WO2014084155A1 - Dispositif de stockage d'électricité, électrode utilisée dans celui-ci, et feuille poreuse - Google Patents

Dispositif de stockage d'électricité, électrode utilisée dans celui-ci, et feuille poreuse Download PDF

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WO2014084155A1
WO2014084155A1 PCT/JP2013/081585 JP2013081585W WO2014084155A1 WO 2014084155 A1 WO2014084155 A1 WO 2014084155A1 JP 2013081585 W JP2013081585 W JP 2013081585W WO 2014084155 A1 WO2014084155 A1 WO 2014084155A1
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storage device
electrode
conductive polymer
electricity storage
carbon material
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Japanese (ja)
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阿部　正男
大谷　彰
岸井　豊
植谷　慶裕
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日東電工株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electricity storage device, an electrode used therefor, and a porous sheet, and more particularly, to such a conventional electric double layer capacitor while maintaining the excellent weight output density and cycle characteristics inherent in the conventional electric double layer capacitor.
  • the present invention relates to an electric double layer capacitor type electricity storage device having a remarkably high weight energy density, an electrode used therefor, and a porous sheet.
  • a lithium secondary battery As a power storage device for a hybrid vehicle or an electric vehicle, a lithium secondary battery is mainly used because of its high energy density, but the performance of the lithium secondary battery is not yet sufficient. That is, the lithium secondary battery has a high energy density but a low output density.
  • the electric double layer capacitor has a very low weight energy density, but inherently has a very high weight output density, and also has excellent cycle characteristics.
  • the electric double layer capacitor inherently has a high weight output density and cycle characteristics, and has excellent characteristics as an electricity storage device, but the only drawback is that the weight energy density is low.
  • an electric double layer capacitor usually uses a polarizable electrode formed using a conductive porous carbon material such as powdered activated carbon or fibrous activated carbon, and has a physical adsorption characteristic of supporting electrolyte ions in an electrolytic solution. Since it is a device that uses electricity to store electricity, its weight energy density is extremely small compared to a battery using a chemical reaction called redox reaction, and it cannot maintain a long-term discharge in actual use. Have a problem.
  • activated carbon used for an electric double layer capacitor is generally manufactured by steam activation and chemical activation of raw materials such as coconut shell carbide, phenol resin carbide, and coal.
  • a solvent extract of coal ashless coal
  • the resulting solid residue is alkali-activated (patented) Document 1), a method in which coal-based pitch is heat-treated in a two-step temperature range of 400 to 600 ° C.
  • the electric double layer capacitor having a polarizable electrode formed by this method is still not sufficiently improved in weight energy density.
  • the proposed electric double layer capacitor and storage battery are not yet sufficient in performance, compared with lithium secondary batteries using lithium-containing transition metal oxides such as lithium manganate and lithium cobaltate for the electrode, The capacity density and energy density are low.
  • the present invention has been made to solve the above-described problems, and provides a novel electricity storage device having a high capacity density and a high energy density, an electrode used therefor, and a porous sheet.
  • the present invention is an electricity storage device having an electrolyte layer, a positive electrode and a negative electrode provided therebetween, and at least one of the electrodes includes at least the following (A), (B), (C), and (D):
  • a power storage device in which the following (B) is fixed in the composite body is a first summary.
  • an electrode for electrical storage devices is an electrical storage device in which the composite is composed of at least (A), (B), (C), and (D) and (B) is fixed in the composite.
  • an electrode be a 2nd summary.
  • porous sheet for an electricity storage device electrode is composed of a composite comprising at least the above (A), (B), (C) and (D), and (B) is fixed in the composite.
  • the porous sheet for an electrical storage device electrode is a third aspect.
  • the present inventors made studies to obtain an electricity storage device having a high capacity density and a high energy density by forming an electrode using a conductive polymer or a porous carbon material. In the process, it was found that the characteristics of the electricity storage device were greatly improved by modifying the porous carbon material with a conductive polymer and combining this material with a thiol compound and an anionic material.
  • “(B) is fixed in the composite” means that the B component is fixed in the composite formed with the other electrode forming material.
  • (B) is fixed and does not move, it has the property that the cation moves, and this means that the electricity storage device using this has a rocking chair type mechanism.
