 10 only is formed on the positive electrode layer 20 and is not formed on other position.Although not shown in this Figure, positive electrode layer 50 is partly exposed by dielectric substrate 40 and forms to make and can carry out collection of energy by the position that is exposed.
In the battery of this example, make on its thickness direction not overlapped because positive electrode layer 20 and positive electrode layer 50 also are arranged in diverse location, even if in being provided in two solid electrolyte layers 40 between the electrode layer, form pin hole, also can avoid two electrode layer short circuits.In addition, in this example, because positive electrode layer 50 self also plays the positive electrode layer collector electrode, thus need not the positive electrode layer collector electrode, and thereby can simplify the structure of battery.
Example 6
In addition, figure 6 illustrates the improvement of example 3.In this battery, collector electrode 10 also is formed on the dielectric base 60, and positive electrode layer 20 is formed on the collector electrode 10.Subsequently, solid electrolyte layer 40 is formed on the positive electrode layer 20, and on this dielectric substrate 40, forms positive electrode layer 50.Fig. 6 has the partial cross section figure that positive electrode layer 50 wherein is arranged in the hull cell of the structure between a pair of positive electrode layer 20.
In this battery, form positive electrode layer 20 so that except the upper surface of covering set electrode 10, also cover its side.Thereby, be intended to increase the contact area between positive electrode layer 20 and the collector electrode 10.In addition, identical with the situation of example 1 to 5, positive electrode layer 50 is not overlapped with positive electrode layer 20 and be not formed on the identical plane.In this battery, positive electrode layer 20 is formed on the corresponding collector electrode 10, and positive electrode layer 50 is formed on the solid electrolyte layer 40.Thereby, even if some conduction dissimilar materialss stick between positive electrode layer 50 and the positive electrode layer 20, also can suppress effectively owing to pass through the short circuit therebetween of the interfacial conductive of this dissimilar materials.Certainly, as described in the above-mentioned example,, also can suppress the short circuit between two electrode layers 20 and 50 by forming positive electrode layer 20 and positive electrode layer 50 at the diverse location when planar observing.
Example 7
Fig. 7 is the longitdinal cross-section diagram according to battery of the present invention, and it comprises the solid electrolyte layer that is made of two-layer.Except solid electrolyte layer 40 by the first dielectric substrate 40L that contacts with positive electrode layer 20 with the second dielectric substrate 40U that contacts with positive electrode layer 50 forms, the battery of this example has and example 1 essentially identical structure.
In this battery, compare with the situation that one deck of the second dielectric substrate 40U identical materials forms by using with solid electrolyte layer 40 wherein, the first dielectric substrate 40L uses the material formation that can reduce with the interface resistance of positive electrode layer 20.For example Li-P-S-N is used for the first dielectric substrate 40L, and Li-P-S-O is used for the second dielectric substrate 40U.
By said structure, compare by the situation that the one deck that uses Li-P-S-O forms with solid electrolyte layer 40 wherein, can reduce the interface resistance between the first dielectric substrate 40L and the positive electrode layer 20.Thereby, can improve battery performance, for example capacity.
(experimental example 1)
According to structure shown in Figure 1, film lithium cell uses aluminium foil as positive collector electrode, LiCoO
2Film forms as positive electrode layer as solid electrolyte layer, lithium metal film as positive electrode layer, Li-P-S-O.At first, the square aluminium foil that has thickness and be 10 μ m and length of side 10cm is fixed on the substrate chuck of stainless steel, and the stainless steel mask of positive electrode is fixed on the above-mentioned aluminium foil.In mask 70, go out as shown in FIG. 8, form 8 both sides stripping fork shape electrode holes 71, in each hole, both sides at the fairlead 71A of the length of width with 1mm and 8cm, on Width, so that the pectination perforation 71B of the length of each width with 1mm and 4mm to be provided in the spacing perpendicular to the 1mm of the direction of fairlead 71A.Two ends in each comb electrode hole 71 do not form pectination perforation 71B.
