WO2010100954A1 - 電極材料及びこの電極材料を含有する電極 - Google Patents
電極材料及びこの電極材料を含有する電極 Download PDFInfo
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- WO2010100954A1 WO2010100954A1 PCT/JP2010/001623 JP2010001623W WO2010100954A1 WO 2010100954 A1 WO2010100954 A1 WO 2010100954A1 JP 2010001623 W JP2010001623 W JP 2010001623W WO 2010100954 A1 WO2010100954 A1 WO 2010100954A1
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- electrode material
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- electrode
- centrifugal force
- metal oxide
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- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000003273 ketjen black Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 9
- -1 titanium alkoxide Chemical class 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- 238000010303 mechanochemical reaction Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 238000000981 high-pressure carbon monoxide method Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/46—Metal oxides
-
- 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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
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- 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
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- 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 an electrode material and an electrode containing the electrode material.
- the present invention has been proposed in order to solve the above-described problems of the prior art, and an object of the present invention is to provide an electrode material capable of improving the capacity characteristics by reducing the content of the carbon material, and the electrode material.
- the object is to provide an electrode containing an electrode material.
- the present inventors have used a mechanochemical reaction described in the specification previously filed by the present applicant and the like, and have a specific surface area of 600 to 600 as a carbon material. It has been found that by using carbon nanotubes of 2600 m 2 / g (hereinafter referred to as SGCNT), an electrode material that can reduce the content of the carbon material and improve the capacity characteristics can be obtained.
- SGCNT carbon nanotubes of 2600 m 2 / g
- Carbon material SGCNT is preferably used as the carbon material constituting the electrode material according to the present invention.
- the above SGCNT is focused on for the following reason.
- carbon nanotubes having a specific surface area of 500 m 2 / g or less form bundles (bundles) due to strong van der Waals force and are micro-aggregated, so that it is difficult to achieve high dispersion.
- carbon nanotubes (SGCNT) as large as 600 to 2600 m 2 / g can be expected to be highly dispersed because there is almost no bundle formation or micro-aggregation due to van der Waals force.
- a material having a large specific surface area such as SGCNT used for the electrode material according to the present invention, is desirable in order to increase the capacitance of the electrochemical capacitor and to increase the energy density.
- the carbon nanotubes may be single-walled, double-walled, multi-walled with three or more layers, and may be mixed.
- the specific surface area of the carbon nanotube used for the electrode of the electrochemical capacitor has been about 500 m 2 / g at most, but the electrode material according to the present invention has a specific surface area to achieve the intended purpose.
- Such a large specific surface area of the carbon nanotubes can be achieved by using those in which bundles are not formed between the carbon nanotubes, or by selectively using very few carbon nanotubes even if they are formed.
- carbon nanotubes with no bundle or very few bundles can be obtained by using, for example, the methods described in Non-Patent Document 1, Non-Patent Document 2, and the like. Further, for commercially available HiPco (manufactured by Carbon Nanotechnologies) having a specific surface area of about several hundred m 2 / g, for example, a means for releasing the bundle structure as described in Non-Patent Document 3 is provided. It can also be obtained using the method of application.
- the SGCNT used in the present invention is preferably a single layer having a diameter of 2 to 4 nm, a length of 0.1 to 10 mm, and a purity of 80 to 99.98%. In the case of two or more layers, those having a diameter of 4 to 10 nm, a length of 0.1 to 10 mm and a purity of 80 to 99.98% are preferable.
- SGCNT used for the electrode material according to the present invention it is preferable to use a material having semiconducting properties in addition to having a large specific surface area as described above. The reason is that, when a capacitor using SGCNT for both electrodes is produced, a high capacity can be obtained when a high voltage is applied to the capacitor.
- the SGCNT used for the electrode material according to the present invention preferably has a density of 0.2 to 1.5 g / cm 3 . This is because if the density is too lower than this range, the material becomes mechanically brittle and sufficient mechanical strength cannot be obtained, and the capacity density per volume becomes low. On the other hand, if it is higher than this range, there is no space for the electrolytic solution to enter, resulting in a decrease in capacity density.
- the metal salt constituting the electrode material according to the present invention is preferably a metal alkoxide, and other examples include chloride salt, nitrate salt, sulfate salt and acetate salt.
- the metal alkoxide is preferably a titanium alkoxide, and preferably has a reaction rate constant of 10 ⁇ 5 mol ⁇ 1 sec ⁇ 1 or more for the hydrolysis reaction of the metal alkoxide. Examples of such metals include tin, zirconia, and cesium.
- reaction inhibitor By adding a predetermined compound that forms a complex with the metal alkoxide as a reaction inhibitor to the predetermined metal alkoxide to which the mechanochemical reaction described in Patent Document 1 is applied, the chemical reaction is prevented from being accelerated too much. can do.
