JP2001076732A - Flexible electrode and electrochemical element using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery simplifying assembly without positioning of a positive electrode and a negative electrode reducing performance defect, and enhancing reliability, and provide a lithium secondary battery with high voltage and high capacity. SOLUTION: An electrode-separator united body is formed by continuously forming a positive electrode 1 on one side of a separator 3 and a negative electrode 2 on the other side so as to have narrower width than the separator. They are stacked to form a battery. Flexible electrodes using a soft binder are used thereto and the positive electrode 1 and the negative electrode 2 are faced through the separator 3, and they are folded up even-numbered times, enveloped with an electrical insulation sealing material 4, and both ends in the folded up direction are interposed between conductive plates 5 to constitute a flat battery. A lithium secondary battery with high voltage and high capacity can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical device for electrochemically moving ions into and out of an electrode, and more particularly to a structure of a lithium secondary battery and its electrode. The present invention relates to a battery or an assembled battery combining a plurality of batteries. Available. In this specification, a battery will be described as an example of an electrochemical element.

[0002]

2. Description of the Related Art As an electrochemical element for electrochemically transferring ions into and out of an electrode, there is, for example, a battery. In a normal battery, a positive electrode that takes in electrons from an external circuit during discharge and a cation from the electrolyte or takes in electrons from an external circuit and releases an anion to the electrolyte, and a negative electrode that operates in the opposite direction to the positive electrode, It has a structure in which the electrodes are opposed to each other via a layer called a separator having no electron conductivity and containing an electrolyte.

[0003] If the electrode is a so-called manganese dry battery, the positive electrode is obtained by piercing a positive electrode mixture prepared by kneading manganese dioxide as an active material, carbon as a conductive agent and an electrolyte with a carbon rod for current collection. The negative electrode is a can of zinc as an active material.

In the battery having such a structure, when an attempt is made to obtain a large current, the current density is increased and only the active material near the current collector is used, so that the practical battery capacity is reduced. In particular, this phenomenon was remarkable in the case of a non-aqueous electrolyte battery using lithium ions, in which the electric conductivity of the electrolyte was small.

[0005] Since a lithium secondary battery is lightweight and can obtain a high voltage, it has been actively developed not only for a small portable electronic device but also for a large storage battery.

In this lithium secondary battery, lithium metal alone was used as a negative electrode material before.
There are problems such as an internal short circuit caused by lithium metal dendritic precipitation. Therefore, in recent years, a method of using carbon as a negative electrode material and inserting and removing lithium ions has become mainstream. The use of this electrode has made it possible to provide a highly safe battery having a voltage equivalent to that of the case of using lithium metal and having no dendritic deposition. The structure of this negative electrode is such that a carbon material such as pyrolytic carbon, carbon black, coke, and graphite is used, and a binder is used for molding to bind the carbon material.

[0007] As a positive electrode material for a lithium secondary battery, a material capable of high voltage and high energy density and capable of inserting and removing lithium ions while maintaining the structure is required. Various materials have been proposed. Have been. For example, T
iS2, MnO2, V2O5, LiCoO2, LiNiO2,
LiMn2O4 and the like. As a constituent material of the positive electrode, these positive electrode active materials are used as main components, and graphite or the like is added to improve conductivity, and a binder is added and bound to provide moldability similarly to the negative electrode. ing.

In a conventional lithium secondary battery, a separator is interposed between the two electrodes, and a non-aqueous organic solvent is used as an electrolyte. The battery has a coin type or a cylindrical prism type.

In general, when obtaining a large current in a battery, attempts have been made to increase the electrode area as much as possible. Particularly in lithium secondary batteries, since an organic solvent having relatively low conductivity is used as the electrolyte,
It is particularly important to increase the area of the electrode.

FIG. 12 is a half sectional side view showing a conventional coin-type battery shown on page 124 of, for example, "Battery Handbook" (edited by Battery Handbook Editing Committee, published by Maruzen 1990).
1 is a positive electrode, 2 is a negative electrode, 3 is a separator, and 4 is a sealing material.

In the flat battery having such a structure, there is a limit in increasing the electrode area. Therefore, a cylindrical battery having a large electrode area by winding up a strip-shaped electrode has been manufactured as a battery of a type that takes a large current so that a large current can be obtained even in the case of an electrolyte having a small electric conductivity. For example, as described in Japanese Patent Application Laid-Open No. 2-51875, a method has been devised to substantially reduce the current density by laminating and winding up a strip-shaped electrode and a separator. In addition, the usual assembling method has been to separately manufacture and laminate a strip-shaped electrode and a separator.

Further, in order to obtain a large area by using a flat electrode, a conventional method has been to adopt a structure in which so-called strip electrodes are connected. Fig. 13 is also the "Battery Handbook"
(Battery Handbook Editing Committee, published by Maruzen 1990) 188
It is a disassembled perspective view which shows the structure of the conventional clad type lead battery shown in the page. Both the strip-shaped positive electrode 1 and the strip-shaped negative electrode 2 are connected like a comb with a current collecting tab and a connecting rod, arranged via a separator, and put in one container.

On the other hand, a lithium secondary battery boasting a high voltage is at most 3 to 4 V. Therefore, when a higher voltage is required, a method of connecting batteries in series is adopted.

In the case where, for example, one battery appears to output 12 V like a lead battery for an automobile, the inside of the tank is divided into a plurality of cells, and each cell is combined with a single cell element in which a positive electrode plate and a negative electrode plate are combined via a separator and an electrolytic cell. Liquid is contained, and one of the separators is a single cell, and the single cells are connected in series via a current collecting tab and a current collecting rod. As in a so-called pack battery, there is also a type in which a cylindrical battery or a square battery assembled as a unit cell and connected in series by spot welding are put in a container. On the other hand, there is a method in which cells are connected in series while forming cells in a so-called bipolar structure, such as that found in a fuel cell or a redox flow battery for power storage.

In a conventional secondary battery, it is general to remove heat generated by charging / discharging to natural heat radiation. Therefore, when a large number of batteries are used in a single room for power storage or the like, they are used. Pay attention to room ventilation and temperature.

In the conventional sealed secondary battery, when an internal pressure is abnormally increased due to gas generation accompanying a charge / discharge reaction or a side reaction, a weak portion is provided in a part of the battery container to release the internal pressure. A method is used to destroy the leverage.

[0017] In this case, the battery becomes unusable because the electrolyte flows out together with the release of the internal pressure. In the open type secondary battery, the gas can always escape, but at the same time, the electrolyte is also scattered, so that the structure is such that the electrolyte can be injected from the outside in a timely manner.

[0018]

Most of the conventional practical secondary batteries have a water-based electrolyte.
Electrodes have low ionic conduction resistance and use electrodes that are stable in air. On the other hand, the performance of a lithium secondary battery is brought out only in an internal environment from which moisture is sufficiently removed. In other words, there is a problem that a stable and high-performance lithium secondary battery cannot be manufactured with the structure and material used for the conventional secondary battery.