LiCoO
2Film (positive electrode layer) melts method by excimer laser and goes up formation in this substrate (aluminium foil).KrF excimer laser with 248nm wavelength is as excimer laser.Film is formed on and carried out under the lasing condition 5 hours, and wherein base reservoir temperature is 500 ℃, and the vacuum degree in oxygen atmosphere is 10
-2Pa, repetition pulse are 10Hz, and energy density is 2j/cm
2In this stage, just before laser film forms, use ar-ion beam to clean the surface of substrate.When using contact pilotage type film thickness instrument that the thickness of the film on the silicon base that provides is in advance measured, find that the thickness of positive electrode layer is 10 μ m, and the capacity of the active positive electrode material that provides is 1.6mAh in whole substrate.In addition, when not forming the resistance of aluminium foil surface of positive electrode layer on measuring it, it is more than the 1M Ω, and finds that electric insulation layer is formed on the surface of aluminium foil.
Remove after this mask,, on whole surface, melt method and form solid electrolyte layer with lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition by excimer laser according to following flow process.Filled in the glove box of argon gas of dew point lithium sulfide (Li therein with-80 ℃
2S), phosphoric sulfide (P
2S
5) and five phosphorous oxide (P
2O
5) mix, and thereby the powder that obtains by so that be placed in the mould, subsequently by exerting pressure, thereby form the target of sheet form.
Target is transferred to the film forming device from glove box, makes target not be exposed to air and be placed in the film forming device, thereby and laser focusing on target, evaporate raw material, in substrate, form film thus.Substrate is heated indistinctively.
Form after the film of solid electrolyte layer, use the ESCA 5400MC analyzing film composition of making by Phi Inc, and find that lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition comprises 26,13,54 and 7 atomic percent respectively.In addition, when the measurement for film thickness, when observing the cross section of the film that forms by scanning electron microscopy (SEM) on silicon base, the film thickness of this solid electrolyte layer is 1 μ m.In addition, on the copper comb electrode is formed at solid electrolyte layer on the substrate of glass, and carry out complex impedance subsequently when measuring, find that the ionic conductivity of solid electrolyte layer is 2 * 10
-4S/cm.
Form thereon in the substrate of collector electrode, positive electrode layer and solid electrolyte layer, fixedly the negative electrode mask.In this negative electrode mask 80, go out as shown in FIG. 9, nine comb electrode holes 81 and 82 form row, and it has the shape that forms comb electrode with the mask 70 (Fig. 8) that is used to form positive electrode layer.Comb electrode hole 81 at the first and the 9th row is side tooth electrode holes, in each hole, it is pectination perforation 81B is formed at fairlead 81A on the direction perpendicular to fairlead 81A a side, and the comb electrode hole 82 at second to the 8th row is both sides pectination perforations, in each hole, promptly perforation 82B in both sides is formed at the both sides of fairlead 82A on the direction perpendicular to fairlead 82A.In addition, be connected to main fairlead 83 by the fairlead 81A in the 9 capable comb electrode holes of arranging and the end of 82A, and, provide square lead fixed hole 84 with 5mm length of side in an end of this main fairlead 83 with 1mm width and 9cm length.This mask 80 is arranged to such an extent that make electrode hole independent when observing in the plane 81 and 82 not overlapping with the positive electrode layer of prior formation.The pectination positive electrode layer and the prior pectination positive electrode layer that forms that form by this mask 80 are arranged in parallel, and distance therebetween is 0.1mm.
By vapour deposition method, the lithium metal film that is used as positive electrode layer is 10
-4Be formed in the substrate that provides mask under the vacuum degree of Pa.Analyze by the icp analysis at the stainless steel-based end (inductively coupled plasma atomic emissions spectrum Inductively Coupled Plasma Atomic EmissionSpectrometry) that is formed at that is used for the film thickness measurement, find that film thickness is 1 μ m.
The battery assessment of the hull cell that then, forms thus.Exposed the aluminum metal surface thereby the end of the rear surface of aluminium substrate slightly frustrates in the hothouse of dew point-60 ℃, and the aluminum lead is welded to this metal surface by ultra-sonic welded.In addition, the lead of Copper Foil is welded to the lead fixed portion of lithium metal film (positive electrode layer) by ultra-sonic welded.In addition, the part outside the end of lead is with polymer system encapsulant with by the sealing of the containment member of aluminium lamination bag system, and making only has the end to be exposed.
