WO2006054779A1

WO2006054779A1 - Charge storing rubber and electric double-layer capacitor, and lithium battery employing it

Info

Publication number: WO2006054779A1
Application number: PCT/JP2005/021493
Authority: WO
Inventors: Kazuhiro Tachibana; Tatuo Nishina; Takashi Endo; Tateaki Ogata; Shinsuke Ohki; Yoshiki Tanaka; Takushi Matsushita; Yasuyuki Okamoto; Mami Endo; Tsuyoshi Watanabe
Original assignee: Fukoku Co., Ltd.
Priority date: 2004-11-19
Filing date: 2005-11-17
Publication date: 2006-05-26
Also published as: JP4901189B2; JP2006173583A

Abstract

A charge storing rubber (electrode) principally comprising rubber and not relying upon a current collector for holding the mechanical strength by utilizing the adhesiveness and flexibility of the rubber. Furthermore, an electrode is obtained without using a process for coating on the current collector. (1) The charge storing rubber is produced by dispersing an ion conductive dispersant and an electron conductive dispersant into a rubber support, and (2) the charge storing rubber is produced by distributing pores permeable by an ion conductive liquid uniformly in a rubber support and dispersing an electron conductive dispersant. (3) The charge storing rubber for electrodes is produced by further dispersing a battery active material into the charge storing rubber of (1), and (4) the charge storing rubber for electrodes is produced by dispersing an electron conductive dispersant and a battery active material into a rubber support not containing an ion conductive dispersant. The charge storing rubber is joined to the current collector and used in an electric double-layer capacitor or a lithium battery.

Description

Power storage rubber, electric double layer capacitor and lithium battery using the same

Technical field

The present invention relates to a power storage rubber and an electric double layer capacitor and a lithium battery using the same as an electrode, and more particularly to a technique for making a rubber a power storage rubber that functions as an electrode. Background technology.

Secondary batteries and capacitors are devices that store electricity. Conventionally, secondary batteries are lead-acid batteries (SLI, power, stationary, and portable), nickel-powered Dome battery (open-type pocket type, open-type) As for capacitors, electric double layer capacitors, redox capacitors, etc. have been put into practical use.

In recent years, the performance of mobile electronic devices such as mobile phones and personal digital assistants has largely depended on the performance of chargeable / dischargeable secondary batteries. It is hoped that this will be realized at the same time.

As a secondary battery that meets these demands, a nickel-metal hydride storage battery with an energy density approximately twice that of a nickel-powered domum storage battery was developed. I'm bathing.

This lithium ion battery has a configuration in which a positive electrode and a negative electrode are disposed in a non-aqueous electrolyte solution, and a positive electrode active material or a negative electrode active material is bound to a current collector surface on each electrode plate. is there. The positive and negative electrode plates used in this battery are generally kneaded in a solvent with an active material (positive electrode active material or negative electrode active material), conductive material (electroconductive dispersion material), binder (binder), etc. Dispersed into a mixture, applied to one or both sides of the current collector, dried, and then pressed as necessary, and then slit into a predetermined shape.

Conventionally, polyvinylidene fluoride (PVDF) has been mainly used in this battery as a binder. However, since this is a non-conductive polymer, an increase in the amount of the battery The ratio of the amount of active material at the electrode decreases, and not only the charge / discharge capacity decreases, but also prevents the movement of electrons, increases the internal resistance of the electrode, increases the charge / discharge cycle life of the battery, and the high-load charge / discharge of the battery. There was a problem of deteriorating ability. In addition, the electrodes became hard and brittle, causing electrode peeling and cracking.

In order to solve these problems, a technology has been developed in which rubber is used as a binder for battery electrodes, utilizing the properties of rubber, such as flexibility, adhesion, heat aging resistance, weather resistance, and cold resistance. These techniques (inventions) are well known (for example, see Patent Documents 1 to 4). Similarly, there is an invention that uses rubber as an electrode binder for electric double capacitors (see, for example, Patent Document 5).

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-133275

Patent Document 2: Japanese Patent Laid-Open No. 2000-2 28 1 9 7

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-1 1 0 1 45

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-55493

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-288 782

In these inventions, by using rubber (elastomer, fluororubber, modified acrylic rubber, synthetic rubber latex) as a binder, “the elastomer binder for the electrode is non-rigid and highly malleable, so it deteriorates. In addition, in order to prevent the active material from detaching, it is possible to maintain the contact between the active material particles ”(paragraph [0036] of Patent Document 1),

“Because flexible fluorine rubber is used as the main component of the binder, the flexibility of the positive electrode mixture coating is improved, so that cracking and peeling from the conductive substrate are suppressed. (Patent Document 2, paragraph [00 1 1]), “Because a predetermined amount of a synthetic rubber-based latex adhesive and a thickener is included as a binder, flexibility and smoothness are improved. Can prevent electrode peeling and cracking. ”(Patent Document 4 paragraph)

[0 1 1 2]) However, if the weight ratio of the binder to the active material is large, the battery capacity is not increased due to the presence of a large amount of material in the electrode plate that does not contribute to the battery reaction. (Patent Document 3, paragraph [0 0 1 6]), when forming the positive electrode mixture layer, the viscosity increases significantly, making it difficult to apply to the positive electrode current collector layer (patent (Paragraph [00 2 3] in Reference 4) and the internal resistance of the electrode is likely to increase (paragraph [00 29] in Patent Reference 5). The binder (rubber) is the It can contain only about 10% by mass (Patent Document 1, Claim 23, Patent Document 2, Paragraph [0 0 3 0], Patent Document 3, Claims 1 to 4, Patent Document 4 Claims 1 and 9, and paragraph [0 0 2 9]) of Patent Document 5.