For example, the maximum current drawn from a lead-acid battery having the same electrode area reaches several tens of times that of a lithium secondary battery. Therefore, in a lithium secondary battery, it is necessary to increase the electrode area by several tens of times so that the same current can be taken out. Therefore, it is necessary to pack large-area electrodes compactly in a battery container.

Further, in the conventional method, since the electrode and the separator are separately manufactured and laminated, it is necessary to position the positive electrode and the negative electrode via the separator, which is important in performance, and requires high-precision assembly. If this alignment is neglected, a capacity shortage occurs due to a short reaction area. Further, in the worst case, there is a problem that the contact between the positive electrode and the negative electrode occurs at the ends, and the function as a battery is impaired.

When cells are connected in series in order to obtain a high voltage, the cells connected by current collector rods or connected by spot welding are fixed in the cells.
When a trouble such as an internal short circuit occurs, the battery cannot be protected by disconnecting the external circuit. In the case of a lithium secondary battery, there is a problem that a serious accident may occur due to a high energy density.

Even if there is no trouble, it is conceivable that the electrolyte is decomposed and depleted due to heat generated by charging and discharging. Since a lithium secondary battery is vulnerable to the intrusion of moisture in the air, it is necessary to avoid the need to externally supply an electrolytic solution.

The present invention has been invented in order to solve the problems relating to these lithium secondary batteries.

That is, an object of the present invention is to provide an electrochemical device which can simplify the assembly of a porous body and an electrode and reduce performance defects due to assembly failure, and to provide a flexible electrode suitable therefor. It is another object of the present invention to provide a safe, high-voltage, large-capacity electrochemical device and an assembled battery obtained by combining the same, and a flexible electrode suitable for the device.

[0025]

A first flexible electrode according to the present invention is a soft electrode composed of monomer units A and B shown below, in which a binder is obtained by graft-polymerizing a crystalline fluorocarbon resin with a fluororubber on a binder. A fluororesin is used. _{A: -CH 2 -CF 2 - B} : -CFCl-CF 2 -

Further, the second flexible electrode according to the present invention comprises:
In the first flexible electrode according to the present invention, the ratio of the binder made of the soft fluororesin to the active material is 0.1% by weight or more.
In the range of 20% by weight, and when preparing the electrode, it is dispersed in 5 to 30 parts by weight of a coating solvent with respect to 1 part by weight of the binder.

Further, the first electrochemical device according to the present invention is a device in which the first or second flexible electrode according to the present invention is opposed with a porous body holding an ion conductive substance interposed therebetween. is there.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The flexible electrode of the present invention is a non-aqueous electrolyte battery electrode comprising a binder and an active material, and a positive electrode and a negative electrode are opposed to and integrated with a porous body (separator) therebetween. It relates to an electrochemical element. When the above-mentioned electrode-separator integrated body is wound or folded to secure a large-area electrode with a compact structure, the electrode-separator plays a role of giving flexibility. The battery sheet thus obtained is rolled up as it is and inserted into a cylindrical can to obtain a cylindrical battery. When the sheets are stacked in a strip shape and inserted into a square can, a square battery can be obtained. Then, the obtained battery undergoes the same battery reaction as the battery according to the conventional method. A plurality of these batteries may be connected to form a battery pack. Hereinafter, embodiments of the present invention will be described with reference to the drawings.

Embodiment 1 FIG. 1 is a perspective view showing a battery sheet according to Embodiment 1 of the present invention. In the figure, 51 is a current collector network with tabs, 52 is a positive electrode active material layer, 53
Is a current collecting copper foil, 55 is a negative electrode active material layer, and 3 is a separator. The separator 3 is a positive electrode active material paste adjusted to a composition of 87 wt% of lithium cobaltate, 8 wt% of graphite powder (KS-6 manufactured by LONZA), and 5 wt% of a binder (polyvinylidene fluoride). In this case, a porous polyethylene film (Thickness: 50 μm) was adjusted to a thickness of 200 μm by a doctor blade method and applied. Next, the negative electrode active material paste adjusted to 95 wt% of mesophase microbead carbon (manufactured by Osaka Gas) and 5 wt% of a binder (polyvinylidene fluoride) was similarly applied to the back surface to a thickness of 200 μm by a doctor blade method. In addition, the positive electrode and the negative electrode active material paste were applied narrower than the width of the porous polyethylene film 3 except for the edge. After drying, the battery sheet is folded in the longitudinal direction of the sheet so as to sandwich the current collector network 51 with tabs, in this case, a stainless steel net with tabs for current collection, with the positive electrode surface of the battery sheet inside, and a copper foil 53 for current collector outside. (Thickness: 20 μm), the entire thickness was adjusted to 150 μm by roller pressing, and the battery sheet shown in FIG. 1 was prepared. In the battery manufactured in this manner, in the charging reaction, electrons are emitted from the positive electrode active material to an external circuit, and at the same time, lithium ions are dissolved in the electrolyte. On the other hand, at the negative electrode, carbon absorbs lithium ions from the electrolyte at the same time as receiving electrons from the external circuit. The discharge reaction proceeds in the opposite direction to the charge.

The produced battery sheet was wound around a copper bobbin, inserted into a stainless steel can, and a stainless steel tab was welded to the positive electrode terminal. Then, lithium perchlorate was dissolved in a mixed solvent consisting of ethylene carbonate, dimethoxyethane and benzene. The electrolytic solution was injected and sealed.

In the above steps, 500 batteries were continuously formed, but none of them failed due to an internal short circuit. In the present invention, the positive electrode is formed on one surface of the separator 3 and the negative electrode is formed on the other surface. Unlike the case where the separator 3 is separately manufactured and laminated, it is not necessary to position the positive electrode and the negative electrode via the separator. The battery could be manufactured without causing a defect due to an internal short circuit even when assembled without the battery. Also, since the number of parts is reduced, the assembling process can be simplified, and the device can be easily created. Also, in the battery of the present invention, both the positive electrode and the negative electrode are formed on the separator with a smaller width than the width of the separator, and when wound up, even if the end faces are shifted, both the positive electrode and the negative electrode are inside the separator. There was no contact and did not hinder the progress of the battery reaction. In addition, since the positive electrode active material and the negative electrode active material surely face each other via the separator, there was no generation of an active material that did not contribute to the reaction due to electrode displacement, and there was no shortage of battery capacity.

In this embodiment, if both the positive electrode and the negative electrode are formed on the separator with a narrower width than the width of the separator, both the positive electrode and the negative electrode may be formed inside the separator even if the end faces are displaced during winding or lamination. So that they do not contact each other and do not hinder the progress of the battery reaction. In addition, since the positive electrode active material and the negative electrode active material surely face each other via the separator, there is no generation of an active material that does not contribute to the reaction due to electrode misalignment, and as a result, there is no shortage of battery capacity.