By using this battery, carried out in 4.2 to 3V voltage ranges charge-discharge cycles test at 1C (C pilot cell capacity) by current stabilization control.Before charging-discharge test, observe the above OCV (open circuit voltage) of 3V.In addition, when battery keeps 24 hours under charged state, do not observe voltage fully and reduce, and confirm between positive electrode layer and positive electrode layer, short circuit not occur.In addition, in this loop test, confirmed the stabilized driving of the circulation more than 1000.
(experimental example 2)
According in the structure shown in Fig. 3, dielectric base is used aluminium oxide, the positive electrode collector electrode is used aluminium foil, positive electrode layer is used LiCoO
2Film, solid electrolyte layer is used Li-P-S-O and positive electrode layer is used the Al-Li alloy film and formed film lithium cell.At first, the square aluminium sheet with 1mm thickness and 10cm length of side is fixed on the stainless steel substrate chuck, and stainless steel mask is fixed on the above aluminium sheet.Mask have in the similar structure shown in Fig. 8.
In this substrate, form aluminium film with 0.1 μ m thickness by vapour deposition method.In addition, melt method by excimer laser and form LiCoO
2Film (positive electrode layer) keeps mask simultaneously.KrF excimer laser with 248nm wavelength is as excimer laser.Film is formed on and carried out under the lasing condition 5 hours, and wherein base reservoir temperature is 500 ℃, and the vacuum degree in oxygen is 10
-2Pa, repetition pulse are 10Hz, and energy density is 2j/cm
2In this stage, just before laser film forms, use ar-ion beam to clean the surface of substrate.When using contact pilotage type film thickness instrument that the thickness of the film on the silicon base that provides is in advance measured, find that the thickness of positive electrode layer is 10 μ m, and the capacity of the active positive electrode material that provides is 1.6mAh in whole substrate.In addition, when not forming the resistance of aluminium foil surface of positive electrode layer on measuring it, it be more than the 1M Ω, and the discovery electric insulation layer is formed on the surface of aluminium foil.
Remove after this mask,, on whole surface, melt method and form solid electrolyte layer with lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition by excimer laser according to following flow process.Filled in the glove box of argon gas of dew point lithium sulfide (Li therein with-80 ℃
2S), phosphoric sulfide (P
2S
5) and five phosphorous oxide (P
2O
5) mix, and thereby the powder that obtains by so that be placed in the mould, subsequently by exerting pressure, thereby form the target of sheet form.
Target is transferred to the film forming device from the gloves feather cockscomb, makes not to be exposed to air and to be placed in the film forming device, thereby and laser focusing on target, evaporate raw material, the film of formation solid electrolyte layer in substrate thus.Heat substrate indistinctively.
Form after the film of solid electrolyte layer, use the ESCA 5400MC analyzing film composition of making by Phi Inc, and find that lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition comprises 26,13,54 and 7 atomic percent respectively.In addition, when observing the cross section of the film that forms for the measurement of film thickness by scanning electron microscopy (SEM) on silicon base, the film thickness of this solid electrolyte layer is 1 μ m.In addition, be formed on the solid electrolyte layer that provides on the substrate of glass, and carry out complex impedance subsequently when measuring, find that the ionic conductivity of solid electrolyte layer is 2 * 10 when the copper comb electrode
-4S/cm.
Form thereon in the substrate of collector electrode, positive electrode layer and solid electrolyte layer, fixedly the negative electrode mask.Have similar structure and size at this negative electrode mask to the negative electrode mask shown in Fig. 9.
By vapour deposition method, the lithium metal film that is used as positive electrode layer is 10
-4Be formed in the substrate that provides mask under the vacuum degree of Pa.Analyze by the suprabasil icp analysis of stainless steel (inductively coupled plasma atomic emissions spectrum Inductively Coupled Plasma Atomic EmissionSpectrometry) that is formed at that is used for the film thickness measurement, find that film thickness is 1 μ m, and aluminium is 3 to 1 to the composition of lithium than (atomic ratio).