In addition, with the aim of improving the effective utilization rate of electrode active materials and improving the charge / discharge performance when applied to Li batteries (primary batteries and secondary batteries), “collecting powdered or granular electrode active materials An electrode bound to a body, comprising a non-aqueous electrolyte and conductive powder, and an isocyanate compound comprising a polyol compound having two or more hydroxyl groups per molecule having an average molecular weight of 60 to 600 An electrode for a Li battery, wherein the electrode active materials and the electrode active materials and a current collector are bound together by a rubber-like binder subjected to a cross-linking reaction. (See Patent Document 6).

Patent Document 6: Japanese Patent Application Laid-Open No. 11-9 7 0 26

The invention of Patent Document 6 states that “Because the binder has almost no electron conductivity and ionic conductivity, the binder inhibits the oxidation-reduction reaction of the electrode active material. In order to solve the problems in the prior art, such as “Drawing is difficult” (paragraph [0 0 0 3]), “a polymer with a three-dimensional network structure (hereinafter referred to as cross-linked A composition comprising an adhesive rubber-like compound containing a non-aqueous electrolyte solution (hereinafter referred to as a binder electrolyte solution) comprising an organic solvent in which conductive powder and electrolyte are dispersed and dissolved in a polymer). The binder is characterized in that the electrode active materials and the electrode active material and the current collector are bound to each other. "In the binder composition, the binder electrolyte is an ion. Conductivity, conductive powder is responsible for electronic conductivity " , “It has a binding function similar to that of a material used as a conventional binder, and has ionic conductivity and electronic conductivity not found in conventional materials” (paragraph [0 0 0 7]). However, since the organic solvent is applied to the current collector in the process of manufacturing the electrode, the adhesive rubber-like compound is not a support, but an electrolyte (ion-conductive dispersion material), conductive powder (electronic Conductive dispersion material), electrode active material is not dispersed on the support.

Further, Patent Document 6 states that “the mixing ratio of the electrode active material and the binder composition varies depending on the type of the electrode active material used and the required mechanical strength, It is preferable that the binder is about 10 to 50 wt% with respect to the total amount of the electrode active material ”(paragraph [0 0 1 6]). More than conventional Although it is shown that the electrode active material is applied to the current collector and dried, the binder solution is applied onto the film (paragraph [0 0 2 2]) alone does not show that an electrode active material is kneaded with rubber to obtain a molded body mainly composed of a rubber-like binder.

In any case, the above-mentioned conventional lithium battery and electric double layer capacitor employ a coating process in close contact with the current collector, so that the drying process is costly, and the current collector and compound (mixture) It was not possible to sufficiently solve the problems of adhesion to the substrate and separation due to expansion and contraction of the active material accompanying the reaction. In addition, since the current collector was responsible for maintaining the mechanical strength, there was a problem that the amount of active material in the battery could not be increased. In addition, since a flammable organic solvent (organic solvent) is used for application to the current collector, there were problems of safety and environmental pollution. Disclosure of the invention

Problems to be solved by the invention

The present invention is intended to solve the above problems, and by utilizing the adhesion and flexibility of rubber, it is mainly rubber and does not rely on a current collector to maintain mechanical strength. The problem is to obtain a storage rubber (electrode) and to obtain an electrode without using a coating process for the current collector. Means for solving the problem

In the present invention, the following means are adopted in order to solve the above problems.

(1) An electricity storage rubber characterized in that an ion conductive dispersion material and an electron conductive dispersion material are dispersed in a rubber support.

(2) The electricity storage rubber according to (1), wherein the ion conductive dispersion is a solid electrolyte.

(3) A power storage rubber characterized in that pores through which an ion conductive liquid permeates are dispersed in a rubber support and an electron conductive dispersing material is dispersed.

(4) Ion conductive dispersion material, electron conductive dispersion material and battery active material on rubber support It is an electricity storage rubber for electrodes characterized by being dispersed.

(5) The electricity storage rubber for an electrode according to (4), wherein the ion conductive dispersion is a lithium salt which dissolves in an organic solvent of an electrolytic solution and is released into an anion.

(6) An electricity storage rubber for an electrode, characterized in that an electron conductive dispersion material and a battery active material are dispersed in a rubber support that does not contain a ionic conductive dispersion material.

(7) the electronically conductive dispersed material, rubber supports 1 00% by mass relative to 60 to 1 00 mass ^_0/0 dispersed that has an electrode for a power storage rubber of the (6), wherein the is there.

(8) The battery active material according to (6) or (7), wherein the battery active material is dispersed in an amount of 10 to 50% by mass with respect to 100% by mass of a rubber support: ^ 'Λ.

(9) The electricity storage rubber for an electrode according to any one of (6) to (8), wherein pores through which the ion conductive liquid permeates are dispersed in the rubber support.

(10) The rubber support is swelled by an organic solvent, so that the ionic conductive liquid penetrates and an ion path becomes possible.