- the reaction is suppressed by adding 1 to 3 mol of a predetermined compound such as acetic acid that forms a complex with metal alkoxide to 1 mol of the metal alkoxide to form a complex.
- a metal-oxide composite nano-particle for example, a lithium-titanium oxide composite nano-particle, which is a precursor of lithium titanate, is produced by firing this reaction. Thus, a crystal of lithium titanate is obtained.
- substances that can form a complex with a metal alkoxide include acetic acid, citric acid, succinic acid, formic acid, lactic acid, tartaric acid, fumaric acid, succinic acid, propionic acid, carboxylic acid such as propionic acid, and EDTA.
- complexing agents represented by amino alcohols such as aminopolycarboxylic acid and triethanolamine.
- the reaction method used in the present invention is a mechanochemical reaction similar to the method shown in Patent Document 1 previously filed by the applicant of the present application, and in a rotating reactor in the course of the chemical reaction.
- a chemical reaction is promoted by applying shear stress and centrifugal force to the reactant.
- the reactor which consists of a concentric cylinder of an outer cylinder and an inner cylinder, is equipped with a through-hole in the side surface of an inner cylinder, and arrange
- the reactant in the inner cylinder is moved to the inner wall surface of the outer cylinder through the through-hole of the inner cylinder by centrifugal force generated by the turning of the inner cylinder, and a thin film containing the reactant is generated on the inner wall surface of the outer cylinder.
- the thickness of the thin film is preferably 5 mm or less, and the centrifugal force applied to the reactant in the inner cylinder of the reactor is preferably 1500 N (kgms ⁇ 2 ) or more.
- the metal alkoxide, the reaction inhibitor, and SGCNT are charged into the inner cylinder of the reactor, and the inner cylinder is swirled to mix and disperse them. Further, while turning the inner cylinder, water is added to cause hydrolysis and condensation reaction to proceed to produce a metal oxide, and the metal oxide and SGCNT are mixed in a dispersed state. With the completion of the reaction, SGCNT in which metal oxide nanoparticles are supported in a highly dispersed state can be obtained.
- the dispersion, hydrolysis, and condensation reaction can proceed simultaneously.
- the metal oxide can be prevented from aggregating by rapidly heating from room temperature to 900 ° C. within 3 minutes in the baking step, crystalline nanoparticles having a small particle size can be formed.
- the carbon in which the metal oxide nanoparticles obtained by the present invention are highly dispersed and supported can be mixed and molded with a binder to form an electrode for an electrochemical element, that is, an electrode for storing electrical energy. Characteristics and high capacity characteristics.
- the electrochemical element that can use this electrode is an electrochemical capacitor or a battery that uses an electrolytic solution containing lithium ions. That is, the electrode of the present invention can occlude and desorb lithium ions and operates as a negative electrode. Therefore, an electrochemical capacitor and a battery can be formed by using an electrolytic solution containing lithium ions and using, as a counter electrode, activated carbon, an oxide or carbon that occludes and desorbs lithium, and the like.
- an electrode material capable of improving the capacity characteristics by lowering the content of the carbon material, and an electrode containing the electrode material.
- FIG. 3 is a drawing-substituting photograph showing a TEM image of the composite of Example 1.
- FIG. The figure which shows the result of the charging / discharging test using the electrode which concerns on this invention.
- Example 1 A mixed solvent was prepared by dissolving acetic acid and lithium acetate in an amount of 1.8 mol of acetic acid and 1 mol of lithium acetate in a mixture of isopropanol and water with respect to 1 mol of titanium alkoxide.
- This mixed solvent, titanium alkoxide, isopropyl alcohol, and SGCNT are put into a swirl reactor, and the inner cylinder is swirled for 5 minutes with a centrifugal force of 66,000 N (kgms -2 ) to form a thin film of reactant on the inner wall of the outer cylinder.
- a chemical reaction was promoted by applying shear stress and centrifugal force to the reaction product to obtain SGCNT carrying a highly dispersed lithium titanate precursor.
- the obtained SGCNT in which the lithium titanate precursor is highly dispersed and supported is dried in vacuum at 80 ° C. for 17 hours to obtain a composite powder in which the lithium titanate precursor is highly dispersed and supported in SGCNT. It was.
- Crystallization of the lithium titanate precursor is progressed by rapidly heating the obtained composite powder, in which the precursor of lithium titanate is highly dispersed in SGCNT, from room temperature to 900 ° C. within 3 minutes in a vacuum.
- a composite powder in which nanoparticles of lithium titanate were highly dispersed and supported on SGCNTs was obtained.
