JPH10223230A - Electrode, lithium secondary battery using the electrode, electric double-layer capacitor, and el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode for a lithium secondary battery which is easily assembled, free from fall-out of electrode material, capable of repeating charging/discharging, and small in capacity degradation by forming an electrode layer of a conductive material, and the binder of straight-chain polymer which is the copolymer of vinylidene fluoride(VDF) and chloride-tri-fluoride ethylene(CTFE). SOLUTION: An electrode layer, including conductive material of positive and negative electrodes and the binder, is formed on a collector to obtain an electrode. The straight-chain polymer of 2×10<4> -1×10<6> in molecular weight of the copolymer of VDF and CTFE is used as the binder. The polymer is diluted using an organic solvent, so as to be of the concentration of 3-30%, and 3-20 pts.wt. of the diluted polymer is preferably used to 100 pts.wt. of the electrode material. When the electrode is applied to a lithium secondary battery, the carbon, lithium metal, its alloy or oxide is used as a negative active material, while the compound or carbon material capable of occluding and discharging the lithium ion is the positive electrode active material, respectively as the conductive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode having good adhesion to a current collector, and a lithium secondary battery, an electric double layer capacitor and the like using the electrode.

[0002]

2. Description of the Related Art Secondary batteries used in notebook personal computers, video cameras and the like are required to have a high energy density and a long charge / discharge cycle life. Conventional secondary batteries include lead-acid batteries, nickel-cadmium batteries,
Nickel-metal hydride batteries and the like have been used, but lithium ion secondary batteries have been proposed or put into practical use as secondary batteries with higher energy density.

For example, Japanese Patent Application Laid-Open No. 63-121260 describes a lithium ion secondary battery using a non-aqueous electrolyte, LiCoO ₂ and / or LiNiO ₂ as a positive electrode, and a carbon material as a negative electrode. ing. This lithium ion secondary battery utilizes an intercalation / deintercalation reaction. Specifically, for example, in the case of a negative electrode, lithium ions or the like enter between layers of the carbon hexagonal mesh surface during charging to receive electrons, and during discharging, lithium between the carbon layers emits electrons and is ionized again. Such a lithium ion secondary battery has a high energy density and a high cycle life, and is excellent in safety because it does not use highly reactive metallic lithium. At present, research and development are under way to achieve higher performance.

An electrode used in a lithium ion secondary battery is manufactured by forming an active material such as a carbon material or an oxide on the surface of a current collector made of a copper foil, an aluminum foil or the like. Specifically, an active material or the like is dispersed in a polymer solution or a polymer dispersion and applied to the surface of a current collector. The polymer for a binder is required to have the following properties.

In the battery assembling process, the coating of the active material does not detach from the current collector and has an adhesive strength that does not cause cracking. The coating does not dissolve in the electrolytic solution. Without detaching from
Must have sufficient bonding strength to prevent cracking, etc.

[0006] In Japanese Patent Application Laid-Open No. 63-121260, polyvinylidene fluoride (PVD) is used as a binder.
F) is used. Incidentally, in order to increase the adhesive strength, it is necessary to add a large amount of PVDF. However, since the binder does not contribute to the battery capacity, using a large amount of the binder decreases the battery capacity. Also, P
Since VDF is dissolved in the non-aqueous solvent of the electrolytic solution, even if it is added in a large amount, there is a problem that repeated charging / discharging causes peeling or cracking of the coating film, thereby reducing the battery capacity.

Further, since PVDF is a crystalline resin, various problems occur in the actual battery manufacturing process. For example, as one of manufacturing processes of a lithium ion secondary battery, there is a process of applying an application solution in which an active material is dispersed in a PVDF solution to a current collector (for example, a copper foil) and drying the same to manufacture an electrode. . In this step, if the drying speed and the like are inappropriate, PV
Since the contraction rate of the DF and the contraction rate of the current collector are significantly different,
The electrode mixture layer is separated from the current collector. Problems such as curling of the electrodes occur even if they do not separate.
In addition, even if there is no problem immediately after coating and drying, the electrode mixture layer may gradually peel off from the current collector with the lapse of time due to internal stress remaining in the electrode.