(8) The electricity storage rubber for an electrode according to any one of (8).

(11) The electrode storage rubber according to (9) or (10), wherein the ion conductive liquid is an electrolytic solution containing an organic solvent and a lithium salt.

(1 2) The above (4) to (11), wherein the electron conductive dispersion material is one or more carbon powders selected from acetylene black, ketjen black, and graphite powder. The electrode storage rubber according to any one of the above.

(1 3) The electricity storage rubber for an electrode according to any one of (4) to (12), wherein the battery active material is a positive electrode active material, and the electrode is a positive electrode.

(14) The electrode storage rubber according to (13), wherein the positive electrode active material is a lithium transition metal composite oxide.

(15) The battery active material for an electrode according to any one of (4) to (12), wherein the battery active material is a negative electrode active material, and the electrode is a negative electrode. .

(16) The electrode storage rubber according to (15) above, wherein the negative electrode active material is a lithium insertion compound.

(17) An electric double layer capacitor, wherein the electric storage rubber according to any one of (1) to (3) is used while being bonded to a current collector. (18) The electric double layer capacitor according to (17), wherein a mass ratio of the current collector to the electricity storage rubber is 1 or less.

(19) A lithium battery characterized by using the electrode storage rubber according to any one of (4) to (16) adhered to a current collector.

(20) The lithium battery according to (19), wherein a mass ratio of the current collector to the electrode storage rubber is 1 or less.

(2 1) The lithium battery according to (19) or (20), wherein the electricity storage rubber for electrodes is vulcanized and bonded to a current collector. The invention's effect

Two or more kinds of electronically conductive dispersing material, ionic conductive dispersing material and battery active material are kneaded and dispersed in rubber, so the rubber has good adhesion and flexibility, so that it can adhere to the current collector. In addition, it has the effect of following the volume change of the active material accompanying charge / discharge. Thereby, rate characteristics and cycle characteristics can be improved.

In addition, since rubber is responsible for mechanical strength, an increase in battery capacity can be expected by increasing the percentage of battery active material and reducing the current collector weight. Similarly, an increase in capacity can be expected for electric double layer capacitors by reducing the current collector weight.

Furthermore, since there is no deterioration due to electrolytes, etc., the electricity storage rubber itself may be recycled. Brief Description of Drawings

FIG. 1 is a diagram schematically showing a conventional battery structure and a battery structure of the rubber main role of the present invention. FIG. 2 is a diagram showing charge / discharge of the storage rubber 5 A / cm ² (1 cyc 1 eg). FIG. 3 is a diagram showing charge / discharge of the storage rubber at 5 μA / cm ² (2 cyc 1 eg). FIG. 4 is a diagram showing charge / discharge 1 μAZcm ² (3 cyc 1 eg) of the storage rubber. FIG. 5 is a diagram (Example 2) showing a cyclic voltammogram (sweep speed 0.1 mV / sec) of the electricity storage rubber (without active material).

Figure 6 shows the cyclic voltammogram (sweep speed 0. FIG. 1 is a diagram (Example 1) showing lm V / sec).

Figure 7 shows the crosscut test.

FIG. 8 is a diagram showing a triode cell fabricated for CV measurement using a storage rubber electrode as a sample electrode.

FIG. 9 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 4.

FIG. 10 is a view showing the results of CV measurement of the electricity storage rubber electrode of Example 5. FIG. 11 shows the results of CV measurement of the electricity storage rubber electrode of Example 6. FIG. 12 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 7. FIG. 13 shows the results of CV measurement of the electricity storage rubber electrode of Example 8. FIG. 14 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 9. FIG. 15 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 10. FIG. 16 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 11; FIG. 17 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 12; FIG. 18 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 13; FIG. 19 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 14; FIG. 20 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 15. FIG. 21 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 16; FIG. 22 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 17; FIG. 23 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 18; FIG. 24 is a diagram showing the results of CV measurement of the electricity storage rubber electrode of Example 19; (Explanation of symbols)

1 Sample electrode 2 Reference electrode '3 Counter electrode 4 Electrolyte Best mode for carrying out the invention

As a result of various studies, the present inventors have discovered that it is possible to construct a battery having excellent rate characteristics and cycle characteristics by utilizing the adhesion and flexibility of rubber. . In addition, unlike conventional batteries, it was discovered that the electrode layer with a rubber support can be expected to increase the capacity of the battery in order to maintain mechanical strength. is there.

In other words, instead of simply using rubber as a binder (binder) and binding battery active materials and conductive assistants as in the past, ion conductive dispersion (solid electrolyte), electronic conductivity Dispersant (conducting aid) and battery active material are uniformly kneaded to form a power storage rubber, or without adding an ion conductive dispersant to the rubber, the electron conductive dispersant and battery active material By uniformly kneading to obtain a power storage rubber, a power storage rubber for an electrode in which these components are uniformly dispersed in a rubber support is obtained (see FIG. 1).

In this case, since the rubber is not a solid solvent but used as a support, it functions not as a solid electrolyte but as a battery electrode (positive electrode or negative electrode) mixture.

In addition, a battery conductive material in which an ion conductive dispersion material and an electron conductive dispersion material are dispersed in a rubber support without dispersing the battery active material, or ion conductivity in the rubber support. The electricity storage rubber, which is a dispersion of the pores through which the liquid penetrates and an electron conductive dispersion material, functions as an electrode of the electric double layer capacitor.