- the amount of titanium alkoxide and SGCNT charged into the swirl reactor was adjusted so that the weight ratio of lithium titanate to SGCNT was about 80:20.
- FIG. 1 A TEM image of the composite thus obtained is shown in FIG. In FIG. 1, it can be seen that 5 to 20 nm lithium titanate nanoparticles are highly dispersed and supported on SGCNT. *
- a mixed solvent was prepared by dissolving acetic acid and lithium acetate in an amount of 1.8 mol of acetic acid and 1 mol of lithium acetate in a mixture of isopropanol and water with respect to 1 mol of titanium alkoxide.
- ketjen black Ketjen Black International Co., Ltd., trade name: ketjen black EC600JD, porosity 78 Vol.%, Primary particle size 40 nm, average secondary particle size 337.8 nm
- Ketjen black carrying a highly dispersed lithium titanate precursor was dried at 80 ° C. for 17 hours in a vacuum to obtain a composite in which the lithium titanate precursor was carried highly dispersed by Ketjen black. A body powder was obtained.
- Comparative Example 2 The weight of ketjen black with respect to 1 mol of titanium alkoxide charged into the swirl reactor was increased to 4/3 times that of Comparative Example 1 to prepare a composite in which lithium titanate was supported on ketjen black. Other conditions are the same as in Comparative Example 1 above. The weight ratio of lithium titanate and ketjen black in Comparative Example 2 was about 60:40.
- FIG. 3 shows the capacity retention rate when the capacity at 1C is 100.
- Example 1 the output (capacity) at 100C shows an excellent rate characteristic of 89% of the capacity at 1C.
- the output (capacity) at 100 C was only a few percent of the capacity at 1 C.
- the output (capacity) at 100C was 80% of the capacity at 1C and the rate characteristics were good, but as shown in Table 1, in Comparative Example 2, the ratio of lithium titanate was as small as 60%, and it was found that the capacity per complex was smaller than that in Example 1.
- Example 1 it is known that when the carbon ratio is low, lithium titanate particles are close to each other and agglomerate, thereby increasing the particle diameter and lowering the output characteristics.
- Comparative Example 1 when the content of ketjen black is 20%, it has been confirmed that the lithium titanate particles are aggregated to increase the particle size and reduce the output characteristics.
- Example 1 it turned out that the outstanding output characteristic is acquired even if content of SGCNT is 20%.
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Abstract
Description
本発明に係る電極材料を構成するカーボン材料としては、SGCNTを用いることが好ましい。なお、本発明において、上記SGCNTに着目したのは、以下の理由による。すなわち、比表面積が500m2/g以下のカーボンナノチューブは、強固なファンデルワールス力によりバンドル(束)を形成し、ミクロ凝集しているため、高分散化が困難であったが、比表面積が600~2600m2/gと大きいカーボンナノチューブ(SGCNT)は、ファンデルワールス力によるバンドル(束)形成、ミクロ凝集がほとんどないため、高分散化が期待できるからである。