Various other binders have been used so far. Among them, a preferred example is a crosslinked polymer. In particular, those cross-linked using a polyamine, polyol or peroxide as a cross-linking agent, for example, vinylidene fluoride-6-propylene copolymer (P (VDF-HFP)), vinylidene fluoride-6-propylene fluoride- At least one kind of fluororubber such as tetrafluoroethylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-propylene-vinylidene fluoride copolymer, or perfluoro-based fluororubber is treated with the crosslinking agent. Some are crosslinked. The amount of the crosslinking agent to be added is generally 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the compound to be crosslinked.

A fluorine-containing compound,
Crosslinked by radiation such as β-rays or γ-rays, for example,
At least one of PVDF, P (VDF-HFP), fluorine-containing thermoplastic rubber and the like may be crosslinked by radiation. These are described in, for example, The Chemical Society of Japan No. 4,
P686,1976 and INDUSTRIAL AND ENGINEERING CHEMISTRY, V
OL.49, No. 10, P1687, 1957, and the like.

In addition, PV having a silane compound grafted thereon
There is also a proposal to use DF cross-linked with water. The silane-crosslinked PVDF is described in, for example, JP-A-2-115234.

[0011] Of the above crosslinked polymers, rubber-based crosslinked polymers are considered to be particularly preferred. By using a rubber-based crosslinked polymer, the internal resistance can be reduced, and the performance under heavy load is particularly improved.

It is stated that the crosslinked polymer may be used as a mixture of two or more kinds. Also, in the binder,
In addition to the crosslinked polymer, polymethyl methacrylate (P
Other polymers such as MMA) and polycarbonate (PC) may be included, but these may be 25% of the total binder.
The content is set to not more than about volume%.

Although the above-mentioned crosslinked polymer is preferable as a binder, a new crosslinking step is required for practical use, which has been a problem in the production.

On the other hand, there is an electric double layer capacitor in which the above binder material is used as an electrode material.
Even when used as a polarizable electrode material for an electric double layer capacitor, improvement in the properties of the binder material is desired as in the lithium secondary battery.

Further, as an EL device, a device having a light emitting layer containing a fluorescent material and a binder is known.
The development of a binder material in this case is also desired.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an easy assembling process which does not require a new cross-linking step and the like, prevents the positive electrode material and the negative electrode material from falling off, and is used when charging and discharging are repeated. For a lithium secondary battery or the like with a small capacity reduction, a lithium secondary battery using this electrode,
An object of the present invention is to provide a multilayer capacitor and an EL element.

[0017]

The above object is achieved by the following constitution. (1) An electrode having an electrode layer containing a conductive material and a binder of a linear polymer that is a copolymer of vinylidene fluoride (VDF) and ethylene chloride trifluoride (CTFE). (2) A lithium secondary battery using the electrode of (1) as a positive electrode or a negative electrode. (3) As the conductive material, a carbon material, a lithium metal, a lithium alloy or a lithium oxide material is used as a negative electrode active material, and a compound or a carbon material capable of intercalating / deintercalating lithium ions is used as a positive electrode active material. Rechargeable lithium battery. (4) An electric double layer capacitor using the electrode of (1). (5) An EL element having a light-emitting layer containing a fluorescent material and a binder of a linear polymer that is a copolymer of vinylidene fluoride (VDF) and ethylene chloride trifluoride (CTFE).

[0018]

When a positive electrode / negative electrode active material coating film is formed on a current collector to form an electrode, a linear chain composed of a copolymer of vinylidene fluoride (VDF) and ethylene chloride trifluoride (CTFE) is used. -Like polymer: P (VDF-CTFE) is used as a binder. The crystallinity of this polymer is reduced due to the presence of the CTFE portion, the elastic modulus is reduced and the elongation is improved as compared with PVDF, and the material is softened. For this reason, when used as a binder for an electrode, the shrinkage is small and the adhesiveness to the current collector is good. Further, a contact resistance is reduced, and a lithium secondary battery or the like having a small internal resistance can be manufactured.

