WO2008123577A1 - 炭素粒子フィルム、積層電極、および電気二重層キャパシタの製造方法 - Google Patents
炭素粒子フィルム、積層電極、および電気二重層キャパシタの製造方法 Download PDFInfo
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- WO2008123577A1 WO2008123577A1 PCT/JP2008/056646 JP2008056646W WO2008123577A1 WO 2008123577 A1 WO2008123577 A1 WO 2008123577A1 JP 2008056646 W JP2008056646 W JP 2008056646W WO 2008123577 A1 WO2008123577 A1 WO 2008123577A1
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- WIPO (PCT)
- Prior art keywords
- particles
- film
- inorganic particles
- current collector
- laminated
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000002245 particle Substances 0.000 title claims abstract description 159
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 119
- 239000003990 capacitor Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000010954 inorganic particle Substances 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 41
- 230000006835 compression Effects 0.000 claims description 13
- 238000007906 compression Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 101150107341 RERE gene Proteins 0.000 claims 1
- 239000010410 layer Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 239000003792 electrolyte Substances 0.000 description 10
- 239000006230 acetylene black Substances 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008119 colloidal silica Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238558 Eucarida Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 241000973887 Takayama Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/22—Devices using combined reduction and oxidation, e.g. redox arrangement or solion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a method for producing a film composed of inorganic particles and carbon particles bound with the inorganic particles, and a method for producing a laminated electrode and an electric double layer capacitor using the method.
- an electric double layer capacitor is used to store electric energy.
- an electrode used for an electric double layer capacitor an electrode in which carbon particles are bound by an organic binder is known.
- Fluororesin is used as the organic binder, and polytetrafluoroethylene (PTFE) is generally used because of its excellent heat resistance, chemical resistance, and electrochemical stability. Since the binding force is usually weak, increasing the amount of PTFE to obtain sufficient binding strength decreases the electrostatic capacity per unit volume of the electrode.
- Japanese Patent Application Laid-Open No. 9-36005 discloses a paste composed of carbon particles and PTFE coated on a current collector that is higher than the melting temperature of PTFE and lower than the decomposition temperature.
- a method of pressing the dried paste is disclosed. ing. According to this method, particles of PTFE heated at a temperature higher than the melting temperature of PTFE and lower than the decomposition temperature melt and enter between the activated carbons while fusing together. By pressing the bow I, it is possible to form an electrode with a high bulk density and high binding strength.
- An object of the present invention is to provide a method for easily producing a carbon particle film having a high bulk density without coating the carbon particles with an organic binder, and thus, a laminated electrode having a large capacitance per unit volume.
- Another object of the present invention is to provide a simple method for producing an electric double layer capacitor having a large capacitance per unit volume. Disclosure of the invention
- One aspect of the present invention is a method for producing a film comprising inorganic particles and carbon particles bound with the inorganic particles, the film comprising a mixture of carbon particles and inorganic particles,
- the method includes a step of increasing the bulk density of the mixture by compressing at a temperature that is not higher than the melting point of the particles and not higher than the melting point of the inorganic particles. Since the film obtained by this method can be used as an electrode film, this method can be used as a method for producing an electrode film.
- Another aspect of the present invention is an application of the above-described film manufacturing method, which is a method for manufacturing a laminated electrode having a current collector and an electrode film laminated on the current collector, and includes the following: It is a method including a process. '
- another aspect of the present invention is also an application of the above-described film manufacturing method, and comprises two laminated electrodes each having a current collector and an electrode film laminated on the current collector, and a separator.
- the electrode is disposed so that the electrodes face each other and the electrode films are separated by a separator, and the stacked electrodes are wound or stacked with the separator interposed between the electrodes.
- a method of manufacturing an electric double layer capacitor comprising the steps of: enclosing the laminated electrodes and the separator in a metal case together with an electrolytic solution, and further comprising the following steps for manufacturing the laminated electrodes.
- the film of the mixture on the current collector is compressed at a temperature below the melting point of the carbon particles and below the melting point of the inorganic particles to increase the bulk density of the mixture, thereby Forming a laminated electrode in which an electrode film made of inorganic particles and a film made of the carbon particles bound with the inorganic particles is laminated on the current collector;
- One aspect of the present invention is a method for producing a film comprising inorganic particles and carbon particles bound with the inorganic particles, the film comprising a mixture of carbon particles and inorganic particles,
- the method includes a step of increasing the bulk density of the mixture by compressing at a temperature that is not higher than the melting point of the particles and not higher than the melting point of the inorganic particles.