Then, carry out thereby the battery assessment of the hull cell that forms.Exposed the aluminum metal surface as lead fixed portion thereby the part of positive electrode layer slightly frustrates in the hothouse of dew point-60 ℃, and the aluminum lead is welded to this metal surface by ultra-sonic welded.In addition, the lead of Copper Foil is welded to the lead fixed portion of lithium-aluminium alloy film by ultra-sonic welded.In addition, the part outside the end of lead is with polymer system encapsulant with by the sealing of the containment member of aluminium lamination bag system, and making only has the end to be exposed.
By using this battery, carried out in 4.2 to 3V voltage ranges charge-discharge cycles test at 1C (C pilot cell capacity) by current stabilization control.Before charging-discharge test, observe the above OCV (open circuit voltage) of 3V.In addition, when battery keeps 24 hours under charged state, do not observe voltage fully and reduce, and confirm between positive electrode layer and positive electrode layer, short circuit not occur.In addition, in this loop test, 1000 stabilized driving have been confirmed with cocycle.
(experimental example 3)
According in the structure shown in Fig. 1, the positive electrode collector electrode is used aluminium foil, positive electrode layer is used LiMn
2O
4Film, solid electrolyte layer is used Li-P-S-O and positive electrode layer is used the lithium metal film and formed film lithium cell.At first, the square aluminium foil with 1mm thickness and 10cm length of side is fixed on the stainless steel substrate chuck, and stainless steel mask is fixed on the aluminium foil top.Mask have in the mask shown in Fig. 8 similar structure and size.
Melt method by excimer laser and in this substrate, form LiMn
2O
4Film (positive electrode layer).KrF excimer laser with 248nm wavelength is as excimer laser.Film is formed on and carried out under the lasing condition 5 hours, and wherein base reservoir temperature is 500 ℃, and the vacuum degree in oxygen is 10
-2Pa, repetition pulse are 10Hz, and energy density is 2j/cm
2In this stage, just before laser film forms, use ar-ion beam to clean the surface of substrate.When using contact pilotage type film thickness instrument that the thickness of the film on the silicon base that provides is in advance measured, find that the thickness of positive electrode layer is 10 μ m, and the capacity of the active positive electrode material that provides is 1.2mAh in whole substrate.In addition, when not forming the resistance of aluminium foil surface of positive electrode layer on measuring it, it be more than the 1M Ω, and the discovery electric insulation layer is formed on the surface of aluminium foil.
Remove after this mask,, on whole surface, melt method and form solid electrolyte layer with lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition by excimer laser according to following flow process.Filled in the glove box of argon gas of dew point lithium sulfide (Li therein with-80 ℃
2S), phosphoric sulfide (P
2S
5) and five phosphorous oxide (P
2O
5) mix, and thereby the powder that obtains by so that be placed in the mould, subsequently by exerting pressure, thereby form the target of sheet form.
Target is transferred to the film forming device from glove box, makes not to be exposed to air and to be placed in the film forming device, thereby and laser focusing on target, evaporate raw material, the film of formation solid electrolyte layer in substrate thus.Heat substrate indistinctively.
Form after the film of solid electrolyte layer, use the ESCA 5400MC analyzing film composition of making by Phi Inc, and find that lithium (Li)-phosphorus (P)-sulphur (S)-oxygen (O) composition comprises 26,13,54 and 7 atomic percent respectively.In addition, when observing the cross section of the film that forms for the measurement of film thickness by scanning electron microscopy (SEM) on silicon base, the film thickness of this solid electrolyte layer is 1 μ m.In addition, be formed on the solid electrolyte layer that provides on the substrate of glass, and carry out complex impedance subsequently when measuring, find that the ionic conductivity of solid electrolyte layer is 2 * 10 when the copper comb electrode
-4S/cm.