The type of rubber is not limited, and conventionally used rubbers such as synthetic rubbers such as SBR and CR, heat resistant rubbers and elastomers can be used. In particular, ethylene propylene diene rubber (EPDM), attalinoletri ^^ butadiene rubber (H—NBR), and acrylic rubber (ACM) are preferable.

As the ion conductive dispersion material, a lithium salt that dissolves in an organic solvent of an electrolyte solution of a non-aqueous electrolyte battery (lithium ion battery) and dissociates into an anion can be used. For example, C 10, B ioC 1 .0O2 ", B 12C 1 ₁₂ ² ", BF ₄ —, PF ₆ —, A s F ₆ —, S b F ₆ _, BR ₄ —, B (A r) ₄ — , A 1 C ₄ —, CF ₃ SO, (CF ₃ S 0 ₂ ) ₂ N —, and (CF ₃ S 0 ₂ ) ₃ C— containing one or more lithium salts. In particular, L i C 10 ₄ and L i PF ₆ are preferred.

The rubber support L i C 1 0 ₄ and L i PF _e, etc. The well dispersed ionic conductivity of the dispersed material, is immersed in the electrolytic solution for lithium ion batteries, L i by organic solvent of the electrolyte solution C

10 ₄ and L i PF 6 or the like is dissolved, because the rubber support is porous, the electrolyte is easily permeates into the rubber supporting bearing member, to improve the ionic conductivity.

In addition, as an ion conductive dispersing material, oxide ion conductor, halide ion conductor, proton conductor, lithium ion conductor, sodium ion conductor, silver ion conductor ON conductor, copper ion conductor, a— 60 L i S '4 0 S i S ₂ amorphous material, L i ₂ S— S i S ₂ system melt quenched glass, L i ₄ T i ₂ ( P 0 ₄ ) ₃ · A 1 P 0 ₄ · Tio ₂ , P EO (polyethylene oxide), PAN (polyacrylonitrile), PMMA (polymethyl methacrylate), P PO (polypropylene oxide) and other solid electrolytes By using it, a fully solid lithium ion secondary battery that does not use organic electrolyte can be expected. This ion conductive dispersion material can also be used for electric double layer capacitors. By dissolving an ionic conductive dispersion material such as Li C 1 O ₄ or Li PF ₆ dispersed in a rubber support in advance with an organic solvent, the pores into which the ionic conductive liquid permeates are dispersed. Can be obtained. It is preferable that the pores through which the ionic conductive liquid permeates are uniformly dispersed.

In addition, a mixture of an electron-conductive dispersant and a battery active material kneaded with a water-extractable compound that does not function as an ion-conductive dispersant, is placed in hot water, and the compound is added. Also by boiling extraction, it is possible to obtain a power storage rubber in which pores through which ionic conductive liquid permeates are dispersed. In this case, it is not necessary for the rubber to contain an ion conductive dispersing material that dissolves in an organic solvent.

Furthermore, if the rubber is made of a material that swells with an organic solvent, the ion conductive liquid penetrates by swelling and the ion conductive liquid penetrates, so that the ion conductive liquid penetrates. It is not necessary to disperse the pores.

In this case, since it is not necessary to perform the boiling treatment as described above, there is an advantage that the process of manufacturing the electrode can be simplified. Also, a coupling agent can be added to the rubber support as an additive, and an electrode can be produced by vulcanization adhesion to the current collector, and sufficient adhesion can be obtained without using rubber glue.

Examples of the ion conductive liquid that can permeate the electricity storage rubber include an electrolytic solution containing an organic solvent and a lithium salt (electrolyte) conventionally used as a nonaqueous electrolytic solution in a lithium battery.

Examples of such ionic conductive liquids include Li BFC (propylene carbonate), Li BF ₄ / GBL (γ-butyrolacton), Li BF ₄ / PC + DME (1,2-dimethoxetane), L i BF 4 / GB L + DME, L i BF ./PC + EMC (ethyl methyl carbonate), L i BF ₄ / PC + MP (propionic acid meso Chill), L i C 1 O / PC, L i C l O ₄ / GBL, L i C 1 O ₄ / PC + DME, L i C 10 ₄ / PC + DME, L i C 1 O-ZG BL + DME, L i C 1 O ₄ / PC + EMC, L i C 1 O 4 / PC + MP, L i PF ₆ / PC, L i PF ₆ / GBL, L i P Fe / GBL + DME, L i P Fe / PC + EMC, L i PF ₆ / PC + MP, L i PF ₆ / PC + DME, L i A s F ₆ / PC, L i A s F ₆ / GBL, L i A s F e / PC + DME, L i A s F ₆ / GBL + DME, L i A s Fe / PC + EMC, L i A s F ₆ / PC + MP, L i CF 3 S Os / PC, L i CF ₃ SO ₃ / GBL, L i CF 3 S Os / PC + DME, L i CF ₃ S 0 ₃ / GBL + DME, L i CF 3 SO ₃ / PC + EMC, L i CF ₃ S Os / PC + MP, L (— CF ₃ SO ₂ ) ₂ N / PC, L i (CF 3 S O2) 2N / GBL, L i (CF 3 S O2) ₂ N / PC + DME, L i (CF ₃ S O2) 2N / GBL + DME, L i (CF 3 S O2) 2 N / PC + EMC, L i (CF 3 S 0 ₂ ) ₂ NZP C + MP, etc.