- the carbon particles in the present invention are particles composed of only carbon or substantially only carbon, and examples thereof include bonbon black such as acetylene black and ketchin black, graphite, carbon nanotube, carbon nano Sphere.
- the carbon particles may be a kind of carbon particles or a mixture of a plurality of kinds of carbon particles. Activated carbon having a large specific surface area is preferably used.
- the carbon particles that the specific surface area contains 1 0 0 0 m 2 / g or more activated carbon good better les.
- the average particle size of the carbon particles is preferably in the range of 1 O nm to 50 m, more preferably in the range of 15 nm to 30; um, and 20 nm to l 0 / xm. More preferably, it is within the range. When two or more types of carbon particles are used, the average particle size of the carbon particles having the largest weight ratio may be within the above range.
- the average particle size of the carbon particles in the present invention is a value determined by dispersing the carbon particles in a liquid medium and measuring the particle size distribution with a laser diffraction / scattering type particle size distribution measuring device.
- the inorganic particles in the present invention are inorganic solid particles other than particles composed only of carbon and particles composed substantially only of carbon. Even if it contains carbon, particles such as metal carbonate, metal cyanate, metal cyanoacid; ⁇ , metal thiocyanate are included in inorganic particles.
- the inorganic particles function as a binder that binds the carbon particles. In a film composed of a mixture of carbon particles and inorganic particles, the mixture is substantially composed of carbon particles and inorganic particles. Therefore, the film obtained by compression does not contain an organic binder such as PTFE, and is substantially In general, it consists of carbon particles and inorganic particles.
- the inorganic particles are preferably siri force particles and alumina or alumina particles, and more preferably silica particles, from the viewpoint of the binding force of the carbon particles and the heat resistance of the resulting film.
- the average particle diameter of the inorganic particles is not more than 110 average particle diameter of the carbon particles, and the average particle diameter of the inorganic particles is 15% of the average particle diameter of the carbon particles. More preferably, it is 0 or less. From the viewpoint of the binding force of the carbon particles, the average particle diameter of the particles is 1/10 or less of the average particle diameter of the carbon particles, and the average particle diameter is in the range of 1 nm to 100 nm. Preferably, the average particle size of the inorganic particles is more preferably in the range of 1 nm to 50 nm. That's right.
- the average particle size of the inorganic particles in the present invention is a value determined by dispersing inorganic particles in a liquid medium and measuring the particle size distribution with a laser diffraction Z scattering type particle size distribution measuring device. Further, from the viewpoint of binding force, it is preferable to use chain-like inorganic particles in which the inorganic particles are chain-like.
- the mixture constituting the film to be subjected to compression preferably contains 100 parts by weight of carbon particles and 10 to 70 parts by weight of inorganic particles from the viewpoint of the binding force by the inorganic particles in the obtained film.
- the amount is further preferably 15 to 50 parts by weight, and more preferably 20 to 45 parts by weight.
- a film made of a mixture of carbon particles and inorganic particles is compressed.
- the film to be subjected to compression can be prepared as follows. First, carbon particles and inorganic particles are dispersed in a liquid medium to produce a dispersion, and then the dispersion is applied onto a suitable substrate to form a dispersion film. Thereafter, by removing the liquid medium from the dispersion liquid film, a film made of a mixture of the carbon particles and the inorganic particles is formed on the substrate.
- the material of the substrate is not particularly limited, but when a metal foil is used, the substrate finally obtained by compression and a film made of a mixture of carbon particles and inorganic particles are laminated thereon.
- the multilayer body can be used as a multilayer electrode for manufacturing an electric double layer capacitor.
- the material of the metal foil is not particularly limited.
- the substrate surface is preferably roughened by etching.
- the liquid medium used for producing the dispersion is not particularly limited, but is preferably water, alcohol, or a mixed solvent thereof because it is easy to remove after coating.
- the silica particles are preferably colloidal in the dispersion from the viewpoint of the binding force of the carbon particles.
- a film comprising a mixture of carbon particles and inorganic particles formed on the substrate as described above is compressed at a temperature that is not higher than the melting point of the carbon particles and not higher than the melting point of the inorganic particles.