A positive electrode active material layer and a negative electrode active material layer can be easily formed on a separator by coating a paste containing an electrochemically active material on one side and the other side of the porous body.

Even in the case of a high-viscosity material or a solid ionic conductive material such as a polymer electrolyte which is difficult to be retained on the porous separator after the formation of the active material layer, the porous separator must be preliminarily applied to the porous separator. It can be applied by holding a conductive substance.

Embodiment 2 FIG. 2 is a perspective view showing a battery sheet according to Embodiment 2 of the present invention, and 54 is a tab-collected copper foil with a tab. Lithium cobaltate 87wt
%, Graphite powder (KS-6 manufactured by Lonza) 8 wt%, and a binder (polyvinylidene fluoride) 5 wt% of a positive electrode active material paste adjusted on a porous polyethylene film (thickness 50 μm) of the separator 3 by a doctor blade method. ,
The thickness was adjusted to 200 μm and applied. Next, it is inverted, and on the back surface, 95 wt% of mesophase microbead carbon (manufactured by Osaka Gas) and a binder (polyvinylidene fluoride)
The negative electrode active material paste adjusted to 5 wt% was applied to a thickness of 200 μm by the same doctor blade method. In addition, the positive electrode and the negative electrode active material paste were applied narrower than the width of the porous polyethylene film 3 except for the edge. After drying,
The positive electrode surface of the battery sheet is set inside, the sheet is folded in the longitudinal direction of the sheet so as to sandwich a stainless steel net 51 with a tab for current collection, and a copper foil 53 (20 μm thick) for tabular current with a tab is applied to the outside to roll the roller. The entire thickness was adjusted to 150 μm by pressing to prepare a strip-shaped battery sheet shown in FIG.

The prepared strip-shaped battery sheets are bundled, the positive electrode tabs are welded to each other, and the negative electrode tabs are welded to each other.
After closing the opening except for the electrolyte injection port, an electrolyte in which lithium perchlorate was dissolved in a mixed solvent of ethylene carbonate, dimethoxyethane and benzene was injected, and the injection port was welded and sealed.

In the above steps, 500 batteries were continuously formed. None of the batteries caused a failure due to an internal short circuit. The same effect as in the above embodiment was obtained.

Embodiment 3 Lithium cobaltate 87
The positive electrode active material paste was adjusted to a composition of 8 wt% of graphite powder (KS-6 manufactured by Lonza) and 5 wt% of binder (polyvinylidene fluoride), and lithium perchlorate was dissolved in 70 vol% of the paste and polyethylene oxide. A positive electrode paste in which 30% by volume of the polymer electrolyte mixed well was prepared. Similarly, negative electrode active material paste 70 adjusted to 95 wt% of mesophase microbead carbon (manufactured by Osaka Gas) and 5 wt% of binder (polyvinylidene fluoride)
A negative electrode paste in which the volume% and the polymer electrolyte were well mixed was prepared. A porous polyethylene film (thickness: 50 μm) of the separator 3 in which a polymer electrolyte has been impregnated in advance.
m) was coated with a positive electrode paste to a thickness of 200 μm by a doctor blade method. Then flip it over and on the back,
Negative electrode paste is also doctor blade method with thickness 200
μm. The positive and negative electrode active material pastes are:
Except for the edge of the porous polyethylene film 3, the coating was narrower than its width. After drying, the battery sheet is folded in the longitudinal direction of the sheet so that the positive electrode surface is on the inside, and a stainless steel net 51 with a tab for current collection is sandwiched, and a copper foil 54 with a tab is formed on the outside.
(Thickness: 20 μm), and the entire thickness was adjusted to 150 μm by a roller press to prepare a strip-shaped battery sheet shown in FIG.

The prepared strip-shaped battery sheets are bundled, and the positive electrode tabs and the negative electrode tabs are welded to each other.
Sealed by welding.

In the above steps, 500 batteries were continuously formed, but none of the batteries caused a failure due to an internal short circuit. In addition, the same effect as in the second embodiment was shown.

Comparative Example 87 wt% of lithium cobaltate and 8 wt% of graphite powder (KS-6 manufactured by Lonza) on both sides of an aluminum foil with tabs (20 μm)
% And a binder (polyvinylidene fluoride) having a composition of 5 wt% were formed by a doctor blade method, and dried to obtain a positive electrode having a thickness of 100 μm by a roller press.

Mesophase microbead carbon (manufactured by Osaka Gas) 95 wt.% On both sides of tabbed copper foil (20 μm)
%, And a binder (polyvinylidene fluoride) adjusted to 5 wt%, a negative electrode active material paste was similarly formed by a doctor blade method, and after drying, a negative electrode having a thickness of 100 μm was formed by a roller press.

As shown in the schematic diagram of FIG. 11, a positive electrode 1, a strip-shaped porous polyethylene film (thickness: 25 μm), a negative electrode 2, and a separator 3 are stacked in this order while passing through a stacking guide 58. And inserted into a stainless steel can, and a stainless steel tab was welded to the positive electrode terminal. Then, an electrolytic solution in which lithium perchlorate was dissolved in a mixed solvent consisting of ethylene carbonate, dimethoxyethane and benzene was injected, and sealing treatment was performed. Reference numeral 57 denotes a rolled-up body of the electrode separator.

In the above steps, 500 batteries were continuously formed, and 10 batteries having a defect due to an internal short circuit occurred.

In the first to third embodiments, a battery has been described as an example of an electrochemical element. However, similar effects can be obtained by applying the present invention to a capacitor.

Embodiment 4 FIG. In the third embodiment, in order to realize a high-voltage, high-capacity battery, a flexible electrode using a soft fluororesin as a binder was employed to form a flat battery having a folded electrode structure. In addition, by stacking them, a safe and high-performance battery pack can be easily obtained. Furthermore, a heat release mechanism and a pressure release mechanism are provided, and the gas composition in the battery is made sufficient for carbon dioxide to suppress a pressure rise and enhance safety. In addition, an electrolyte supply mechanism is provided to achieve a longer life.

Embodiment 5 FIG. 3 is a cross-sectional view illustrating an example of a flat lithium secondary battery according to Embodiment 5 of the present invention. A battery element is formed by evenly folding the electrode-separator integrated body having the positive electrode 1 formed on one surface of the separator 3 and the negative electrode 2 formed on the opposite surface of the separator 3, and forming an electrically insulating sealing material 4 around this. Are arranged and sandwiched between two conductive plate members 5 to form a flat unit cell. By doing so, the large electrode area electrode can be compactly packed in the battery container, and a high voltage, large capacity battery can be obtained.
In addition, since the electrode and the separator are formed as an integral body, it can be formed easily with less performance defects. Also,
The flat shape is suitable for forming an assembled battery.

The material of the electrically insulating sealing material and the conductive plate material is not particularly limited, but polypropylene, polyethylene or the like is preferred as the sealing material. Examples of the conductive plate include copper, aluminum, nickel, iron, and stainless steel.