As the electron conductive dispersing material, carbon, metal (iron and steel, etc.), alloys, ceramics, glass powder or particles conventionally used as conductive aids for batteries can be used. In particular, at least one carbon powder selected from acetylene black, ketjen black, and graphite powder is preferable. More preferred is a mixture of acetylene black and ketjen black, a mixture of graphite powder and ketjen black.

The electron conductive dispersing material can be dispersed in an amount of 60 to 100 mass% with respect to 100 mass% of the rubber support. If the amount of the electron conductive dispersing material is small, it will not function as a battery, and if it is too large, kneading into rubber becomes difficult, so the above range is preferable.

The battery active material is a positive electrode active material when the storage rubber according to the present invention is used as the positive electrode of the battery, but Li C o 0 ₂ and Li C r O ₂ conventionally used for lithium batteries. , L i N i O ₂ , L i Mn O2, L i Mn ₂ O ₄ , L i V ₂ 0 ₄ , L i F e O ₂ , L i VO ₂ , L i T i 0 ₂ , L i S c Lithium transition metal composite oxides such as O ₂ and Li Y0 ₂ can be used. In particular, Li Mn ₂ O ₄ is preferable.

The battery active material (positive electrode active material) can be dispersed in an amount of 10 to 50% by mass with respect to 100% by mass of the rubber support. If the battery active material is small, it will not function as a battery, and if it is too much, the behavior as a battery will not be seen, so the above range is preferable. As the positive electrode active material, one having an average particle diameter of 10 to 30 m can be used.

The battery active material becomes a negative electrode active material when the power storage rubber of the present invention is used as the negative electrode of the battery. However, synthetic graphite (graphite), natural graphite, and non-graphite that have been conventionally used for lithium batteries. Carbonized, Amorphous cobalt-substituted lithium nitride, Amorphous tin composite oxide, SnO— B ₂ O ₃ — P ₂ 0 ₅ melt-quenched glass, Amorphous S i O ₂ — S n O Lithium insertion materials or compounds such as amorphous amorphous materials can be used.

The electric storage rubber according to any one of (1) to (3) of the present invention (one that does not disperse the battery active material) or the electric storage for electrode according to any one of (4) to (16) The conductive rubber (in which the battery active material is dispersed) can be made into an electric double layer capacitor or battery by adhering to the current collector.

As the current collector, aluminum foil, stainless steel foil or the like can be used, and it can be bonded to the storage rubber by thermocompression bonding and using Z or rubber paste. In that case, it is preferable to use the same kind of rubber paste as that of the rubber support (power storage rubber).

In addition, a coupling agent can be added to the rubber support and vulcanized and bonded to the current collector. For vulcanization adhesion, a method is adopted in which a current collector is placed on an unvulcanized electricity storage rubber, and primary vulcanization is performed by hot pressing, and the rubber is vulcanized and bonded to the current collector at the same time. it can. The hot pressing is preferably performed at 165-175 ° C for 8-12 minutes. In the case of vulcanization bonding, rubber glue may or may not be used. As the coupling agent, a silane force coupling agent is preferable.

When the electricity storage rubber of the present invention is applied to an electric double layer capacitor or a battery, the weight of the current collector can be reduced because the rubber bears the mechanical strength, and the electricity storage rubber (ionic conductive dispersion material, The mass ratio of the current collector to the electron conductive dispersion material (including the mass of the battery active material) can be 1 or less. Example 1

Acrylic-tolyl butadiene rubber (H—NBR) is used as the raw rubber, and 40 wt% ionic conductive dispersion (L i C 10 ₄ ), 90 wt% compared to 100 wt% rubber. Of electron conductive dispersion (acetylene black 80 wt% and ketjen bra 10 wt%), 40 wt% positive electrode active material (L i Mn ₂ O ₄ ), knead in an open gate, and vulcanize at 180 ° C for 10 minutes A power storage rubber sheet was obtained. The electricity storage rubber sheet was cut out into a 1 cm × 1 cm test tube, 1 Om 1 of PC (manufactured by Kishida Chemical Co., Ltd.) was added, and the test tube was covered with a silicon rubber cap. Thereafter, it was treated for 6.0 hours with an ultrasonic cleaner (10:00 W4 2 KHz, yamato 2 5 1 0). This stainless steel foil (S US 3 0 4, two Rako) 1 cm ² area entrapment has the electrolyte and _{(L i C 1 0 4 /} PC + DME) immersed as set by the sample electrode in. Example 2 — —.

Without adding positive electrode active material (L i Mn ₂ 0 ₄ ), rubber (H—NBR) 100 wt%, 40 wt% Li C 10 ₄ , acetylene black 80 wt%, and ket A mixed material of 10 wt% rack was added, kneaded with an open roll, and vulcanized at 180 ° C. for 10 minutes to obtain a power storage rubber sheet. This electricity storage rubber sheet was cut out by 1 cm × 1 cm and treated in the same manner as in Example 1. This stainless steel foil (SU S 3 04, leek co) is 1 cm ² area sandwiched between and the electrolyte solution and _{(L i C 1 0 4 PC} + DME) immersed as set by the sample electrode. A charge / discharge test was performed using the sample electrodes obtained in Example 1 and Example 2. The reference electrode was Li / Li ⁺ , and the counter electrode was metallic lithium. The current density was 5 A / cm ² and 1 μA / cm ² , and the cut-off potential was 2.8 to 4.4 V (vs L i no L i ⁺ ).