  • At least one of the electrodes is a complex composed of at least the following (A), (B), (C), and (D), and the following (B) is in the complex. Since it is fixed, it is excellent in high capacity density and high energy density.
  • A Conductive polymer.
  • B Anionic material.
  • C Porous carbon material.
  • D Thiol compounds.
  • the electrical storage device is an electrode for electrical storage devices, and is an electrical storage device in which the composite is composed of at least (A), (B), (C), and (D) and (B) is fixed in the composite. If it is an electrode, the electrical storage device using this will become excellent in a high capacity
  • porous sheet for a device electrode is composed of a composite comprising at least (A), (B), (C) and (D), and (B) is fixed in the composite. If the porous sheet for an electricity storage device electrode is used, an electricity storage device using the sheet will be excellent in high capacity density and high energy density.
  • an electricity storage device of the present invention is an electricity storage device having an electrolyte layer 3 and a positive electrode 2 and a negative electrode 4 provided therebetween, at least one of the electrodes being at least the following (A ), (B), (C), and (D), and the following (B) is fixed in the composite.
  • A Conductive polymer.
  • B Anionic material.
  • C Porous carbon material.
  • D Thiol compounds.
  • the most characteristic feature of the present invention is that it has an electrode made of a composite having (A), (B), (C), and (D) as constituent elements. I will explain later.
  • the conductive polymer (A) is an electrode active material whose conductivity is changed by ion insertion / extraction, such as polyacetylene, polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide. , Polyphenylene oxide, polyazulene, poly (3,4-ethylenedioxythiophene), and various derivatives thereof.
  • polyaniline, polypyrrole, polythiophene, or a conductor of these polymers having a large electrochemical capacity and capable of chemical oxidative polymerization is preferably used.
  • polyaniline derivative examples include at least a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m-methoxyaniline, m
  • polymers such as m-substituted anilines such as -ethoxyaniline and m-phenylaniline.
  • polypyrrole derivative examples include substitution of alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylaryl groups, arylalkyl groups, alkoxyalkyl groups, etc. at positions other than the 2-position and 5-position of pyrrole. Those having at least one group can be exemplified.
  • Preferable specific examples include, for example, 3-methylpyrrole, 3-ethylpyrrole, 3-ethenylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-phenylpyrrole, 3-phenoxypyrrole, 3-p-toluylpyrrole, 3-benzylpyrrole, 3-methoxymethylpyrrole, 3-p-fluorophenylpyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-diethenylpyrrole, 3,4-dimethoxypyrrole, 3, 4-diethoxypyrrole, 3,4-diphenylpyrrole, 3,4-diphenoxypyrrole, 3,4-di (p-toluyl) pyrrole, 3,4-dibenzylpyrrole, 3,4-dimethoxymethylpyrrole, 3 , 4-di (p-fluorophenyl) pyrrole and the like. These may be used alone
  • polythiophene derivatives examples include 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4- (2 ′, 2′-diethylpropylene) dioxythiophene, 3,4- ( List polymers such as 2,2-diethylpropylenedioxy) thiophene, 3-methylthiophene, 3-ethylthiophene, 3- (4-octylphenyl) thiophene, hydroxymethyl (3,4-ethylenedioxy) thiophene Can do. These may be used alone or in combination of two or more.
  • the porous carbon material (C) is a material having a porous structure mainly composed of a carbon material, and activated carbon that has been subjected to chemical or physical treatment (activation, activation) in order to increase adsorption efficiency.
  • activated carbon subjected to the chemical treatment include phenol resin activated carbon, coconut shell activated carbon, and petroleum coke activated carbon.
  • activated carbon subjected to the above physical treatment include activated carbon obtained from a steam activation treatment method, activated carbon obtained from a molten KOH activation treatment method, and the like. Among these, it is preferable to use activated carbon obtained by a steam activation treatment method in that a large capacity can be obtained.
  • activated carbon for electric double layer capacitors having a large specific surface area is preferably used. It is preferable to use activated carbon having an average particle size of 20 ⁇ m or less and a specific surface area of 1000 to 3000 m 2 / g so as to obtain an electricity storage device having a large capacity and a low internal resistance.