- the bulk density of the above mixture is increased to produce a high bulk density Finolem consisting of carbon particles and inorganic particles.
- the temperature at the time of compression is preferably in the range of 10 to 50 ° C. By compressing at such a temperature, the carbon particles can be firmly bound without melting the film.
- the film obtained by compression may be used as it is laminated with the substrate, or may be used as a single layer film by removing the substrate by melting or peeling it.
- a film made of carbon particles and inorganic particles produced by the above method can be suitably used as an electrode. Since such a film has a high bulk density, the electrode has a large surface area per unit volume and a large capacitance. In the production of a film used as an electrode, it is preferable to use activated carbon having a large surface area as the main material of carbon particles.
- activated carbon within a range of 1 m or more and 30 / m or less.
- Activated carbon having such an average particle size can be obtained by adjusting the particle size by pulverizing commercially available activated carbon with a pulverizer such as a ball mill.
- a pulverizer such as a ball mill.
- the balls and the pulverization container are preferably made of a non-metal such as alumina or agate in order to avoid mixing metal powder.
- the laminated electrode to be produced is a laminated body having a current collector and an electrode film laminated on the current collector, and the production method includes the following steps.
- a film of the mixture on the current collector is below the melting point of the carbon particles, and
- An electrode film comprising a film composed of the inorganic particles and the carbon particles bound by the inorganic particles by compressing the mixture at a temperature lower than the melting point of the machine particles to increase the bulk density of the mixture. Forming a laminated electrode laminated on the current collector.
- silica particles are preferably used as the inorganic particles, and in particular, an aqueous colloid of silica or hydrated particles, so-called colloidal silica is preferably used.
- Colloidal silica not only suppresses the aggregation of carbon particles in the dispersion, but also forms a dispersion film by coating the dispersion on a current collector, and further removes the liquid medium from the dispersion film to remove carbon.
- it When forming a film composed of a mixture of particles and inorganic particles, it also functions as a binder for closely adhering the carbon particles or the carbon particles and the current collector.
- an organic binder such as a resin is required in the electrode in order to bring the carbon particles into close contact with each other or between the carbon particles and the current collector.
- carbon particles or carbon particles and a current collector are brought into close contact with each other with inorganic particles, thereby producing an effect of increasing the capacitance.
- the dispersion includes a method in which a predetermined amount of carbon particles and inorganic particles are added to a liquid medium and mixed, a method in which a liquid medium is added to a mixture in which a predetermined amount of carbon particles and inorganic particles are mixed, and the inorganic particles are liquid
- a method in which carbon particles are added to and mixed with an inorganic particle dispersion liquid dispersed in a body medium, an inorganic particle dispersion liquid in which inorganic particles are dispersed in a liquid medium, and a carbon particle dispersion in which carbon particles are dispersed in a liquid medium For example, a method of mixing a liquid and a method of adding and mixing inorganic particles into a carbon particle dispersion in which carbon particles are dispersed in a liquid medium.
- a known mixer When mixing, a known mixer can be used. Since the inorganic particles and the carbon particles are easily dispersed more uniformly, it is preferable to adjust the dispersion by a method in which the carbon particles are added and dispersed in the inorganic particle dispersion in which the inorganic particles are dispersed in the liquid medium.
- carbon particles having a large surface area that is, fine particles. Since the carbon particles are finely pulverized and screened, the dispersion liquid obtained by pulverizing the inorganic particles and the mixed liquid in which the carbon particles are mixed in a liquid medium is obtained. Preferred to use That's right.
- the fine particles easily aggregate in the liquid medium.
- the inorganic particles and the carbon particles having an average particle size larger than the inorganic particles coexist in the liquid medium, and are pulverized. Since it adheres to the fine particles, it is presumed to have an effect of suppressing aggregation of the carbon fine particles in the dispersion.
- the material for the current collector aluminum, copper, iron and the like are preferable. Of these, aluminum is preferred because it is light and has low electrical resistance.
- the shape of the current collector is preferably a film shape having a thickness of 20 / m or more and 100 ⁇ or less because it is easy to produce a wound electrode or a laminated electrode. In order to improve the adhesion between the current collector and the electrode film, the current collector surface is preferably etched and roughened.