Figure 2 shows the charge / discharge of the storage rubber at 5 μA / cm ² (1 cyc 1 e).

X-axis time (s), Y-axis potential (V), and charge / discharge of sample electrode (with active material) in Example 1 0 seconds 3.2 2.3 V, 10 seconds 4.2 V, 20 seconds 4. 2 8 V, 30 seconds 4. 3 3 V, 40 seconds 4. 3 7 V, 50 seconds 4. 4 V, 60 seconds 3. 2 2 V, 70 seconds 2. 8 2 V, 7 2 seconds 2.8 V. 0 second for charge / discharge of sample electrode (no active material) in Example 2. 3. 16 V, 10 seconds 4. 25 V, 20 seconds 4. 34 V, 30 seconds 4.4 V, 40 Sec 3.1 2 V, 4 8 sec 2.8 V.

Figure 3 shows the charge / discharge of the storage rubber at 5 μA / cm ² (2 cyc 1 eg).

Similarly, charge / discharge of the sample electrode (with active material) in Example 1 is 0 seconds 3. 15 V, 10 seconds 4. 1 7 V, 20 seconds 4. 35 V, 30 seconds 3. 8 V, 4 8 seconds 2.8 V. Charge / discharge of the sample electrode of Example 2 (without active material) 0 seconds 3. 1 3, 1 0 seconds 4. 2 2 V, 2 0 seconds 3. 8 5 V, 3 0 seconds 3.3 2 V, 4 It was 0 seconds 2. 8 2 V, 4 2 seconds 2.8 V.

Figure 4 shows the charge and discharge of the storage rubber 1 μ μcm ² (3 cyc 1 eg).

Similarly, charge / discharge of the sample electrode (with active material) of Example 1 is 0 second 3. 12 V, 20 seconds 3. 6 6 V, 60 seconds 3. 8 9 V, 24 0 seconds 4.2 3 V, 5 20 seconds 4.3 V, 1 2 60 seconds 4.4 V, 1 2 70 seconds 3.93 V, 1 2 80 seconds 3.66 8 V, 1 300 seconds 3. 4 2 V, 1 3 2 0 seconds 3. 2 8 V, 1 3 5 0 seconds 3. 1 0 V, 1 4 8 0 seconds 2.8 V. In charge and discharge of the sample electrode (without active material) in Example 2 0 seconds 3. 1 2 V, .5 seconds 3. 4 2 V, 1 0 seconds 3. 6 V, 3 0 seconds 3. 8 8 V, 7 0 sec 4. IV, 24 0 sec 4. 2 7 V, 7 80 sec 4. 3 9, 8 8 2 sec 4. 4 V, 8 9 2 3. 9 V, 9 0 2 sec 3. 74 V 94 2 seconds 3.4 V, 9 8 2 seconds 3. 2 V, 1 1 1 2 seconds 2. 9 1 V, 1 2 7 2 seconds 2.8 V.

FIG. 5 shows the cyclic voltammogram (sweep speed 0. l mVZ sec) of the electricity storage rubber (without active material) of Example 2. When the potential is 3 V, the current is 1 from 0 ^ A.

4 μA, 3.5 is -0.1 8 and 0, 4 is 0 and 0.1 μΑ, 4-

At 5 V, they were 0 · 3 μΑ and 1 μΑ, and at 4.6 V, they were 1.4 Α.

FIG. 6 shows the cyclic voltammogram (sweep speed 0. l mVZ sec) of the electricity storage rubber (with active material) of Example 1. 3. From 1 I V to 4.0 4 V, the current was 0 μA, for 4.4 · 4 V, 0 Ι μ Α and 0.5 Α, and for 4.6 V, 0.8 Α. From these results, it is considered that the electricity storage rubber of the present invention has battery characteristics and operates as a battery electrode. Example 3

Using rubber (H—NB R) kneaded with N a C 1, active material (L i Mn ₂ 0 ₄ ) and electron conductive dispersion (acetylene black and ketjen black) force rubber 1 0 0 wt %, Li Mn 2 O 4: 40 wt%, acetylene black (hereinafter abbreviated as AB) and ketjen black (hereinafter abbreviated as KB): 9 0 wt% (ratio of AB 8 0 · KBIO) In addition to adding a silane coupling agent, The mixture was kneaded in a roll and subjected to primary vulcanization at 180 ° C for 5 minutes. Then, NaC1 was boiled and extracted at 100 ° C. By this treatment, a power storage rubber sheet was obtained in which the pores through which the ion conductive liquid permeated the rubber support were uniformly dispersed, and acetylene black and Li Mn ₂ O ₄ were dispersed. This electricity storage rubber sheet was bonded by crimping at 80 ° C. for 30 minutes to an aluminum foil that had been subjected to alkaline degreasing and coated with rubber paste. Thereafter, secondary vulcanization was performed in an oven at 150 ° C for 1 hour to obtain a sample.