  • the porous surface of the porous carbon material (C) coated with the conductive polymer (A) is particularly preferably used. It is done.
  • the coating of the conductive polymer (A) on the porous carbon material (C) is a method of immersing the porous carbon material (C) in a solution obtained by dissolving the conductive polymer (A) in an appropriate solvent and drying it.
  • Electrolytic method Porous carbon material (C) is immersed in polymerization solution during chemical oxidative polymerization of conductive polymer (A), and conductive polymer (A) is attached to the surface of porous carbon material (C) (Hereinafter, referred to as “in situ polymerization method”).
  • the in-situ polymerization method is particularly preferably used because a uniform thin film can be obtained.
  • the method described in Patent Document 6 Japanese Patent Laid-Open No. 2012-33783
  • the coating thickness of the conductive polymer (A) is 0.1 to 500 nm, preferably 0.5 to 50 nm. If it is too thin, it will be difficult to obtain a storage battery with a high capacity density, and if it is too thick, it will be difficult for ions to diffuse and it will be difficult to obtain a high capacity density.
  • the weight ratio of the conductive polymer (A) to the composite of the conductive polymer (A) and the porous carbon material (C) is 0.5 to 40%, preferably 1 to 10%.
  • the electrode for an electricity storage device of the present invention is usually made of a material containing the conductive polymer (A) and the porous carbon material (C), the anionic material (B) and the thiol compound (D) described below. It consists of a porous sheet used.
  • numerator is used preferably, and since especially polycarboxylic acid can also serve as a binder, it is used more suitably.
  • polycarboxylic acid examples include polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, polyaspartic acid, and the like.
  • Polymaleic acid is particularly preferably used. These may be used alone or in combination of two or more.
  • the polymer such as the polycarboxylic acid
  • the polymer has a function as a binder and also functions as a fixed anion.
  • a compound in which a carboxylic acid having a carboxyl group in the molecule is converted to a lithium type can be mentioned.
  • the exchange rate for the lithium type is preferably 100%, but the exchange rate may be low depending on the situation, and is preferably 40 to 100%.
  • the anionic material (B) is usually 1 to 100 parts by weight, preferably 2 to 70 parts by weight, based on a total of 100 parts by weight of the conductive polymer (A) and the porous carbon material (C). Preferably, it is used in the range of 5 to 40 parts by weight. If the amount of the anionic material (B) is too small, it tends to be impossible to obtain an electricity storage device excellent in energy density. On the other hand, if the amount of the anionic material (B) is too large, the energy density is high. There is a tendency that an electricity storage device cannot be obtained.
  • thiol compound (D) examples include compounds represented by the following general formula (1).
  • R represents an aliphatic or aromatic organic group, S represents sulfur, y represents an integer of 1 or more, and n represents an integer of 2 or more.
  • thiol compound (D) examples include thioglycol represented by HSCH 2 CH 2 SH and 2,5-dimercapto-1,3,4- represented by C 2 N 2 S (SH) 2.
  • Thiadiazole hereinafter referred to as “DMcT”
  • s-triazine-2,4,6-trithiol represented by C 3 H 3 N 3 S 3
  • 7-methyl represented by C 6 H 6 N 4 S 3 -2,6,8-trimercaptopurine
  • 4,5-diamino-2,6-dimercaptopyrimidine represented by C 4 H 6 N 4 S 2 etc.
  • a disulfide compound such as a compound in which all of the compound is substituted with an alkali metal or a compound in which these compounds are converted into multimers by disulfide bonds is preferably used.
  • the thiol compound (D) is usually 1 to 100 parts by weight, preferably 2 to 70 parts by weight, based on the total weight of 100 parts by weight of the conductive polymer (A) and the porous carbon material (C). Preferably, it is used in the range of 3 to 40 parts by weight. If the amount of the thiol compound (D) with respect to (A) + (C) is too small, there is a tendency that an electricity storage device having excellent energy density cannot be obtained. On the other hand, the thiol compound with respect to (A) + (C) Even if the amount of the compound (D) is too large, an energy storage device having a high energy density tends not to be obtained.
  • the electrode according to the electricity storage device of the present invention is composed of a composite comprising at least the above (A), (B), (C), and (D), and is usually formed on a porous sheet.