The reason why the number of times the battery element is folded is defined as an even number is that if the number is an odd number, only the positive electrode or the negative electrode is provided on both the front and rear surfaces of the folded battery element. If it is an even number of times, if the back of the battery element is a positive electrode, the surface will always be a negative electrode. Although high assembly accuracy is required for positioning the positive electrode and the negative electrode via the separator, the positive and negative electrodes and the separator may be stacked as separate parts and folded to manufacture a battery element.

Although the number of times of folding is not specified at all, it is preferably about 4 to 16 times in consideration of the complexity of assembly. The width and length of the battery element are determined by the electrode area to be formed and the number of times of folding. Regarding the thickness of the battery element, the thickness of the separator is about 25 to 50 μm, and the thickness of the positive electrode and the negative electrode is 50 to 500 μm.

Embodiment 6 FIG. Next, an easily foldable flexible electrode suitable for the flat lithium secondary battery having the above-mentioned folded electrode structure according to the sixth embodiment of the present invention will be described. A flexible electrode characterized by using a soft fluororesin composed of the following monomer units A and B obtained by graft polymerizing a crystalline fluororesin on a fluororubber as a binder. Further, a binder obtained by adding the above-mentioned fluororesin and one or more kinds of fluororesins as a binder may be used. . _{A: -CH 2 -CF 2 - B} : -CFCl-CF 2 -

Conventionally, such a soft fluororesin has the same performance as that of a fluororesin most frequently used in an electrode for a lithium secondary battery, and has been improved to improve mechanical strength. And Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. 8-206615 discloses a production method and performance thereof. Since such a soft fluororesin is a fluorocopolymer obtained by graft-polymerizing a crystalline fluororesin to a fluororubber, the flexibility of the fluororubber can be improved while maintaining the same performance as a conventional fluororesin. It is a fluororesin that combines. When this soft fluororesin is used as a binder, it is possible to produce a high-performance and highly flexible electrode not available in the conventional binder.

The soft fluororesin can be used not only alone but also by mixing it with another crystalline fluororesin or the like to maintain flexibility while maintaining the properties of the base resin. The resin to be mixed is not particularly limited, but among the fluororesins, polyvinylidene fluoride (PV
It is particularly compatible with dF).

In a flexible electrode using such a binder, if the ratio of the binder to the active material is small, the active material cannot be bonded, resulting in a decrease in battery capacity. It will cause the electrode reaction to be hindered.
Preferably, it is in the range of 1% by weight to 10% by weight.
In addition, in the case of preparing by dispersing in a coating solvent in preparing the electrode, from the viewpoint of the hardness of the paste at the time of coating,
The ratio of the coating solvent to 1 part by weight of the binder is 5 to 30.
It is desirable that the amount be part by weight, preferably 8 to 20 parts by weight. As an example of a manufacturing method, there is a method in which the binder is dissolved in a coating solvent to prepare a binder solution, and an active material or the like dispersed in the solution is formed on a substrate or an electrode current collector.

For example, 33 parts by weight of an N-methylpyrrolidone (NMP) solution as a coating solvent and a soft fluororesin (Cefral Soft: Central Glass) as a binder
3 parts by weight were dissolved to form a binder solution, and 58 parts by weight of LiCoO2 powder as a positive electrode active material and 6 parts by weight of graphite powder as a conductive agent were dispersed in this solution to prepare a coating solution. The liquid is collected to a thickness of 20
An electrode sheet according to one embodiment of the flexible electrode of the present invention having a thickness of about 300 μm was obtained by applying a coating having a width of 30 cm on an aluminum foil having a thickness of 30 μm and drying. This sheet is about 80 × 10
The sample was cut out into mm and used as a test sample.

Using the prepared sample, the tensile strength and the elongation strain were measured by a tensile strength measuring device, and the mechanical strength was evaluated. The result is shown by the characteristic curve a in the characteristic diagram of FIG.
Shown in The vertical axis represents load, and the horizontal axis represents elongation. Also, the evaluation result of the electrode sheet (conventional example) similarly prepared except that the binder was changed to PVdF is similarly shown in a characteristic curve c of FIG. A characteristic curve b in FIG. 4 shows another electrode sheet evaluation result similarly prepared except that the binder was changed to a mixed powder (1: 1) of PVdF and a soft fluororesin.

FIG. 4 shows a non-aqueous electrolyte battery electrode.
With respect to an electrode to which an electrode active material or the like is adhered by a binder, by using a soft fluororesin obtained by graft-polymerizing a crystalline fluororesin to a fluororubber as a binder, an electrode flexibility that cannot be obtained with a conventional binder is obtained. Indicates that you can now.

The solvent is not particularly limited as long as it can dissolve the binder. Examples of the solvent include N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF) and the like. Although the active material is not particularly limited, examples thereof include carbon materials such as graphite, glassy carbon, carbon black, coke, pyrolytic carbon, and carbon fiber, TiS2, MoS2, and MnO.
2, V2O5, V6O13, LiCoO2, LiNiO2, Li
Inorganic compounds such as Mn2O4 are listed. Examples of the current collector include foils such as copper, aluminum, nickel, iron, and stainless steel, meshes, and expanded metals.

When the electrode prepared as described above using the binder is used in a non-aqueous electrolyte battery, it can be used also as a negative electrode or a positive electrode. The electrolyte or electrolyte of such a battery is not particularly limited. Instead, the same thing as the conventional one can be used.

As described above, in the electrode in which the powdered active material is bound by the binder, not only the performance but also the mechanical properties are often influenced by the performance of the binder. Therefore, in the present invention, by paying attention to the binder for bonding the active material and the like, a flexible electrode excellent in processability is produced by finding a binder excellent in mechanical strength without affecting the battery performance. Indicates that you can do it.

By applying the above binder to a binder for bonding an active material in an electrode for a non-aqueous electrolyte battery, it is possible to obtain electrode flexibility that cannot be obtained with a conventional binder. By using the electrode manufactured in this manner, it is easy to manufacture a folded electrode or a wound electrode in a large electrode area, and a useful result for improving battery performance is brought.

Embodiment 7 The battery pack according to Embodiment 7 of the present invention is formed by stacking the above-mentioned flat lithium secondary batteries in order to obtain a high voltage. At this time, the flat batteries are fixed to each other by applying a surface pressure in the stacking direction and are electrically connected to each other, but this connection is configured to be cut off by relaxing the surface pressure.

FIG. 5 is a schematic diagram showing an example of an assembled battery according to Embodiment 7 of the present invention. As shown in FIG. 5, a spring 12 is inserted between the stacked flat batteries 11 shown in FIG. When surface pressure is applied by the tightening rod 13,
The spring 12 contracts, and the electrical connection between the flat batteries 11 is maintained. It is necessary to loosen the surface pressure to cut off the electrical connection of the flat battery 11 when a short circuit occurs inside the assembled battery. In this case, a current several times to several tens times that of a normal current flows, so that abnormal heat generation occurs and the battery temperature rises rapidly. At the same time, the pressure inside the unit cell, which is abnormally heated, also rises rapidly. Detecting these sudden changes in temperature and pressure, the tightening rod 13
The flat battery 1 with the restoring force of the spring 12
The gap between the two is empty, and the electrical connection can be cut off.
Therefore, the battery can be protected.