- the dispersion can be applied using an application device such as a handy film ablator, a bar coater, or a die coater.
- the liquid medium is removed from the formed dispersion to form a film made of a mixture of carbon particles and inorganic particles on the current collector.
- a method for removing the liquid medium first dry at 10 to 30 minutes at a temperature of 50 to 80 ° C, and then further at a temperature of 10:00 to 200 ° C :! Drying for 60 minutes is preferable from the viewpoint of increasing the binding force of the carbon particles.
- the film made of the mixture is compressed at a temperature not higher than the melting point of the carbon particles and not higher than the melting point of the inorganic particles, thereby increasing the bulk density of the mixture.
- a laminated electrode in which an electrode film made of a film made of the carbon particles bonded with the inorganic particles is laminated on the current collector can be obtained.
- the current collector can be removed by peeling or melting the current collector to obtain an electrode film consisting of only carbon particles and inorganic particles. Since such an electrode film has a larger amount of carbon per unit volume than a conventional electrode, since there is no current collector, an electric double layer capacitor having a large capacitance can be obtained by using this electrode film. I can expect that.
- the electrode film and laminated electrode produced by the method of the present invention can be used as an electrode of, for example, a dry cell, a redox capacitor, a hybrid capacitor, and an electric double layer capacitor. In particular, it is suitable as a constituent member of an electric double layer capacitor.
- As an electric double layer capacitor there is a separator between two electrodes, a capacitor filled with an electrolyte between the separator and each electrode, and a solid electrolyte (gel electrolyte) between the two electrodes. Examples include filled capacitors.
- the positive electrode is positively charged (+)
- the negative electrolyte forms an electric double layer at the positive electrode interface
- the negative electrode is negatively charged (one) at the same time, and the positive electrolyte is electrically charged at the negative electrode interface.
- Electric energy is stored by forming a double layer. Even if charging is stopped, the electric double layer is retained. When it is discharged, the electric double layer is released and electric energy is released.
- the electric double layer capacitor may be a single cell including two electrodes, that is, a positive electrode and a negative electrode, or may be a capacitor in which a plurality of cells are combined.
- two laminated electrodes each having a current collector and an electrode film laminated on the current collector and a separator are disposed so that the electrode films face each other.
- the electrode films are arranged so as to be separated by a separator, and both laminated electrodes are wound or laminated with the separator interposed between the electrode films, and both the laminated electrodes and the separator are wound or laminated.
- a method for producing an electric double layer capacitor having a step of encapsulating a metal case together with an electrolytic solution, and further comprising the following steps for producing each of the laminated electrodes.
- two disk-shaped multilayer electrodes and a separator are arranged so that the electrode films of both multilayer electrodes face each other, and Two electrode films are arranged so that they are separated by a separator, and are stacked with a separator interposed between both electrode films, and are enclosed in a coin-type case together with an electrolyte solution.
- the separator are arranged so that the electrode films face each other and the electrode films are separated by a separator, and the separator is interposed between the electrode films, and the cylindrical case together with the electrolyte
- the electrolytic solution a mixture of an electrolyte and a solvent can be used.
- the electrolyte is particularly limited It may be an inorganic electrolyte or an organic electrolyte. Inorganic electrolytes are usually mixed with water and used as an electrolyte.
- the organic electrolyte is usually used as an electrolyte mixed with a solvent containing an organic polar solvent as a main component.
- an insulating film having a large ion permeability and a predetermined mechanical strength is used.
- paper making of natural fibers such as natural cellulose and Manila hemp; paper making of regenerated fibers and synthetic fibers such as lotion, vinylon, and polyester; and paper making by mixing the natural fibers with the regenerated fibers and the synthetic fibers
- Non-woven fabrics such as polyethylene non-woven fabrics, polypropylene non-woven fabrics, polyester non-woven fabrics, polybutylene terephthalate non-woven fabrics *; porous films such as porous polyethylene, porous polypropylene, porous polyester; para-type wholly aromatic polyamide, fluoride Examples thereof include vinylidene, tetrafluoroethylene, a copolymer of vinylidene fluoride and propylene hexafluoride, and a resin membrane such as a fluorine-containing resin such as fluorine rubber.
- Activated carbon and acetylene black were used as the carbon particles.