  • the thickness of the electrode is preferably 1 to 1000 ⁇ m, more preferably 10 to 700 ⁇ m. In other words, if the thickness is too thin, there is a tendency to become an electricity storage device in which sufficient capacity cannot be obtained. Conversely, if the thickness is too thick, it becomes difficult for ions to diffuse inside the positive electrode, and a desired output cannot be obtained. This is because there is a tendency.
  • the thickness of the electrode is obtained by measuring the electrode using a dial gauge (made by Ozaki Mfg. Co., Ltd.) whose tip shape is a flat plate having a diameter of 5 mm, and obtaining the average of 10 measured values with respect to the surface of the electrode. .
  • a dial gauge made by Ozaki Mfg. Co., Ltd.
  • the thickness of the composite is measured in the same manner as described above, the average of the measured values is obtained, and the thickness of the current collector is subtracted.
  • the thickness of the electrode can be obtained.
  • the electrode according to the electricity storage device of the present invention is formed, for example, as follows.
  • the porous carbon material (C) coated with the conductive polymer (A) is immersed in a solution of the thiol compound (D) to adsorb the thiol compound (D) to the porous carbon material (C).
  • an anionic material (B) is dissolved in water to form an aqueous solution, and a porous carbon material (C) powder coated with a conductive polymer (A) in which the thiol compound (D) is adsorbed is necessary.
  • a conductive assistant such as conductive carbon black or a binder such as vinylidene fluoride is added and sufficiently dispersed to prepare a paste.
  • An electrode can be obtained as a body (porous sheet).
  • the anionic material (B) is arranged as a mixture of the conductive polymer (A), the porous carbon material (C), and the thiol compound (D), Fixed to. And the anionic material (B) fixedly arranged in the vicinity of the conductive polymer (A) in this way is also used for charge compensation during oxidation-reduction of the conductive polymer (A).
  • the thiol compound (D) effectively causes an oxidation-reduction reaction by the catalytic function of the conductive polymer (A) as an electrode active material, contributing to an increase in capacity of the electrode.
  • an anionic material (B) is fixedly disposed in the vicinity of the conductive polymer (A), and further, the porous carbon material (C) and the thiol Conjugation with the system compound (D) leads to an appropriate electrode active material concentration environment, and facilitates the movement of ions that are inserted into and desorbed from the conductive polymer (A). .
  • the porosity (%) of the electrode can be calculated by ⁇ (apparent volume of electrode ⁇ true volume of electrode) / apparent volume of electrode ⁇ ⁇ 100, preferably 50 to 80%, more preferably 60 to 70. %.
  • the apparent volume of the electrode means “electrode area of the electrode ⁇ electrode thickness”. Specifically, the volume of the electrode material, the volume of the void in the electrode, and the space of the uneven portion on the electrode surface Consists of total volume.
  • the true volume of the electrode refers to the “volume of the electrode constituent material”. Specifically, using the constituent weight ratio of the positive electrode constituent material and the true density value of each constituent material, The average density is calculated, and it is obtained by dividing the total weight of the electrode constituent materials by this average density.
  • polyaniline 1.2 As the true density (true specific gravity) of each constituent material used above, polyaniline 1.2, activated carbon 2.0, polyacrylic acid 1.2, DMcT 1.0 g, and Denka black (acetylene black) 2.0 were used. .
  • the electrode which concerns on this invention can be used for both the positive electrode and negative electrode of an electrical storage device, it is preferable to use as a positive electrode especially. That is, as shown in FIG. 1, the electrode according to the present invention includes any one of a positive electrode 2 and a negative electrode 4 in an electricity storage device provided with an electrolyte layer 3 and a pair of electrodes (positive electrode 2 and negative electrode 4) facing each other. However, it is preferable to use as the positive electrode 2.
  • the structure of an electrical storage device is demonstrated about the case where the electrode which concerns on the electrical storage device of this invention is used as the positive electrode 2.
  • FIG. 1 the structure of an electrical storage device is demonstrated about the case where the electrode which concerns on the electrical storage device of this invention is used as the positive electrode 2.
  • the electrolyte layer used in the electricity storage device of the present invention is composed of an electrolyte.
  • a sheet formed by impregnating a separator with an electrolytic solution or a sheet formed of a solid electrolyte is preferably used.