The chemical resistance of P (VDF-CTFE) of the present invention is as follows.
Like VDF copolymer main chain / PVDF side chain polymer, P (V
DF-HFP), except for chlorinated solvents.
It is dissolved at room temperature in a limited solvent such as N, N-dimethylformamide, N-methylpyrrolidone. If heated,
It is soluble in ketones and carbonates. In any case, a uniform solution can be obtained by stirring with a magnetic stirrer or the like. As a result, the electrodes can be easily formed.

Also, the electrodes of the electric double layer capacitor and the EL
Even when applied to the light emitting layer of the device, it shows good characteristics,
Shows good durability.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail.

The electrode of the present invention comprises a conductive material and P (VD
An electrode layer containing a linear polymer binder which is F-CTFE) is formed on the current collector. Then, such an electrode is used for a positive electrode or a negative electrode, and a carbon material, a lithium metal, a lithium alloy or an oxide material is used for a negative electrode active material as the conductive material, and lithium ions can be intercalated and deintercalated. By using a compound or a carbon material for the positive electrode active material, a lithium secondary battery with favorable characteristics can be obtained.

The carbon material used as the active material is, for example,
Mesocarbon microbeads (MCMB), natural or artificial graphite, resin fired carbon material, carbon black,
What is necessary is just to select suitably from carbon fiber, polyacene, etc.

The compound capable of intercalating / deintercalating lithium ions is preferably a compound oxide containing lithium. For example, LiCo _x Ni ₁ -xO
₂ (0 ≦ X ≦ 1), LiMn ₂ O ₄ , LiV ₂ O _{4 and the} like.

In the present invention, the above-mentioned negative electrode active material and / or positive electrode active material, preferably both an active material and the above-mentioned P (V
DF-CTFE) to form a current collector with a linear polymer binder.

P (VD used as a binder in the present invention
F-CTFE) is obtained when VDF: CTFE = 1: 1.
The copolymer is mainly an alternating copolymer, but a copolymer having any other composition can also be synthesized. P (VDF-CTF of the present invention)
The CTFE molar ratio in E) is preferably in the range of 5 to 50%. Further, the molecular weight is required to be 20,000 or more, particularly about 30,000 or more, as Mw in terms of the strength of the material. The upper limit of Mw is 1,000,000
It is about 0. Since this copolymer is essentially low in hygroscopicity (<0.05%), it is not always necessary to carry out a drying treatment at the time of use, but it may be subjected to normal pressure or vacuum drying at 100 ° C. or lower. Such P (VDF-CTFE)
Is sold by Solvay Japan, Ltd. in the 30,000 series under the trade name "31508".

In order to synthesize this polymer, two components, VDF and CTFE, may be copolymerized using a peroxide as a catalyst, like other fluororesins. The copolymer is not dissolved in an electrolyte such as ethylene carbonate or diethyl carbonate at room temperature, and when an electrode containing such a copolymer is used for a lithium secondary battery, an electric double layer capacitor, or the like, Cycle characteristics and storage characteristics are improved.

The electrode using the above polymer may contain a low molecular weight component as a constituent polymer. The molecular weight is 100 to 10,000, particularly 300 to 5,000
The degree is preferred. Such low molecular weight components include P
VDF, ethylene chloride trifluoride (PCTFE), P (V
DF-CTFE), among which PCTFE is commercially available as Daifoil of Daikin Industries, Ltd. having several molecular weights (500 to 1300). These are usually liquids / fluids and P
It easily dissolves in a solution of (VDF-CTFE) and shows high compatibility even after forming an electrode. Since these also have a function as a plasticizer, the mechanical properties of the electrode can be controlled by adding them. Depending on the purpose, the amount of addition is preferably 40% by weight or less, more preferably 5 to 40% by weight, based on the whole polymer. However, the strength of the electrode tends to decrease.

In manufacturing an electrode, first, an electrode material such as a carbon material is dispersed in a polymer solution to prepare a coating solution. The solvent used for the coating solution may be appropriately selected from various solvents in which the polymer can be dissolved. For example, N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like may be used. Can be. The dissolution method is simply by stirring using a magnetic stirrer or the like. The concentration and viscosity of the coating solution may be appropriately determined according to the coating means, but usually, the concentration of the polymer in the solvent is preferably 3 to 30% by weight. The amount of the polymer is preferably about 3 to 20 parts by weight based on 100 parts by weight of the electrode material. For example, if the electrode material is a carbon material,
Carbon material: polymer = 85 to 94: 15 to 6% by weight is preferable. When the amount of the polymer is too small, the adhesiveness becomes insufficient, and when the amount of the polymer is too large, the battery capacity, the capacitor capacity, and the like decrease.