- the activated carbon one obtained by grinding Kuraray Chemikare Co., Ltd. PR-15 with a ball mill for 24 hours was used.
- the average particle size of the activated carbon after milling as measured with a laser diffraction / scattering particle size distribution analyzer (HORIBALA-910) using water as a medium was 8.1 1 15 / zm.
- Denka black (average particle size: 36 nm) from Denki Kagaku Kogyo was used for the acetylene black.
- the inorganic particles were used Nissan Chemical Industries, Ltd. colloidal silica Snowtex PS- S (solid concentration 2 0 weight 0/0). This is an aqueous colloid of spherical silica particles having an average particle diameter of 10 to 50 nm, which are bound in a chain having a length of 50 to 200 nm.
- colloidal silica 1 1.7 2 g was added to activated carbon 5.0 g and acetylene black 0.6 25 5 g, and pure water was further added and mixed to prepare a dispersion having a solid content of 32% by weight. .
- the minute The solid content of the liquid dispersion was 5.0 g of activated carbon, 0.625 g of acetylene black, and 2.34 g of silica particles. That is, the amount of silica particles per 100 parts by weight of carbon particles was 46.9 parts by weight.
- the above dispersion was applied using a handy film applicator to form a dispersion film, and then at 60 ° C.
- Both the laminates were compressed at room temperature and 50 kgf Zcm 2 for 3 minutes to obtain two laminate electrodes comprising a current collector and an electrode film made of a compressed film. None of the laminated electrodes were cracked, and the thicknesses of the electrode films in the laminated electrodes were 91 ⁇ and 61 / m, respectively.
- the obtained two laminated electrodes were cut to 1.5 cm ⁇ 2. O cm and dried sufficiently. Then, an electric double layer capacitor was assembled in a glove box using stainless steel as a collector electrode. The two laminated electrodes are arranged so that both electrode films face each other, and are laminated with natural cellulose paper interposed between the two electrode films as a separator, and these are electrolyte solutions manufactured by Takayama Pharmaceutical Co., Ltd. LI PASTE— An electric double layer capacitor was obtained by enclosing it in an aluminum case together with PZTEMAF 14N.
- the obtained electric double layer capacitor was charged at a constant current of 30 OmAZg until the voltage reached 2.8 V, and then discharged at a constant current of 30 OmA / g until the voltage reached OV, and the capacitance was measured. did.
- Two laminates were obtained in the same manner as in Example 1 except that the thickness of the film made of the mixture of carbon particles and inorganic particles in the laminate before compression was 80 ⁇ and 65 m, respectively.
- the two laminates were compressed at room temperature and 100 kgf / cm 2 for 3 minutes to obtain two laminated electrodes comprising a current collector and an electrode film made of a compressed film. There is no crack in any laminated electrode.
- the thicknesses of the electrode films in the layer electrode were 70 / m and 55 ⁇ , respectively.
- an electric double layer capacitor was assembled in the same manner as in Example 1, and the capacitance was measured. The results are shown in Table 1.
- Activated carbon and acetylene black were used as the carbon particles.
- the activated carbon used was obtained by grinding Kuraray Chemical Co., Ltd. PR-15 with a ball mill for 24 hours.
- the average particle diameter of the activated carbon after milling was 8.115 / zm, measured using a laser diffraction / scattering particle size distribution analyzer (HOR I BA LA-910) using water as the medium.
- Denka black average particle size: 36 nm
- Denki Kagaku Kogyo was used for the acetylene black.
- colloidal silica snowtex P S_S solid content concentration 20% by weight
- Colloidal silica (15.63 g) was added to activated carbon (5.0 g) and acetylene black (0.625 g), and pure water was further added and mixed to prepare a dispersion having a solid content concentration of 32% by weight.
- the composition of the dispersion liquid was 5 g of activated carbon, 0.625 g of acetylene black, and 3.126 g of silica force particles. That is, the amount of silica particles relative to 100 parts by weight of carbon particles was 62.52 parts by weight.
- the dispersion was applied using a handy film applicator to form a dispersion film, and then at 60 ° C.
- the mixture was further heated for 10 minutes at 150 ° C. for 1 hour to remove water as a solvent, and two laminates were obtained in which films made of carbon particles and sili- force particles were laminated on a current collector.
- the thickness of the film in the laminate was 75 ⁇ and 85, respectively.