Form thereon in the substrate of collector electrode, positive electrode layer and solid electrolyte layer, fixedly the negative electrode mask.Although this negative electrode mask has similar structure and size to the negative electrode mask shown in Fig. 9, the mask of Shi Yonging is different with it in this example because comb electrode hole 81 and 82 and the connecting portion of main fairlead 83 all form and have the ligament hole.2 chain lines promptly as in Fig. 9 are shown, comb electrode hole 81 and 82 with the connecting portion of main fairlead 83, formation has the width little ligament hole 85 of width than fairlead 81A and 82A and main fairlead 83.In this situation, the part that is formed by comb electrode hole 81 and 82 is the district that divides, and the part that is formed by main fairlead 83 is a wire portion, and the ligament portion of the positive electrode layer that forms in the ligament hole is a melting end.The width in this ligament hole is 0.1mm.
By vapour deposition method, the lithium metal film that is used as positive electrode layer is 10
-4Be formed in the substrate that provides mask under the vacuum degree of Pa.Be formed at the suprabasil icp analysis of stainless steel (Inductively Coupled Plasma Atomic Emission Spectrometry) analysis by what be used for that film thickness measures, find that film thickness is 1 μ m.
Then, carry out thereby the battery assessment of the hull cell that forms.Exposed the aluminum metal surface thereby the end of the rear surface of aluminium substrate slightly frustrates in the hothouse of dew point-60 ℃, and the aluminum lead is welded to this metal surface by ultra-sonic welded.In addition, the lead of Copper Foil is welded to the lead fixed portion of lithium metal film by ultra-sonic welded.In addition, the part outside the end of lead is with polymer system encapsulant with by the sealing of the containment member of aluminium lamination bag system, and making only has the end to be exposed.
So this battery that forms is placed in the glove box of circulation A r gas wherein, has carried out in 4.3 to 3.3V voltage ranges charge-discharge cycles test at 1C (C pilot cell capacity) by current stabilization control.Before charging-discharge test, observe the above OCV (open circuit voltage) of 3V.In addition, when battery keeps 24 hours under charged state, do not observe voltage fully and reduce, and confirm between positive electrode layer and positive electrode layer, short circuit not occur.In addition, in this loop test, also confirmed stabilized driving.
Then, during charging and discharge test, one of comb electrode of positive electrode layer is run through from above by metal needle so that cause short circuit between the collector electrode of part positive electrode layer and positive electrode layer.After metal needle penetrates immediately, have the 0.1mm width and connect this comb electrode portion and main lead-in wire between ligament be melted; But other comb electrode portion continues stable charge-discharge cycles and does not cause any anomalous event.
(experimental example 4 to 7)
According to the method described in experimental example 1, use different positive electrode layer materials to form the film lithium cell that has in the structure shown in Fig. 1, and this battery is carried out testing similar in appearance to the charge-discharge cycles of experimental example 1.Shown in the following table according to the material and the result of the test of the material of the positive electrode layer of independent experimental example, positive electrode layer (active positive electrode material), positive electrode collector electrode.In all experimental example shown in the following table, confirmed to realize 1000 stabilized driving, and obtained preferred charge-discharge cycles performance with cocycle.
Table
| The positive electrode layer material | Active positive electrode material | The positive electrode collector electrode | The charge-discharge cycles performance | |
| Experimental example 4 | Si-Li(1:1) | LiCoO 2 | Al | Well |
| Experimental example 5 | The Sn element | LiCoO 2 | Al | Well |
| Experimental example 6 | Bi-Li(1:1) | LiCoO 22 | Al | Well |
| Experimental example 7 | The In element | LiCoO 2 | A1 | Well |
(experimental example 8)
Then, formed battery with reference to the example 7 of figure 7.The structural similarity of the basic structure of this battery and experimental example 1.But, this battery different with in experimental example 1, because Li-P-S-O is as second dielectric substrate in experimental example 1, and before this second dielectric substrate formed by the laser ablation method, Li-P-S-N formed as first dielectric substrate.In this example, lithium phosphate sputter under the pressure of 100mm Torr (0.13Pa) in the mist of the oxygen of nitrogen that comprises 20 volume % and 80 volume % makes formation have the Li-P-S-N film of the thickness of 0.1 μ m.Interface resistance between the first dielectric substrate 40L and the positive electrode layer 20 is 1000 Ω cm
2Below, and the interface resistance between the second dielectric substrate 40U and the positive electrode layer 50 is 10000 Ω cm
2Below.