The means for applying the coating liquid to the current collector is not particularly limited, and may be appropriately determined according to the material and shape of the current collector. Generally, a doctor blade method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a metal mask printing method, a gravure coating method, a screen printing method and the like are used. Thereafter, if necessary, a rolling treatment is performed by a flat plate press, a calender roll, or the like.

The current collector may be appropriately selected from ordinary current collectors according to the shape of the device such as a battery and an electric double layer capacitor, the method of arranging the current collector in the case, and the like. Generally, aluminum or the like is used for the positive electrode, copper or the like is used for the negative electrode.
Nickel or the like is used. The current collector may be a foil or a mesh (grid).

A coating solution is applied to the current collector and dried to form a coating film. The thickness of the coating film after drying is 100 to 400 μm
It is preferable to set the degree.

When the electrode of the present invention is used as an electrode of a lithium secondary battery, the electrolyte is prepared by dissolving a lithium-containing electrolyte in a non-aqueous solvent. Examples of the lithium-containing electrolyte include LiClO ₄ , LiBF ₄ , LiPF ₆ ,
LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiA
It may be suitably selected from sF ₆ like. As a non-aqueous solvent,
For example, ethers, ketones, carbonates, and the like can be selected from organic solvents exemplified in JP-A-63-121260.

The charge / discharge cycle life is remarkably improved by using the above polymer binder. When the polymer is not used as a binder of the active material, the polymer gradually dissolves in the electrolytic solution, and thus the battery capacity is gradually reduced by repeated charge and discharge.

Although the structure of the lithium secondary battery using the electrode of the present invention is not particularly limited, it is usually composed of a positive electrode, a negative electrode, and a separator provided as necessary, and is applicable to a sheet type battery or a cylindrical type battery. Is done. The electrolyte is not particularly limited to a liquid electrolyte, and a solid polymer electrolyte or the like may be used. In this case, the P (VDF
-CTFE) may be used.

The electrode of the present invention is also effective for an electric double layer capacitor.

The current collector used for the polarizable electrode may be a conductive rubber such as a conductive butyl rubber or the like, or may be formed by spraying a metal such as aluminum or nickel. A metal mesh may be provided.

For the electric double layer capacitor, an electrolyte solution is used in addition to such a polarizable electrode. As the electrolyte solution, an organic solvent system is preferable. It is also possible to use a polymer electrolyte or the like, and in that case, it is possible to use P (VDF-CTFE) of the present invention as a polymer of the gel electrolyte.

As the electrolyte salt, (C ₂ H ₅ ) ₄ NB
F ₄ , (C ₂ H ₅ ) ₃ CH ₃ NBF ₄ , (C ₂ H ₅ ) ₄ PB
F _4, and the like.

The organic solvent may be any of various known ones. Electrochemically stable non-aqueous solvents such as propylene carbonate, ethylene carbonate, γ-butyrolactone, acetonitrile, N, N-dimethylformamide, Preference is given to 2-dimethoxyethane, sulfolane or nitromethane alone or as a mixture.

The concentration of the electrolyte in such an organic solvent-based electrolyte solution may be 0.1 to 3 mol / l.

The structure of the electric double layer capacitor in which the electrode of the present invention is used is not particularly limited, but usually, a pair of polarizable electrodes is arranged via a separator. An electrolyte solution is impregnated, and an insulating gasket is arranged around the polarizable electrode and the separator. Such an electric double layer capacitor may be any type called a coin type, a sheet type, a cylindrical type, or the like.