For example, if the uncut portion 14 which is a part of the tightening rod 13 is made of a material which is blown off by the ambient temperature, when the temperature around the tightening rod abnormally rises, the tightening rod breaks and the surface pressure can be reduced. Tightening rod 13
The ambient temperature at which the cut-off portion 14 is blown is set at a temperature exceeding the normal temperature of the battery.
It is preferable to cut off at the above. As a material that melts at such a temperature, a so-called wood alloy (melting range of 60 ° C.) is used.
(.About.72.degree. C.).

Embodiment 8 FIG. In the seventh embodiment, the surface pressure is relaxed by fusing off the cut-off portion 14 of the tightening rod 13. However, a part of the tightening rod 13 is made thinner, or the tensile strength is changed by changing the material. By forming a weak portion, the tightening rod may be broken by an increase in surface pressure due to a sudden increase in abnormal internal pressure of the battery, and the surface pressure may be reduced. It is desirable that the internal pressure of the unit cell does not exceed 1 MPa as the surface pressure at which the fastening rod cuts, and therefore it is preferable to cut at 0.8 to 0.9 MPa.

Embodiment 9 Further, the surface pressure can be relaxed against a sudden temperature rise or a pressure rise by a method other than a method of destructively relaxing the surface pressure such that the clamping rod is broken. That is, a part of the tightening rod is connected with an electromagnet, a temperature sensor and a strain gauge attached to the battery, for example, a temperature sensor such as a thermocouple or a strain gauge detects temperature rise and pressure rise, and a signal current is supplied to the electromagnet to connect the tightening rod. Is to solve. The temperature at which the connection of the clamping rod is cut off is about 60 ° C or more,
The pressure is desirably about 0.8 to 0.9 MPa.

Embodiment 10 FIG. Embodiment 9
Is shown in which the spring 12 is inserted between the flat batteries 11, but the flat batteries may be formed in a leaf spring shape, and this may be used. Is empty, and the electrical connection can be quickly established. A similar effect is achieved.

Embodiment 11 FIG. Heat generation inside the battery is determined by the current flowing during charging or discharging and the internal resistance of the battery. The current flowing varies depending on the use of the battery, and the internal resistance of the battery is not always constant. However, in the case of a lithium secondary battery, on average, the ratio of the electric energy required for charging to the electric energy obtained by discharging, that is, the charging / discharging energy efficiency is about 80% or more. 20%. However, the energy per 1 kg of the battery, that is, the weight energy density is as high as about 120 W / kg. Therefore, when the specific heat of the battery is 0.8, the battery temperature increases by 0.12 ° C. per second, and in the adiabatic state, 7.2 ° C for 1 minute charge / discharge
Also rises. A small cell has a relatively large surface area and is cooled by natural heat radiation from the surface. However, a large battery is difficult only by natural heat radiation from the surface. Also,
In an assembled battery, it is difficult to lower the temperature of the battery disposed inside the assembled battery only by natural heat radiation from the surface of the assembled battery even in a combination of small batteries.

In the large battery according to the eleventh embodiment of the present invention, the heat dissipating mechanism composed of, for example, a set of heat dissipating fins and pins is provided on the outer peripheral portion of the folded electrode or the wound electrode in the large electrode area. Is provided so that heat generated by charging and discharging can be quickly removed. Excessive rise in battery temperature is prevented.

Embodiment 12 FIG. FIG. 6 is a schematic diagram showing an example of a battery pack according to Embodiment 12 of the present invention. As shown in FIG. 6, a heat radiation mechanism 21 for removing heat generated inside the battery is provided on the outer peripheral portion of the battery pack, so that an excessive rise in battery temperature can be reduced. Heat dissipation mechanism 21
Is similar to a general heat exchanger so-called radiator.

Embodiment 13 FIG. FIG. 7 is a partially enlarged schematic view showing an example of an assembled battery according to Embodiment 13 of the present invention, in which a heat collecting plate 31 for effectively removing heat at the center of the battery is attached to the unit cell 11. For example, as shown in FIG.
When the cell 11 is a flat battery, the heat collecting plate 31 is
The layers are stacked so as to enter between the two. The heat collecting plate 31 is connected to the heat radiating mechanism 21 via the electric insulating layer 32.
The reason why the electric insulating layer 32 is provided is to prevent an internal short circuit between the unit cells 11 in the assembled battery. Of course heat collecting plate 31
It is an unnecessary layer when it has electrical insulation. However, a material having good thermal conductivity suitable for the heat collecting plate, for example, a material such as carbon, aluminum, or copper generally has good electric conductivity. For the electrical insulating layer 32, a metal oxide such as alumina having relatively good thermal conductivity is used.

Embodiment 14 FIG. An example of an electrolyte replenishment mechanism provided in the battery pack to prevent the exhaustion of the electrolyte will be described. The electrolyte replenishment mechanism is a liquid electrolyte reservoir made of a porous body placed in contact with the assembled battery in the battery container, and a liquid guide part made of a porous body having a different liquid absorbing power connecting the electrolyte reservoir and the separator of the unit cell. It is composed of The porous body has a property of sucking a liquid into a hollow portion (pore) therein, for example, like a sponge. On the other hand, some force is required to take out the liquid in the pore. This is because the pore has a cylindrical shape and the entrance radius and the surface tension of the liquid, as well as the liquid absorption power of the pore determined by the contact angle between the liquid and the porous body, which is determined as shown in the following equation . Since the separator and the electrode are porous, in order to absorb spontaneously from the electrolyte reservoir, which is also a porous body, when the electrolyte is insufficient, the absorbing power of the porous body of the reservoir is determined by the absorbing power of the separator and the electrode. Must be set smaller. This is because the liquid in the pore having a strong liquid absorption does not move unless an external force is applied to the pore having a low liquid absorption. The most common method of controlling the liquid absorption is to consider the following equation. Therefore, in the electrolyte replenishment mechanism of the present invention, by adjusting the radius of the pores of the porous body, the liquid absorbing power of the porous body of the reservoir is made smaller than the liquid absorbing power of the porous body of the separator and the electrode,
It prevents electrolyte depletion. Long life. P = 2σ cos θ / r P: Liquid absorption (N / m ² ) σ: Surface tension (N / m) θ: Contact angle (degree) r: Radius (m)

When a plurality of batteries stacked in series are supplied with electrolyte from a common reservoir, in a liquid-junction state where the battery and the reservoir are always connected by the electrolyte, the battery between the stacked batteries transmitted through the liquid-junction part Since a short-circuit current flows and self-discharge of the battery occurs, it is not preferable that there is a liquid junction at all times.