  • the sheet made of the solid electrolyte itself also serves as a separator.
  • examples of the electrolyte constituting such an electrolytic solution include protons, alkali metal ions, quaternary ammonium ions, At least one cation such as quaternary phosphonium ion and sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroarsenic ion, halogen ion, phosphate ion, sulfate ion, nitrate ion
  • a combination of at least one kind of anions such as the above is preferably used.
  • At least one organic solvent such as carbonates, alcohols, nitriles, amides, ethers and the like is used in addition to water.
  • electrolytic solution what melt
  • the negative electrode is formed using a negative electrode active material.
  • a negative electrode active material for example, metallic lithium, a carbon material in which lithium ions can be inserted / extracted during oxidation / reduction, a transition metal oxide, silicon, tin, and the like are preferably used.
  • “use” means not only the case where only the forming material is used, but also the case where the forming material is used in combination with another forming material. Is used at less than 50% by weight of the forming material.
  • the electricity storage device uses a separator in addition to the positive electrode, the electrolyte layer, the negative electrode, and the like.
  • a separator can be used in various modes.
  • an insulating porous sheet that can prevent an electrical short circuit between the positive electrode and the negative electrode, is electrochemically stable, has a large ion permeability, and has a certain mechanical strength.
  • a porous sheet made of a resin such as paper, non-woven fabric, polypropylene, polyethylene, or polyimide is preferably used. These may be used alone or in combination of two or more.
  • the electrolyte layer 3 is a sheet
  • the assembly of the electricity storage device using the above materials is preferably performed in an atmosphere of an inert gas such as ultra-high purity argon gas in a glove box.
  • metal foils and meshes such as nickel, aluminum, stainless steel, and copper are appropriately used as the current collectors (1, 5 in FIG. 1) of the electrode 2 and the negative electrode 4.
  • the electricity storage device of the present invention is formed into various shapes such as a laminate cell, a porous sheet type, a sheet type, a square type, a cylindrical type, and a button type.
  • the capacity density per weight of the porous carbon material coated with the conductive polymer is usually 100 mAh / g or more, preferably 150 mAh / g or more.
  • the water-activated activated carbon (made by JFE Chemical Co., Ltd.) JSC18) 50 g (activated carbon / aniline weight ratio 40) was added and subjected to ultrasonic dispersion treatment with an ultrasonic homogenizer for 2 minutes to suspend the activated carbon in the aniline / oxidant aqueous solution.
  • the aniline / oxidant aqueous solution in which the activated carbon was suspended was placed under a reduced pressure of 30 hPa, defoamed for 5 minutes, and impregnated with the aniline / oxidant aqueous solution into the pores of the activated carbon. Thereafter, the aniline / oxidant aqueous solution was returned to atmospheric pressure and stirring was continued.
  • the aniline / oxidant aqueous solution which was initially colorless and transparent, continued to be transparent during the treatment so far. Thereafter, oxidative polymerization of aniline was started in the aniline / oxidant aqueous solution, and as the water proceeded, the water-soluble color changed from blue to blue-green and further to black-green.
  • the aniline oxidation polymer thus obtained was filtered under reduced pressure to obtain a black powder. This was washed with acetone, filtered again under reduced pressure, and this operation was performed three times in total.
  • the obtained black powder was vacuum-dried at room temperature for 10 hours in a desiccator to obtain 51.2 g of a conductive polyaniline / activated carbon composite having tetrafluoroboric acid as a dopant.
  • the weight increase of the conductive polyaniline / activated carbon composite thus obtained was 1.2 g based on the weight of the activated carbon used. That is, the proportion of the weight increase in the composite was 2.3% by weight.
  • the specific surface area of this conductive polyaniline / activated carbon composite by BET method was 1600 m 2 / g.
  • anionic material (B) Using polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 800,000), 1 ⁇ 2 equivalent lithium hydroxide of carboxylic acid was added in an aqueous solution, and 4.5 wt% concentration of uniform and viscous poly An aqueous acrylic acid solution was prepared. In the polyacrylic acid, about 50% of the carboxyl groups were lithium-chlorinated.
  • a nonwoven fabric (manufactured by Hosen Co., Ltd., TF40-50, porosity: 55%) was prepared.