In the above example, the case where the electrode of the present invention is used for a lithium secondary battery or an electric double layer capacitor has been described. However, the application is limited to the electrode of such a secondary battery or electric double layer capacitor. Is not
Various changes and improvements are possible. For example, a change to an EL (electroluminescence) element is conceivable. That is, by using the above-mentioned linear polymer of P (VDF-CTFE) as a binder of the rare-earth fluorescent material of the dispersion EL, the electrode surface (hole injection transport layer, electron injection transport layer) can be formed. Has good adhesion and the production cost can be reduced.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. <Example 1> 79 g of N, N-dimethylformamide was mixed with C
TFE ratio: about 15 mol%, molecular weight: Mw = 120,0
P (VDF-CTFE) of 00: 20 g was added, and the mixture was stirred with a magnetic stirrer and dissolved. Next, a high-purity natural graphite NG was added to a kneader (Labo Plastmill manufactured by Toyo Seiki).
7 (manufactured by Kansai Thermochemical) and 19 g of the above solution were added and kneaded for 1 hour. 30 g of this clay-like kneaded material and D
Place MF in a 16g beaker and use a mixer at 1000rpm
and kneaded for 2 hours. The resulting coating solution is applied to a 12 mm square titanium plate (1 mm thick) with a metal mask at 10 mm x 10 m.
m. Also, apply this coating solution to a thickness of 15 μm.
, 45mm wide and 150mm long copper foil 0.8m gap
m using an applicator. These are 150
Vacuum dried at 2 ° C. for 2 hours to remove the solvent. The composition of this electrode is P (VDF-CTFE): graphite = 6: 94 (% by weight). A titanium wire was spot-welded to the titanium plate as a lead to form an electrode. At this time, the thickness of the coating film is 0.
2 to 0.3 mm.

Using this electrode as a working electrode, a charge / discharge test was performed as in the following Examples and Comparative Examples. A lithium plate connected to a titanium wire was used for the counter electrode and the reference electrode, and a 1 M lithium perchlorate dissolved in a mixed solvent of ethylene carbonate: diethyl carbonate (1: 1 by volume) was used as the electrolyte. Was. And 0.25
Charge / discharge was performed at a constant current of mA in the range of 0 to 3 volts vs Li / Li +. FIG. 1 shows a cross-sectional view of a cell for measuring charge / discharge characteristics. 1 is a glass beaker of 100 cm ³ , 2 is a silicon stopper, 3 is a working electrode, 4 is a counter electrode, 5 is a reference electrode, 8 is a Luggin tube, and 9 is an electrolyte.

A so-called grid test was performed as an adhesion test on the copper foil. Specifically, a multi-cross cutter (Model 295) manufactured by Eriksen West Germany was used to make 11 vertical and horizontal cut lines in the coating film, and peeling of the coating film in 100 squares formed. The ratio was checked.

The result of the charge / discharge test was 2 g / g of graphite.
The charge capacity at the cycle is as large as 360 mAh / g,
The capacity deterioration rate represented by the following equation was as small as 0.6%, indicating good battery characteristics.

The capacity deterioration rate = {(discharge capacity at the second cycle) − (discharge capacity at the 30th cycle)} / (discharge capacity at the second cycle) × 100 [%] Also in the adhesion test, peeling was observed. The result was 0, which was a good result.

Comparative Example 1 PVDF as a binder
An electrode was produced in the same manner as in Example 1 except that (KYNAR741, manufactured by Elf Atochem) was used.

As a result, the discharge capacity in the second cycle was 32
At 0 mAh / g, the capacity deterioration rate was as large as 10%. Also in the adhesiveness test, the adhesive strength was low, with 50 peeled out of 100 pieces.

Example 2 P (VDF-CTF in electrode)
An electrode was produced in the same manner as in Example 1, except that the weight percentage of E) was changed to 12 weight%.

As a result, the discharge capacity in the second cycle was 36
The battery capacity was as large as 0 mAh / g and the capacity deterioration rate was as small as 0.5%, indicating good battery characteristics. Also, in the adhesion test, none was peeled off, indicating good adhesion.

Comparative Example 2 PVDF as Binder
An electrode was produced in the same manner as in Example 2 except that (KYNAR741) was used.

As a result, the discharge capacity in the second cycle was 32
At 0 mAh / g, the capacity deterioration rate was as large as 8%. In the adhesion test, 50 pieces peeled off.