Embodiment 15 FIG. Embodiment 15 of the present invention
In order to solve the above problem, the electrolyte replenishing mechanism of the electrochemical element further reduces the liquid absorbing force of the connecting portion between the reservoir and the separator and the liquid conducting portion as compared with the reservoir, the separator and the electrode. With such a configuration, the liquid guide portion is in a liquid-free state and does not cause a liquid junction unless excessive electrolyte is included. When the electrolyte is insufficient, the electrolyte is replenished, and a decrease in battery efficiency can be prevented. The pore diameter of the separator is desirably less than 1 μm from the viewpoint of preventing internal short circuit. Therefore, the pore diameter of the liquid conducting part is 1 μm
The above is desirable. In this embodiment, the separator is a porous body in which the volume of pores having a pore diameter of less than 1 μm is 50% or more of the total pore volume, and the liquid conducting portion has a pore diameter of 1 μm.
The above-mentioned pores are made of a porous material having a volume of 50% or more of the total pore volume.

The shortage of the electrolyte in the battery is mainly caused by the decomposition of the electrolyte. Decomposition of the electrolyte causes an increase in the internal pressure of the battery.
Since it is considered that the shortage of the electrolyte causes an increase in the internal resistance, it is considered that there is a correlation between the shortage of the electrolyte and the increase of the internal pressure.

When the internal pressure of the battery is applied to the reservoir and the pressure is equal to or greater than the difference between the liquid absorbing power of the connecting portion and the liquid absorbing force of the reservoir, the electrolytic solution is pushed into the connecting portion from the reservoir, and the liquid junction is formed. Is formed. When a liquid junction is formed, the electrolyte is supplied from the reservoir to the separators and the electrodes that are insufficient. When the internal pressure release mechanism operates to lower the internal pressure of the battery, the liquid junction is eliminated again due to the difference in the liquid absorption force between the connection portion and the reservoir.

Embodiment 16 FIG. To prevent the internal pressure of the cell from rising, make the sealing part of the cell permeable to gas, prepare a container for storing and sealing the assembled battery, and prevent moisture from the atmosphere from mixing. However, a valve for adjusting the internal pressure release mechanism so that the pressure in the battery container is not excessively high is attached to the battery container.

A conventional release mechanism is provided with a part destroyed by an increase in internal pressure in a part of the container, and is based on a so-called rupture disk. Since this method is self-destructive, it is difficult to reuse the whole once it works. This is a fatal effect, especially for lithium secondary batteries that do not like the incorporation of moisture from the atmosphere, and should be said to be the ultimate safety device.

On the other hand, there are so-called check valves and relief valves, which operate at a predetermined pressure and stop at a pressure lower than the predetermined pressure to maintain the internal pressure. Its basic structure is to produce a force that antagonizes internal pressure,
For example, a release port is held by a valve body connected to a compressed spring. To release the internal pressure and reduce the pressure to a predetermined pressure or less, it is only necessary to attach such a conventionally known check valve to the container.

However, as described above, in order to operate the electrolyte replenishment mechanism using the increase in the internal pressure of the battery, the internal pressure is released at a certain pressure A, then reduced to a pressure B smaller than the pressure A, and the internal pressure is released. It must end.
Pressure B and pressure A are set so as to sandwich pressure C at which the electrolyte replenishment mechanism starts operating. The pressure A is a safety upper limit pressure. As a relief valve that operates as described above, a valve as shown in the schematic diagram of FIG. 8 was mounted on the battery container.

The operation will be described with reference to FIG. The pressure inside the battery is applied to the valve element 41, and the valve element 41
Are held down by a spring A42 that generates a force corresponding to
The spring A42 is housed in the spring case 43, and is supported by the retaining pin 44 together with the spring case 43. Retaining pin 44
Is interlocked with the valve body 41. The spring case 43 has a pressure B
Is held down by a spring B45 that generates a force corresponding to

When the internal pressure of the battery exceeds the pressure A, the valve element 41 drops, and the internal pressure is released from the release port 46. At the same time valve body 4
When the retaining pin 44 interlocked with 1 comes off, the valve element 41 retracts together with the spring case 43 and compresses the spring B45. When the battery internal pressure decreases and becomes equal to or less than the pressure B, the spring B45 returns,
The valve body 41 is pushed back together with the spring case 43, and the retaining pin 44
Is returned, and the release port 46 is closed again. By acting in this manner, it is possible to prevent the battery internal pressure from rising too much. The pressure A is desirably less than 1 MPa, which does not become a so-called high-pressure gas. The pressure B may be lower than the pressure A, but is so-called atmospheric pressure 0.1MP.
It is desirable to be between a and 0.3 MPa.

Next, a description will be given of suppression of a rise in battery internal pressure. In the case of a lithium secondary battery, the increase in battery internal pressure is the decomposition of an organic solvent that is an electrolyte. The organic solvent is, for example,
The decomposition reaction of propylene carbonate, which is often used as an electrolyte for a lithium secondary battery, is as shown in Chemical formula 1. In this case, propene gas generated when propylene carbonate is decomposed is a source of increasing the pressure in the battery container.

[0084]

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It has been found that the addition of lithium carbonate to the electrolytic solution has the effect of suppressing the generation of gas, and this was achieved. In a lithium secondary battery using an electrolyte obtained by dissolving a lithium salt in an organic solvent, the electrolytic solution was used. By containing lithium carbonate, gas generation due to decomposition of the organic solvent in the electrolytic solution is suppressed. As a result, an excessive increase in the battery internal pressure can be suppressed, and safety is improved. Although the details thereof are not clear, in a closed system such as a battery, it is considered that when a large amount of lithium carbonate, which is a reaction product, exists in the system, equilibrium transfer occurs and the reaction hardly proceeds.

It was also found that when lithium oxide and carbon dioxide gas coexist, the gas generation rate is similarly reduced. Therefore, carbon dioxide was contained in the container for storing the battery, and lithium oxide was contained in the electrolytic solution. As a result, the gas generation rate was able to be reduced, and an increase in the internal pressure of the battery was suppressed. Further, as shown in the characteristic diagram of FIG. 9, the time-dependent change of the battery internal pressure differs depending on the carbon dioxide gas concentration. The vertical axis represents the battery internal pressure, the horizontal axis represents time, and the characteristic curve d represents the carbon dioxide 10
0% battery internal pressure rise curve, characteristic curve e is carbon dioxide 50%
The characteristic curve f of the battery internal pressure rise curve is a battery internal pressure rise curve of carbon dioxide gas 0%. It can be seen that the lower the carbon dioxide gas concentration, the faster the internal pressure of the battery rises. This is because the carbon dioxide gas, lithium oxide and lithium carbonate are in an equilibrium relationship as shown in Chemical formula 2, so that when the carbon dioxide gas concentration is high, lithium carbonate is generated and the same effect as when lithium carbonate is added appears. Conceivable.