- the two laminates were compressed at room temperature and 50 kgf Zcm 2 for 3 minutes to obtain two laminated electrodes comprising a current collector and an electrode film made of a compressed film. None of the laminated electrodes were cracked, and the thicknesses of the electrode layers in both laminated electrodes were 70 ⁇ and 73 ⁇ , respectively.
- Example 4 Two laminates were obtained in the same manner as in Example 3 except that the thickness of the film made of the mixture of carbon particles and silica particles was 9 ⁇ and 100 im, respectively. The laminate was compressed at room temperature and 100 kg Zcin 2 for 3 minutes to obtain two laminate electrodes comprising a current collector and an electrode film made of a compressed film. There was no crack in any of the laminated electrodes, and the thicknesses of the electrode films in both laminated electrodes were 79 m and 95 ⁇ , respectively.
- Example 2 Two laminates were obtained in the same manner as in Example 1, except that the thickness of the film composed of the mixture of carbon particles and inorganic particles in the laminate before compression was 130 / zm and 110 ⁇ , respectively. It was. An electric double layer capacitor was assembled in the same manner as in Example 1 except that the laminates were used as laminate electrodes without being compressed, and the capacitance was measured. The results are shown in Table 1.
- Example 3 Two laminates were obtained in the same manner as in Example 3 except that the thickness of the film made of the mixture of carbon particles and silica particles was 80 Mm and 85 ⁇ , respectively.
- An electric double layer capacitor was assembled and the capacitance was measured in the same manner as in Example 1 except that both laminates were used as laminated electrodes without being compressed. The results are shown in Table 1.
- the electric double layer capacitors of Examples 1 and 2 provided with the laminated electrodes obtained by compression are more electrostatic per unit volume than the electric double layer capacitor of Comparative Example 1 provided with the uncompressed laminated electrodes. Large capacity.
- the electric double layer capacitors of Examples 3 and 4 provided with the laminated electrodes obtained by compression were more static per unit volume than the electric double layer capacitor of Comparative Example 2 provided with the uncompressed laminated electrodes. It can be seen that the electric capacity is increasing. In the examples, since the film thickness was reduced by the compression, it can be seen that the bulk density of the film was increased by the compression. Industrial applicability
- a film and an electrode film having high strength and density which are composed of an insulator and carbon particles bound with the inorganic particles, without causing damage.
- a laminated electrode having a large capacitance per unit volume and an electric double layer capacitor having a large capacitance per unit volume can be easily obtained.
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US12/593,565 US20100175822A1 (en) | 2007-03-30 | 2008-03-27 | Methods for producing carbon particle film, laminated electrode, and electric double layer capacitor |
EP08739754A EP2144260A1 (en) | 2007-03-30 | 2008-03-27 | Method for producing carbon particle film, laminated electrode, and electric double layer capacitor |
CN2008800099908A CN101647078B (zh) | 2007-03-30 | 2008-03-27 | 碳粒子膜、层叠电极、及双电层电容器的制造方法 |
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JP2007091206 | 2007-03-30 | ||
JP2007-091206 | 2007-03-30 |
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WO2008123577A1 true WO2008123577A1 (ja) | 2008-10-16 |