<Example 3> P (VDF-C having a CTFE ratio of about 15% and a molecular weight of 120,000 as a binder was used.
Using TFE), a positive electrode using lithium cobalt oxide as a positive electrode active material was produced. Acetylene black (Denka Black HS-100, manufactured by Denki Kagaku Kogyo) was used as a conductive assistant. The composition was lithium cobalt oxide: P (VDF-
CTFE): acetylene black = 82: 9: 9 (% by weight). Except for these points, an electrode was prepared and evaluated in the same manner as in Example 1. Using this electrode as a working electrode and a lithium plate as a counter electrode and a reference electrode, a voltage of 3.0 mA to 4.2 V vs. 0.5 mA was used.
Charge / discharge was performed in the range of Li / Li +.

As a result, the discharge capacity in the second cycle was 15
The battery performance was as large as 0 mAh / g, and the capacity deterioration rate was as small as 0.5%.

Comparative Example 3 PVDF as Binder
A positive electrode was produced in the same manner as in Example 3 except that (KYNAR741) was used.

As a result, the discharge capacity in the second cycle was 10
At 0 mAh / g, the capacity deterioration rate was as large as 8%.

Example 4 The electrode of Example 3 was used as the positive electrode 13, and the electrode of Example 1 was used as the negative electrode 12.
A titanium wire 14 is connected to each of the negative electrodes 12 as an external terminal, and these are connected to a polyethylene separator 15 by using a mixed solvent of ethylene carbonate and diethyl carbonate (1: 1 by volume) in which 1M LiClO ₄ is dissolved as an electrolyte. When the lithium secondary battery was sealed in the battery case 11 together with the liquid 16 as shown in FIG. 2, good battery characteristics were exhibited.

<Example 5> A coating solution of activated carbon powder was obtained in the same manner as in Example 1 and dried to form a sheet. After processing the sheet-shaped electrode material into a tablet having a diameter of 6 mm and a thickness of 0.5 mm, a current collector consisting of a 100 μm aluminum layer was formed on one surface of the tablet by a plasma spraying method to obtain a polarizable electrode. This was used to make a coin-type electric double layer capacitor. Diameter 10 for separator
The polarizable electrodes were opposed to each other through a polypropylene porous membrane having a thickness of 1 mm, and then a 1 mol / l propylene carbonate solution using tetraethylammonium borofluoride as an electrolyte was injected as an electrolyte solution and sealed. This electric double layer capacitor showed good characteristics.

The effects of the present invention are clear from the results of the above examples.

[0062]

As described above, according to the present invention, the production is easy without requiring a new cross-linking step in the assembling step,
Electrodes for lithium secondary batteries, electric double layer capacitors, etc., which can prevent the positive electrode material and the negative electrode material from falling off and have a small capacity reduction upon repeated charge / discharge, lithium secondary batteries using this electrode, and electric An electrochemical device such as a multilayer capacitor can be realized.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a cell for measuring charge and discharge characteristics.

FIG. 2 is a cross-sectional view of a lithium secondary battery that is an example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Beaker 2 Silicon stopper 3 Working electrode 4 Counter electrode 5 Reference electrode 8 Luggin tube 9 Electrolyte 11 Battery case 12 Negative electrode 13 Positive electrode 14 Titanium wire (external terminal) 15 Separator 16 Electrolyte

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuhide Oe 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation

Claims (5)

[Claims] 1. A conductive material, comprising: vinylidene fluoride (VD)
F) An electrode having an electrode layer containing a binder of a linear polymer which is a copolymer of trichloroethylene (CTFE) and ethylene chloride. 2. A lithium secondary battery using the electrode of claim 1 as a positive electrode or a negative electrode. 3. A carbon material, a lithium metal, a lithium alloy or a lithium oxide material as a negative electrode active material, and a compound or a carbon material capable of intercalating / deintercalating lithium ions as a positive electrode active material. Lithium secondary battery used as the material. 4. An electric double-layer capacitor using the electrode according to claim 1. 5. A fluorescent material, comprising: vinylidene fluoride (VD)
F) having an emission layer containing a binder of a linear polymer that is a copolymer of F) and ethylene chloride trifluoride (CTFE);
L element.