[0087]

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Therefore, even when the carbon dioxide gas is sealed in the battery container, lithium carbonate is generated and the decomposition reaction of the electrolytic solution is suppressed, so that an increase in the internal pressure of the battery is suppressed. Therefore, the step of sealing the battery container is performed in a carbon dioxide gas atmosphere, and the surrounding carbon dioxide gas is simultaneously sealed.
Alternatively, the battery container may be hermetically sealed while spraying carbon dioxide gas on the battery parts, and the sprayed carbon dioxide gas may be simultaneously sealed in the container.

Further, as shown in the characteristic diagram of the internal pressure of the battery which was made higher than the constant pressure by the carbon dioxide gas, the battery produced as shown in FIG. The time required to reach pressure is long. This is also due to the effect of suppressing the decomposition of the electrolytic solution by the carbon dioxide gas. In FIG. 10, the vertical axis represents the battery internal pressure, the horizontal axis represents time, a characteristic curve g represents a battery internal pressure rise curve of 0% carbon dioxide gas, and a characteristic curve h represents a battery internal pressure rise curve after decomposition of the positive electrode carbonate. .

In the present specification, the description has been made by taking the decomposition of propylene carbonate as an example. However, the same effect can be obtained for ethylene carbonate that undergoes the same decomposition. Similar effects can be obtained even if lithium carbonate or lithium oxide is not directly added to the electrolytic solution but is contained in components inside the battery such as a negative electrode and a separator.

However, in the case where the positive electrode contains lithium carbonate, it has been found that the internal pressure rises quickly during overcharge. This is because lithium carbonate is decomposed into carbon dioxide and lithium oxide by overcharging. In the present embodiment, by utilizing this, lithium carbonate is added to the positive electrode, and after assembling into a battery, the lithium carbonate is decomposed by intentionally overcharging or heating to decompose the carbonate in the battery container. Generating gas. Thereby, the concentration of carbon dioxide in the battery can be increased without decomposing the electrolytic solution. When the amount of lithium carbonate added to the positive electrode is 1% by weight or less, the addition effect is not substantially observed, and the addition amount is preferably small, and addition of 2% by weight is practically sufficient.
1-2% by weight is suitable. It should be noted that not only lithium carbonate but also other carbonates can provide similar effects.

[0092]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a more specific example will be described. Embodiment 1 FIG. 33 parts by weight of an NMP solution as a coating solvent and 3 parts by weight of a soft fluororesin as a binder are dissolved to form a binder solution.
A coating liquid was prepared by dispersing 58 parts by weight of oO2 powder and 6 parts by weight of graphite powder as a conductive agent. This coating liquid was applied to a 20 μm-thick aluminum foil as a current collector to a width of 30 cm, and dried to prepare an electrode sheet having a thickness of about 300 μm. The length was 151 cm.

As a coating solvent, 33 parts by weight of an NMP solution
Dissolve 3 parts by weight of a soft fluororesin as a binder to form a binder solution, and disperse 62 parts by weight of mesophase microbead carbon (hereinafter abbreviated as MCMB) powder (manufactured by Osaka Gas) and 2 parts by weight of lithium carbonate as a negative electrode active material in this solution. Then, a coating liquid was prepared. This coating solution was applied on a copper foil having a thickness of 20 μm as a current collector, and dried to prepare an electrode sheet having a thickness of about 300 μm. The width of the electrode was 31 cm and the length was 151 cm.

The prepared positive and negative electrodes are arranged such that the active material layers face each other with a porous polypropylene film (thickness: 50 μm) serving as a separator therebetween, and the widthwise positive electrode edge does not protrude beyond the widthwise edge of the negative electrode. Then, the battery element was folded four times in a length direction every 30 cm. The length of the separator was 155 cm. At the start and end of the folding, the separator protruded by about 2 cm from the positive electrode and the negative electrode.

The produced 30 cm square battery element was fitted into two 1.5 mm thick, 5 mm wide polyethylene frames, and a separator protruding from the battery element and a liquid guide portion (FIG. 2) for connecting the separator to the electrolyte reservoir were used. A porous film made of polypropylene (50 μm thick) with a polyethylene frame, sandwiched between two stainless steel plates with a thickness of 0.1 mm, and heat-sealed while pressing the periphery to form a square plate A single cell was prepared.

The polyethylene frame has a width of 3 mm and a depth of 0.5 mm.
Are formed at intervals of 3 mm so as to connect the inside and the outside of the frame, and the separator and the liquid guide portion are sandwiched between the grooves. The heat fusion temperature is desirably set to 135 to 160 ° C. at which polyethylene is fused and polypropylene is not melted. The separator used had a pore volume of about 0.1 μm or less with a pore volume of 50% of the total pore volume. The liquid conducting portion (reservoir connection porous body) used had a pore volume having a pore diameter of about 1 μm or less and 50% of the total pore volume.

Forty flat plate cells were stacked in series, and a brass plate spring was sandwiched between the flat plate cells to form an assembled battery using a hard polyethylene plate as a holding plate. The fastening rod used was an aluminum pipe connected with a wood alloy.

An aluminum plate having a thickness of 1 mm was sandwiched between five unit cells as a heat collecting plate. A heat dissipation mechanism connected to an aluminum heat collecting plate and an alumina layer was provided on two opposing sides of the four outer sides of the battery. The heat radiating mechanism is made of aluminum, and radiating fins having a width of 10 mm and a length of 12 cm are arranged at intervals of 10 mm along a stacking direction of 31 pieces on one side.

On the remaining two sides, an electrolyte reservoir is arranged. The electrolyte reservoir is made of a hard polypropylene case packed with a nonwoven fabric made of polypropylene, and a liquid conducting portion (reservoir connection porous sheet) coming out of each battery.
Is sandwiched.

The assembled battery in which the heat radiating mechanism and the electrolytic solution reservoir are arranged is housed in a stainless steel battery container, and the positive electrode terminal and the negative electrode terminal which are attached to the container lid provided with the pressure control valve via an insulating layer are connected to the assembled battery. After welding out the positive electrode lead and the negative electrode lead, the inlet of the container lid is aligned with the position of the electrolyte reservoir, and the container lid is welded to the battery container.

The whole container is vacuum (-750 mmHg or less)
After that, an electrolyte obtained by dissolving lithium perchlorate at 1 mol / l in a 1: 1 mixed solvent of ethylene carbonate and dimethoxyethane is poured into the liquid inlet. The injection is performed in a dry box in a dry carbon dioxide atmosphere. After the injection is completed, the injection port is welded and sealed.

The battery assembled in this manner was charged to an initial cell voltage of 4.2 V, and then charged to an average cell voltage of 3.2 V.
It operated at 6 V and an average assembled battery voltage of 144 V, and obtained an output of 1.3 kW.