When assessment during thus obtained hull cell, the battery that confirms this example can have and is the battery of experimental example 15 times current capacity roughly.
The technique practicality
But can preferably be used as the recharge secondary cell according to battery of the present invention, and more specifically, in the situation of not using electrolyte solution, above battery can be preferably as all solid lithium secondary battery with outstanding security, heat resistance and cryogenic property. For example, expect that this battery is used as the power supply of various portable or mobile type electric power and electronic installations. In addition, have outstanding heat resistance and jumbo battery of the present invention and can also be acted on the battery that is placed on the electric substrate in the reflow step by for example usefulness, the brazing that goes between in this reflow step is carried out in heating furnace simultaneously, and battery of the present invention can also be used as for the stand-by power supply of electronic circuit of automobile etc. and require the main power source of heat resistance.
Claims (7)
1. film lithium cell comprises: positive electrode layer, positive electrode layer, be arranged at therebetween solid electrolyte layer and at least one collector electrode; Described at least one collector electrode is connected at least one positive electrode layer and positive electrode layer, and wherein said positive electrode layer and positive electrode layer are arranged on when not opposed facing position when the stacked direction of described layer is seen,
Wherein said positive electrode layer is not arranged on the identical plane with positive electrode layer.
2. according to the film lithium cell of claim 1,
Wherein said collector electrode comprises metal,
One of electrode layer directly is formed on the segment set electrode and is not arranged at therebetween electric insulation layer, and
Electric insulation layer is formed on the surface of other parts of described collector electrode, does not form one of described electrode layer thereon.
3. according to the film lithium cell of claim 1, wherein said collector electrode is formed in the SI semi-insulation substrate, thereby and forms the Zone Full of the upper surface of one of electrode layer covering set electrode or the side surface of covering set electrode and upper surface.
4. according to the film lithium cell of claim 1 or 2, wherein said positive electrode layer comprises and is selected from by the Li metal or can forms a kind of material of the group of the material of alloy or its mixture or alloy composition with the Li metal, and described positive electrode layer is also as collector electrode.
5. according to the film lithium cell of claim 4, wherein saidly can comprise at least a material that is selected from the group of forming by aluminium (Al), silicon (Si), tin (Sn), bismuth (Bi) and indium (In) with the material that the lithium metal forms alloy.
6. according to the film lithium cell of claim 4, wherein said positive electrode layer comprises:
A plurality of subregions;
The leading part that is used for power scavenging; With
Subregion is connected to the melting end of leading part, and
When some subregions and the collector electrode short circuit faced with it, leading part and melted by the melting end between the subregion of short circuit.
7. according to the film lithium cell of claim 1 or 2, wherein said solid electrolyte layer has first dielectric substrate of facing described positive electrode layer and second dielectric substrate of facing described positive electrode layer, and described first dielectric substrate has the composition different with second dielectric substrate.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2005274719 | 2005-09-21 | ||
| JP274719/2005 | 2005-09-21 | ||
| JP220687/2006 | 2006-08-11 |
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| CN103268930B (en) * | 2013-05-17 | 2015-09-09 | 哈尔滨工业大学 | The preparation method of lithium battery and lithium ion battery electrode, solid electrolyte film |
| CN108011078B (en) * | 2016-11-01 | 2020-02-14 | 中山大学 | Flexible substrate-based electrode assembly and preparation method of lithium-oxygen thin film battery |
| CN108023145B (en) * | 2016-11-01 | 2019-11-19 | 中山大学 | Electrode assembly, lithia hull cell and preparation method |
| CN111656563B (en) * | 2017-09-05 | 2023-04-04 | 罗伯特·博世有限公司 | Surface coating for ceramic electrolyte particles |
| CN112349886B (en) * | 2019-08-06 | 2022-04-29 | 北京梦之墨科技有限公司 | Self-generating electrode material, negative electrode and self-generating structure |
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