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PCT/JP2008/056646 WO2008123577A1 (ja) | 2007-03-30 | 2008-03-27 | 炭素粒子フィルム、積層電極、および電気二重層キャパシタの製造方法 |
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US (1) | US20100175822A1 (ja) |
EP (1) | EP2144260A1 (ja) |
JP (1) | JP5336752B2 (ja) |
KR (1) | KR20090125167A (ja) |
CN (1) | CN101647078B (ja) |
TW (1) | TW200902142A (ja) |
WO (1) | WO2008123577A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110292568A1 (en) * | 2008-11-28 | 2011-12-01 | Sumitomo Chemical Company, Limited | Electrode film, electrode, method for manufacturing the electrode, and electrical storage device |
US8332541B2 (en) | 2008-06-27 | 2012-12-11 | Qualcomm Incorporated | Methods and apparatus for communicating and/or using discovery information |
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KR20160146754A (ko) * | 2014-04-28 | 2016-12-21 | 구라레 케미칼 가부시키가이샤 | 에너지 저장 디바이스의 전극용 다공질 탄소 재료 및 그 제조 방법 |
KR102362887B1 (ko) * | 2018-01-03 | 2022-02-14 | 주식회사 엘지에너지솔루션 | 리튬이차전지용 음극의 전리튬화 방법 및 이에 사용되는 리튬 메탈 적층체 |
TWI718931B (zh) | 2020-04-14 | 2021-02-11 | 國立勤益科技大學 | 具二氧化矽微球之超級電容器電極及其製備方法 |
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JPS61292908A (ja) * | 1985-06-17 | 1986-12-23 | ザ スタンダ−ド オイル カンパニ− | 二重層コンデンサ−用の電極の製造法 |
JPH0845793A (ja) * | 1994-08-02 | 1996-02-16 | Asahi Glass Co Ltd | 電気二重層コンデンサ |
JPH0936005A (ja) | 1995-07-18 | 1997-02-07 | Toyota Motor Corp | 電気二重層キャパシタ用電極の製造方法 |
JP2002353074A (ja) * | 2001-05-28 | 2002-12-06 | Showa Denko Kk | 電気二重層コンデンサ、該コンデンサに用いる電極用ペースト及び電極 |
JP2004290543A (ja) * | 2003-03-28 | 2004-10-21 | Nissan Chem Ind Ltd | アルデヒド類消臭剤組成物 |
JP2007035769A (ja) * | 2005-07-25 | 2007-02-08 | Tdk Corp | 電気化学素子用電極の製造方法および電気化学素子の製造方法 |
Family Cites Families (1)
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CN101160635B (zh) * | 2005-04-26 | 2010-12-15 | 日本瑞翁株式会社 | 电化学元件电极用复合粒子 |
-
2008
- 2008-03-26 JP JP2008080091A patent/JP5336752B2/ja not_active Expired - Fee Related
- 2008-03-27 KR KR1020097021034A patent/KR20090125167A/ko not_active Application Discontinuation
- 2008-03-27 EP EP08739754A patent/EP2144260A1/en not_active Withdrawn
- 2008-03-27 WO PCT/JP2008/056646 patent/WO2008123577A1/ja active Application Filing
- 2008-03-27 US US12/593,565 patent/US20100175822A1/en not_active Abandoned
- 2008-03-27 CN CN2008800099908A patent/CN101647078B/zh not_active Expired - Fee Related
- 2008-03-28 TW TW097111182A patent/TW200902142A/zh unknown
Patent Citations (6)
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JPS61292908A (ja) * | 1985-06-17 | 1986-12-23 | ザ スタンダ−ド オイル カンパニ− | 二重層コンデンサ−用の電極の製造法 |
JPH0845793A (ja) * | 1994-08-02 | 1996-02-16 | Asahi Glass Co Ltd | 電気二重層コンデンサ |
JPH0936005A (ja) | 1995-07-18 | 1997-02-07 | Toyota Motor Corp | 電気二重層キャパシタ用電極の製造方法 |
JP2002353074A (ja) * | 2001-05-28 | 2002-12-06 | Showa Denko Kk | 電気二重層コンデンサ、該コンデンサに用いる電極用ペースト及び電極 |
JP2004290543A (ja) * | 2003-03-28 | 2004-10-21 | Nissan Chem Ind Ltd | アルデヒド類消臭剤組成物 |
JP2007035769A (ja) * | 2005-07-25 | 2007-02-08 | Tdk Corp | 電気化学素子用電極の製造方法および電気化学素子の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US8332541B2 (en) | 2008-06-27 | 2012-12-11 | Qualcomm Incorporated | Methods and apparatus for communicating and/or using discovery information |
US20110292568A1 (en) * | 2008-11-28 | 2011-12-01 | Sumitomo Chemical Company, Limited | Electrode film, electrode, method for manufacturing the electrode, and electrical storage device |
Also Published As
Publication number | Publication date |
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CN101647078B (zh) | 2011-07-27 |
TW200902142A (en) | 2009-01-16 |
CN101647078A (zh) | 2010-02-10 |
KR20090125167A (ko) | 2009-12-03 |
JP5336752B2 (ja) | 2013-11-06 |
EP2144260A1 (en) | 2010-01-13 |
US20100175822A1 (en) | 2010-07-15 |
JP2008277784A (ja) | 2008-11-13 |
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