  • Example 1 ⁇ Manufacture of composite sheet electrode> To 100 ml of a 2.5 wt% acetone solution of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) (manufactured by Kanto Chemical), 4.00 g of the porous carbon material powder coated with the conductive polymer was added for 24 hours. After soaking, the solution was filtered off and dried at 100 ° C. Furthermore, when vacuum-dried and weighed, 12% by weight of DMcT was adsorbed to the porous carbon material powder coated with the conductive polymer. 4.48 g of this treated powder was mixed with 0.53 g of conductive carbon black (Denka Black, Denki Black).
  • DMcT 2,5-dimercapto-1,3,4-thiadiazole
  • Etching aluminum foil for electric double layer capacitors (Hosen Co., Ltd.) using a tabletop automatic coating device (manufactured by Tester Sangyo Co., Ltd.) with a doctor blade type applicator with a micrometer at a coating speed of 10 mm / sec. Manufactured, 30 CB).
  • a tabletop automatic coating device manufactured by Tester Sangyo Co., Ltd.
  • a doctor blade type applicator with a micrometer at a coating speed of 10 mm / sec.
  • Manufactured, 30 CB Manufactured, 30 CB
  • the positive electrode active material layer composed of a porous carbon material coated with polyaniline, polyacrylic acid, DMcT, and conductive carbon black had a thickness of 312 ⁇ m and a porosity of 72%.
  • the produced positive electrode sheet and the prepared separator were vacuum-dried at 100 ° C. for 5 hours using a vacuum dryer. Then, the following assembly was performed in a glove box with a dew point of ⁇ 100 ° C. in an ultrahigh purity argon gas atmosphere.
  • the porous membrane obtained above was punched into a disc shape with a punching jig on which a punching blade having a diameter of 15.95 mm was installed to form a positive electrode, and a stainless steel HS cell (treasure) for non-aqueous electrolyte secondary battery experiments.
  • the positive electrode and the prepared negative electrode were placed facing each other correctly, and the separator was positioned so that they did not short-circuit.
  • the positive electrode sheet and the separator were vacuum-dried at 100 ° C. for 5 hours in a vacuum dryer before being assembled to the HS cell.
  • the prepared electrolyte solution was inject
  • covered the conductive polymer, and the cell which is an electrical storage device was completed. That is, the amount of electrolytic solution (mg) / porous carbon material coated with a conductive polymer (mg) 4.5 (mg / mg).
  • Example 2 A cell was prepared and evaluated in the same manner as in Example 1 except that the amount of electrolytic solution (mg) was 3.75 times that of the porous carbon material (mg) coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • Example 3 A cell was prepared and evaluated in the same manner as in Example 1 except that the amount (mg) of the electrolyte was 3.25 times the weight (mg) of the porous carbon material coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • Example 4 A cell was prepared and evaluated in the same manner as in Example 1 except that the amount (mg) of the electrolytic solution was 2.50 times the weight (mg) of the porous carbon material coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • Example 1 In Example 1, instead of 4.00 g of the porous carbon material powder coated with the conductive polymer, 4.00 g of the porous carbon material powder not coated with the conductive polymer is used, and the adsorption treatment with DMcT is not performed.
  • the positive electrode active material layer made of activated carbon, SBR, poly (N-vinylpyrrolidone) and conductive carbon black had a thickness of 321 ⁇ m and a porosity of 63%.
  • the discharge capacity of the battery using this electrode was converted to the weight of the porous carbon material coated with the conductive polymer, it was 73 mAh / g. Furthermore, it was 13.3 mAh / g when converted to the total weight of the weight of the porous carbon material coated with the conductive polymer and the amount of the electrolytic solution used.
  • Table 1 Table 1 below, FIG. 2 and FIG.
  • Comparative Example 2 A cell was prepared and evaluated in the same manner as in Comparative Example 1 except that the amount of electrolytic solution (mg) was 3.75 times that of the porous carbon material (mg) not coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • Comparative Example 3 A cell was prepared and evaluated in the same manner as in Comparative Example 1 except that the amount of electrolytic solution (mg) was 3.25 times that of the porous carbon material (mg) not coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • Comparative Example 4 A cell was prepared and evaluated in the same manner as in Comparative Example 1 except that the amount of electrolytic solution (mg) was 2.50 times that of the porous carbon material (mg) not coated with the conductive polymer. The results are shown in Table 1 below, FIG. 2 and FIG.