A cross force test was conducted to examine the adhesion between the sample and the aluminum foil. A 1 cm square was cut into 1 mm width and 1 mm width, and a cellophane tape (N I CH I BAN: trade name, manufactured by Nichiban) was applied and tested (see Fig. 7).

As a result of performing a cross-cut test on the sample of Example 3, the rubber remaining amount after the test was 100%. Therefore, in general, it was confirmed that it has sufficient adhesion to an aluminum material that is preferable as a current collector because of its characteristics. That is, in the present invention, it is possible to follow the deformation of the current collector, so that sufficient adhesion can be ensured, a peeling problem hardly occurs, and a flexible electrode can be obtained. Example 4

H—NBR is used as the raw rubber, and the active material (L i Mn ₂ 0 ₄ ) and electron-conducting dispersive material (acetylene black and ketjen black) force rubber 1 00 wt%, L i Μη: 40 wt%, AB and K ：: 90 wt% (AB 80 · KB 10 ratio) Add silane coupling agent and knead with open roll to make unvulcanized rubber sheet 1 Primary vulcanization was carried out by hot pressing at 70 ° for 1 minute. This electrical storage rubber sheet was baked on aluminum foil that had been subjected to alkaline degreasing and coated with rubber paste in an oven at 1 80 ° C. After that, the samples were bonded by thermocompression bonding, followed by secondary vulcanization in an oven at 150 ° C. for 1 hour to obtain a sample.

A sample was obtained in the same manner as in Example 4 except that EPDM was used as the raw rubber. Example 6

Graphite powder (hereinafter abbreviated as G) is used instead of AB as the electron conductive dispersion material, so that G and KB: 75 wt% (ratio of G 55 · KB 20) A sample was obtained in the same manner as Example 4 except for kneading. Example 7

A sample was obtained in the same manner as in Example 6 except that EPDM was used as the raw rubber. Example 8

A method of vulcanization and adhesion without thermocompression bonding as an adhesion method, that is, by placing an aluminum foil that has been subjected to alkali degreasing on an unvulcanized rubber sheet and hot pressing at 170 ° C for 10 minutes A sample was obtained in the same manner as in Example 7 except that the primary vulcanization was performed and the method of adhering to the aluminum foil at the same time as vulcanizing the rubber was adopted. Example 9

For using H- NBR as a raw material rubber, by pulverizing i Mn ₂ 〇 ₄ as an active material that was used was the average particle diameter 2 m, when the wearing vulcanization, the rubber cement in aluminum foil A sample was obtained in the same manner as in Example 8 except that it was applied. Example 1 0

A sample was obtained in the same manner as in Example 9 except that EPDM was used as the raw rubber. Example 1 1

A sample was obtained in the same manner as in Example 8 except that Li Mn ₂ O ₄ was used as the active material and the average particle size was 2 / im. Example 1 2 Adhesion method is vulcanization adhesion without thermocompression bonding, that is, primary vulcanization is carried out by placing alkali degreased aluminum foil on unvulcanized rubber sheet and heat pressing at 70 ° C for 10 minutes. A sample was obtained in the same manner as in Example 5 except that a method was employed in which the rubber was vulcanized and the method of adhering to the aluminum foil at the same time was adopted. Example 1 3

A sample was obtained in the same manner as in Example 12 except that a rubber paste was applied to the aluminum foil during vulcanization adhesion. Example 14

A sample was obtained in the same manner as in Example 12 except that Li Mn ₂₀ ₄ was pulverized to an average particle size of 2 μm as the active material. Example 15

A sample was obtained in the same manner as in Example 13 except that i Mn ₂ 0 was pulverized to an average particle size of 2 μm as the active material. Example 16

Adhesion method is vulcanization adhesion without thermocompression bonding, that is, primary vulcanization is carried out by placing alkali degreased aluminum foil on unvulcanized rubber sheet and heat pressing at 70 ° C for 10 minutes. A sample was obtained in the same manner as in Example 4 except that a method was used in which the rubber was vulcanized and the method of adhering to the aluminum foil at the same time was adopted. Example 1 7

A sample was obtained in the same manner as in Example 16 except that 100% by weight of rubber was added so that Li Mn ₂ O ₄ : 50 wt%. Example 18

Added to 100 wt% of rubber so that L i Mn ₂ 0 ₄ : 10 wt% A sample was obtained in the same manner as in Example 16 except that. Example 1 9

A sample was obtained in the same manner as in Example 16 except that it was added so that AB and KB were 70 wt% (ratio of AB 60 · KB 10) with respect to 100 wt% of rubber.

(Comparative Example 1)

A sample was obtained in the same manner as in Example 16 except that 100 wt% of rubber was added so that AB and KB were 50 wt% (ratio of AB 45 · KB 5). Table 1 summarizes the materials and manufacturing methods of the samples prepared in Examples 1 to 19 and Comparative Example 1. table 1

Examples 4 to 19 and samples prepared in Comparative Example 1 (electric storage rubber electrode) were used as sample electrodes, and a tripolar cell as shown in FIG. 8 was prepared and CV measurement was performed.

Set the sample electrode (1) so that it is immersed in an electrolyte solution of 1.5 cm ² , use metallic lithium as the reference electrode (2) and the counter electrode (3), and 1 mL as the electrolyte solution (4). i BF «, PC + DME (1: 1) was used.