Embodiment 2 FIG. PVd as binder for electrode production
A battery was assembled in the same manner as in Example 1 except that the mixed powder of F and the soft fluororesin (1: 1) was used.

The battery assembled in this manner had an average cell voltage of 3.6 V and an average battery voltage of 14
Operating at 4 V, an output of 1.3 kW was obtained.

Embodiment 3 FIG. Lithium carbonate 3
A battery was assembled in the same manner as in Example 1 except that 3 parts by weight of lithium oxide was used instead of the parts by weight.

The battery assembled in this manner had an average cell voltage of 3.6 V and an average battery voltage of 14 V, as in Example 1.
Operating at 4 V, an output of 1.3 kW was obtained.

Embodiment 4 FIG. A battery was assembled in the same manner as in Example 1, except that the injection was performed in a dry box in a dry air atmosphere while blowing carbon dioxide gas around the injection port when the electrolyte was injected.

The battery assembled in this manner had an average cell voltage of 3.6 V and an average assembled battery voltage of 1 as in the first embodiment.
Operating at 44 V, an output of 1.3 kW was obtained.

Embodiment 5 FIG. NMP solution 33 as a coating solvent
3 parts by weight of a soft fluororesin as a binder are dissolved in parts by weight to form a binder solution. In this solution, 58 parts by weight of LiCoO2 powder as a positive electrode active material, 6 parts by weight of graphite powder as a conductive agent, and 1 part by weight of lithium carbonate are dispersed. To prepare a coating solution. This coating liquid was applied to a 20 μm-thick aluminum foil as a current collector to a width of 30 cm, and dried to prepare an electrode sheet having a thickness of about 300 μm.
The length was 151 cm.

The following steps are performed in the same manner as in Example 1.
After assembling the battery by performing the injection process in a dry box in a dry air atmosphere, perform the initial charge to 4.5 V,
The pressure regulating valve was operated by generating carbon dioxide gas in the battery container, and the inside of the battery container was set to an atmosphere sufficient for carbon dioxide gas.

The battery assembled in this manner had an average cell voltage of 3.6 V and an average assembled battery voltage of 1 as in Example 1.
Operating at 44V, an output of 1.3 kW was obtained.

[0112]

Since the present invention is configured as described above, it has the following effects.

Electrochemically absorbing ions with the binder,
A non-aqueous electrolyte battery electrode made of an active material capable of discharging, and a soft fluororesin composed of the following monomer units A and B obtained by graft-polymerizing a crystalline fluororesin on a fluororubber as a binder. A: —CH ₂ —CF ₂ —B: —CFCl—CF ₂ — A flexible electrode with high performance and high flexibility can be obtained. By using the above-mentioned soft fluororesin as a binder, a flexible electrode having high performance and high flexibility can be obtained, so that the processability is improved and the degree of freedom of the electrode structure is increased. The manufacture of cylindrical spirals and folded electrodes is facilitated.

Also, since the ratio of the binder made of the soft fluororesin to the active material was in the range of 0.1% by weight to 20% by weight, the battery performance was good, and 5 to 30 parts by weight with respect to 1 part by weight of the binder. The coating (electrode preparation) is facilitated because the coating solvent is dispersed in the coating solvent.

Further, since the above-mentioned flexible electrodes are opposed to each other with the porous body holding the ion-conductive substance therebetween to form an electrochemical element, at least one electrode can be bonded to the porous body to prevent displacement. And stable contact can be ensured. Moreover, when the electrode-separator integrated body thus formed is wound or folded to secure a large-area electrode with a compact structure, flexibility can be provided. A plurality of batteries thus obtained can be connected to form a battery pack.

[Brief description of the drawings]

FIG. 1 is a perspective view of a battery sheet according to Embodiment 1 of the present invention.

FIG. 2 is a perspective view of a battery sheet according to Embodiment 2 of the present invention.

FIG. 3 is a sectional view showing a battery according to a fifth embodiment of the present invention.

FIG. 4 is a characteristic diagram showing an elongation percentage of an electrode showing an effect of a flexible electrode according to a sixth embodiment of the present invention.

FIG. 5 is a schematic diagram showing an assembled battery according to Embodiment 7 of the present invention.

FIG. 6 is a schematic diagram showing a battery pack according to Embodiment 12 of the present invention.

FIG. 7 is an enlarged schematic view of a part of a battery pack according to Embodiment 13 of the present invention.

FIG. 8 is a schematic diagram of a pressure control valve of a battery internal pressure release mechanism according to Embodiment 16 of the present invention.

FIG. 9 is a characteristic diagram showing a change over time of a battery internal pressure with respect to a carbon dioxide gas concentration according to a sixteenth embodiment of the present invention.

FIG. 10 is a characteristic diagram showing a change over time in battery internal pressure according to Embodiment 16 of the present invention.

FIG. 11 is a schematic diagram of a battery assembly method in a comparative example according to Embodiment 3 of the present invention.

FIG. 12 is a half sectional side view showing a conventional coin-type battery.

FIG. 13 is an exploded perspective view showing a structure of a conventional clad type lead battery.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Electrically insulating sealing material 5 Conductive plate material 11 Flat cell 12 Spring 13 Tightening rod 14 Cut off part 21 Heat dissipation mechanism 31 Heat collecting plate 32 Electric insulating layer 41 Valve body 42 Spring A 43 Spring case 44 Fastening Pin 45 Spring B 46 Release port 51 Tabbed current collector network 52 Positive electrode active material layer 53 Current collecting copper foil 54 Tabbed current collecting copper foil 55 Negative electrode active material layer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01M 10/40 H01M 10/40 Z (72) Inventor Hisashi Shioda 8-1-1 Honcho Tsukaguchi, Amagasaki City Mitsubishi Electric Corporation Central Research Laboratory (72) Inventor Takashi Nishimura 8-1-1, Tsukaguchi-Honmachi, Amagasaki-shi Mitsubishi Electric Corporation Central Research Laboratory (72) Inventor Shigeru Aihara 8-1-1, Tsukaguchi-Honcho, Amagasaki-shi Mitsubishi Electric Chuo Research Center Inside

Claims (3)

[Claims] An electrode for a non-aqueous electrolyte battery comprising a binder and an active material capable of electrochemically absorbing and discharging ions, wherein the binder is obtained by graft-polymerizing a crystalline fluororesin to a fluororubber. A flexible electrode comprising a soft fluororesin composed of monomer units A and B shown below. _{A: -CH 2 -CF 2 - B} : -CFCl-CF 2 - 2. The ratio of the binder made of a soft fluororesin to the active material is in the range of 0.1% by weight to 20% by weight, and 5 parts per 1 part by weight of the binder is used in preparing an electrode.
2. The flexible electrode according to claim 1, wherein the flexible electrode is dispersed in about 30 parts by weight of a coating solvent. 3. An electrochemical device wherein the flexible electrode according to claim 1 or 2 faces a porous body holding an ion conductive substance.