  • the capacity of the example is larger than that of the comparative example, and even if the amount of the electrolyte is reduced, the capacity relative to the total weight of the porous carbon material coated with the conductive polymer and the amount of the electrolyte in the example. It was found that the density did not decrease. From these results, it can be seen that the example is superior in capacity density to the comparative example, and from the result of FIG. 3, the example does not decrease the capacity density even when the electrolyte weight decreases. This is evident from the increasing trend. The present inventors confirmed that Examples 1 to 4 were excellent in charge / discharge rate.
  • the electricity storage device of the present invention can be suitably used as an electricity storage device such as a lithium secondary battery or a high-capacity capacitor.
  • the electricity storage device of the present invention can be used for the same applications as conventional secondary batteries and electric double layer capacitors.
  • portable electronic devices such as portable PCs, cellular phones, and personal digital assistants (PDAs), Widely used in driving power sources for hybrid electric vehicles, electric vehicles, fuel cell vehicles and the like.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Selon l'invention, afin d'obtenir un nouveau dispositif de stockage d'électricité ayant une densité de capacité élevée et une densité d'énergie élevée, l'invention concerne un dispositif de stockage d'électricité qui comprend une couche d'électrolyte (3) et une électrode positive (2) et une électrode négative (4) qui sont agencées de façon à prendre en sandwich la couche d'électrolyte (3), au moins une des électrodes dans ledit dispositif de stockage d'électricité étant un composite qui est composé des composants (A), (B), (C) et (D) décrits ci-dessous et le composant (B) étant immobilisé dans le composite. (A) un polymère conducteur (B) un matériau anionique (C) un matériau carboné poreux (D) un composé de thiol
PCT/JP2013/081585 2012-11-28 2013-11-25 Dispositif de stockage d'électricité, électrode utilisée dans celui-ci, et feuille poreuse WO2014084155A1 (fr)

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CN114649509A (zh) * 2022-04-07 2022-06-21 楚能新能源股份有限公司 一种制备锂离子电池正极的方法
WO2023216610A1 (fr) * 2022-05-11 2023-11-16 厦门海辰储能科技股份有限公司 Suspension de batterie, feuille d'électrode positive, feuille d'électrode négative et batterie au lithium

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WO2019044792A1 (fr) * 2017-08-31 2019-03-07 出光興産株式会社 Charbon actif, matériau d'électrode et électrode dans laquelle un matériau d'électrode est utilisé

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JPH117959A (ja) * 1997-06-13 1999-01-12 Yazaki Corp 電極材料、その製造方法及び二次電池
JP2001266885A (ja) * 2000-03-23 2001-09-28 Matsushita Electric Ind Co Ltd 複合電極組成物、その製造方法およびリチウム電池
WO2012141166A1 (fr) * 2011-04-11 2012-10-18 横浜ゴム株式会社 Composite polymère conducteur/matière carbonée poreuse et matière d'électrode l'utilisant

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JPH117959A (ja) * 1997-06-13 1999-01-12 Yazaki Corp 電極材料、その製造方法及び二次電池
JP2001266885A (ja) * 2000-03-23 2001-09-28 Matsushita Electric Ind Co Ltd 複合電極組成物、その製造方法およびリチウム電池
WO2012141166A1 (fr) * 2011-04-11 2012-10-18 横浜ゴム株式会社 Composite polymère conducteur/matière carbonée poreuse et matière d'électrode l'utilisant
JP5136733B2 (ja) * 2011-04-11 2013-02-06 横浜ゴム株式会社 導電性高分子／多孔質炭素材料複合体およびそれを用いた電極材料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114649509A (zh) * 2022-04-07 2022-06-21 楚能新能源股份有限公司 一种制备锂离子电池正极的方法
WO2023216610A1 (fr) * 2022-05-11 2023-11-16 厦门海辰储能科技股份有限公司 Suspension de batterie, feuille d'électrode positive, feuille d'électrode négative et batterie au lithium

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