(Measurement condition)

Sweep speed: 0.1 mV / s e c

Sweep range: 2.8 V or 3.0 V to 4.4 V (changed according to natural potential)

Figures 9 to 24 show the results of CV measurements performed on samples prepared in Examples 4 to 19 as described above.

From the data shown in FIGS. 9 to 21, it is considered that the electricity storage rubber of the present invention has battery characteristics and is operating as a battery electrode.

In addition, from the data shown in FIG. 22 (using the sample of Example 17) and FIG. 23 (using the sample of Example 18), the content of the electrode active material is 50 mass. / ₀ and even if many, were found to function as an electrode even if 1 0 wt% and less, 40 wt

% Is preferable because the electrode capacity increases as shown in FIG. 21 (using the sample of Example 16).

The content of the electron conductive dispersant (conducting aid) is 70 mass as shown in Figure 24 (using the sample of Example 19). Even when the amount was reduced to ₀ , the manganese peak could be confirmed, indicating that it functions as a battery. When the content of the conductive additive was 50% by mass (Comparative Example 1), no behavior as a battery was observed. Industrial applicability

Since the electricity storage rubber of the present invention functions as a capacitor and a battery electrode, it can be used for electric double layer capacitors, lithium batteries and the like.

Claims

The scope of the claims

1. An electricity storage rubber characterized in that an ion conductive dispersion material and an electron conductive dispersion material are dispersed in a rubber support.

2. The electricity storage rubber according to claim 1, wherein the ion conductive dispersion is a solid electrolyte.

3. A power storage rubber characterized in that pores through which an ion conductive liquid permeates into a rubber support are dispersed and an electron conductive dispersion material is dispersed.

4. An electricity storage rubber for an electrode, characterized in that an ion conductive dispersion material, an electron conductive dispersion material and a battery active material are dispersed on a rubber support.

5. The electrode storage rubber according to claim 4, wherein the ion conductive dispersion is a lithium salt that dissolves in an organic solvent of an electrolytic solution and dissociates into an anion.

6. An electricity storage rubber for an electrode, wherein an electron conductive dispersion material and a battery active material are dispersed in a rubber support that does not contain an ion conductive dispersion material.

7. The electrical storage capacity for an electrode according to claim 6, wherein the electronically conductive dispersion material is dispersed in an amount of 60 to 100 mass% with respect to 100 mass% of the rubber support. Rubber.

8. The battery power storage rubber according to claim 6, wherein the battery active material is dispersed in an amount of 10 to 50% by mass with respect to 100% by mass of the rubber support.

9. The electricity storage property for an electrode according to any one of claims 6 to 8, wherein pores through which the ion conductive liquid permeates are dispersed in the rubber support. Rubber.

10. The electricity storage rubber for an electrode according to claim 9, wherein the ion conductive liquid is an electrolytic solution containing an organic solvent and a lithium salt.

11. The rubber support according to any one of claims 6 to 8, wherein the rubber support is swollen by an organic solvent so that an ion conductive liquid can permeate and an ion path is possible. The electricity storage rubber for electrodes according to one item.

12. The electrode conductive liquid according to claim 11, wherein the ion conductive liquid is an electrolytic solution containing an organic solvent and a lithium salt.

13. The electron conductive dispersion material is one or more carbon powders selected from acetylene black, ketjen black, and graphite powder. The electrical storage rubber | gum for electrodes as described in any one of term.

14. The electron conductive dispersion material is one or more carbon powders selected from acetylene black, ketjen black, and graphite powder. Electric storage rubber for electrodes.

15. The electron conductive dispersion material is one or more carbon powders selected from acetylene black, ketjen black, and graphite powder. Power storage rubber for electrodes.

16. The electric storage rubber for an electrode according to any one of claims 4 to 8, wherein the battery active material is a positive electrode active material, and the electrode is a positive electrode.

17. The electrode storage rubber according to claim 16, wherein the positive electrode active material is a lithium transition metal composite oxide.

18. The electric storage rubber for an electrode according to claim 9, wherein the battery active material is a positive electrode active material, and the electrode is a positive electrode.

19. The battery rubber according to claim 11, wherein the battery active material is a positive electrode active material and the electrode is a positive electrode.

20. The electrode storage rubber according to any one of claims 4 to 8, wherein the battery active material is a negative electrode active material, and the electrode is a negative electrode.

21. The electricity storage rubber for an electrode according to claim 20, wherein the negative electrode active material is a lithium insertion compound.

2 2. An electric double layer capacitor using the electricity storing rubber according to any one of claims 1 to 3 in contact with a current collector.

23. The electric double layer capacitor according to claim 22, wherein a mass ratio of the current collector to the electricity storage rubber is 1 or less.

24. A lithium battery comprising the electrode storage rubber according to any one of claims 4 to 8 adhered to a current collector.

25. The lithium battery according to claim 24, wherein a mass ratio of the current collector to the electrode storage rubber is 1 or less.

2 6. A lithium battery comprising the electrode storage rubber according to claim 9 adhered to a current collector.

27. A lithium battery comprising the electrode storage rubber according to claim 11 adhered to a current collector.

28. The lithium battery according to claim 27, wherein the electrode storage rubber is vulcanized and bonded to a current collector.