本発明に係る電極材料を構成する金属塩としては、金属アルコキシドが好ましく、その他に、塩化物塩、硝酸塩、硫酸塩、酢酸塩等を挙げることができる。また、前記金属アルコキシドとしては、チタンアルコキシドが好ましく、その他、金属アルコキシドの加水分解反応の反応速度定数が10-5mol-1sec-1以上のものが好ましい。このような金属としては、スズ、ジルコニア、セシウム等を挙げることができる。
上記特許文献1に記載されたメカノケミカル反応を適用する所定の金属アルコキシドに、反応抑制剤として該金属アルコキシドと錯体を形成する所定の化合物を添加することにより、化学反応が促進しすぎるのを抑制することができる。
なお、本発明で用いる反応方法は、本出願人等が先に特許出願した上記特許文献1に示した方法と同様のメカノケミカル反応であって、化学反応の過程で、旋回する反応器内で反応物にずり応力と遠心力を加えて化学反応を促進させるものである。
本発明により得られた金属酸化物ナノ粒子を高分散担持させたカーボンは、バインダーと混合、成型し、電気化学素子の電極、すなわち電気エネルギー貯蔵用電極とすることができ、この電極は高出力特性、高容量特性を示す。
(実施例1)
チタンアルコキシド1モルに対して、酢酸1.8モル、酢酸リチウム1モルとなる量の酢酸と酢酸リチウムをイソプロパノールと水の混合物に溶解して混合溶媒を作製した。この混合溶媒とチタンアルコキシド、イソプロピルアルコール、SGCNTを旋回反応器内に投入し、66,000N(kgms-2)の遠心力で5分間、内筒を旋回して外筒の内壁に反応物の薄膜を形成すると共に、反応物にずり応力と遠心力を加えて化学反応を促進させ、チタン酸リチウムの前駆体を高分散担持したSGCNTを得た。
チタンアルコキシド1モルに対して、酢酸1.8モル、酢酸リチウム1モルとなる量の酢酸と酢酸リチウムをイソプロパノールと水の混合物に溶解して混合溶媒を作製した。この混合溶媒とチタンアルコキシド、イソプロピルアルコール、ケッチェンブラック(ケッチェン・ブラック・インターナショナル社製、商品名:ケッチェンブラックEC600JD、空隙率78Vol.%、一次粒子径40nm、平均二次粒径337.8nm)を旋回反応器内に投入し、66,000N(kgms-2)の遠心力で5分間、内筒を旋回して外筒の内壁に反応物の薄膜を形成すると共に、反応物にずり応力と遠心力を加えて化学反応を促進させ、チタン酸リチウムの前駆体を高分散担持したケッチェンブラックを得た。
旋回反応器内に投入するチタンアルコキシド1molに対するケッチェンブラックの重量を比較例1の4/3倍に増加させて、チタン酸リチウムがケッチェンブラックに坦持された複合体を作製した。その他の条件は上記比較例1と同様である。なお、比較例2におけるチタン酸リチウムとケッチェンブラックの重量比は約60:40であった。
(1)充放電挙動
実施例1で得られた複合体粉末8重量部と、2重量部のPVdF(ポリビニリデンフルオライド)をNMP(N-メチルピロリドン)溶液中で混合し、スラリーを作製した。作製したスラリーを銅箔上に塗布し、真空中、100℃で4時間乾燥することによって電極を作製した。得られた電極に、対極としてリチウム箔をセパレータを介して対向させ、電解液として1M LiBF4/EC:DMC(vol.1:1)を注入することによって、コインタイプのセルを作製した。また、比較例1及び比較例2で得られた複合体についても、同様にしてセルを作製した。
実施例1、比較例1及び比較例2で得られた複合体粉末8重量部と、2重量部のPVdF(ポリビニリデンフルオライド)をNMP(N-メチルピロリドン)溶液中で混合し、スラリーを作製した。作製したスラリーを銅箔上に塗布し、真空中、100℃で4時間乾燥することによって電極を作製した。得られた電極に、対極としてリチウム箔をセパレータを介して対向させ、電解液として1M LiBF4/EC:DMC(vol.1:1)を注入することによって、コインタイプのセルを作製した。作製したセルについて、電圧範囲1.0~3.0V、Cレート範囲1~100Cでの充放電測定を行ったところ、図3に示すような結果が得られた。なお、図3は、1Cでの容量を100とした場合の容量維持率を示したものである。
Claims (9)
- 化学反応の過程で、旋回する反応器内で反応抑制剤を含む反応物にずり応力と遠心力を加えて生成した金属酸化物ナノ粒子と、旋回する反応器内でずり応力と遠心力を加えて分散した比表面積が600~2600m2/gであるカーボンナノチューブとからなり、前記金属酸化物ナノ粒子を前記カーボンナノチューブに高分散担持させたことを特徴とする電極材料。
- 前記旋回する反応器内で、反応抑制剤を含む反応物を含む薄膜を生成し、この薄膜にずり応力と遠心力を加えて化学反応を促進、制御させたことを特徴とする請求項1に記載の電極材料。
- 前記反応器が、外筒と内筒の同心円筒からなり、内筒の側面に貫通孔を備えるとともに、外筒の開口部にせき板を配置してなり、内筒の旋回による遠心力によって、内筒内の反応抑制剤を含む反応物を内筒の貫通孔を通じて外筒の内壁面に移動させ、外筒の内壁面に反応抑制剤を含む反応物を含む薄膜を生成させると共に、この薄膜にずり応力と遠心力を加えて化学反応を促進、制御させたことを特徴とする請求項2に記載の電極材料。
- 前記薄膜が、その厚さが5mm以下であることを特徴とする請求項2又は請求項3に記載の電極材料。
- 前記反応器の内筒内の反応物に加えられる遠心力が、1500N(kgms-2)以上であることを特徴とする請求項1乃至請求項4のいずれか1項に記載の電極材料。
- 前記化学反応が、金属塩の加水分解反応および/または縮合反応であることを特徴とする請求項1乃至請求項5のいずれか1項に記載の電極材料。
- 前記金属酸化物が、チタン酸リチウムであることを特徴とする請求項1乃至請求項6のいずれか1項に記載の電極材料。
- 請求項1乃至請求項7のいずれか1項に記載の電極材料を含有することを特徴とする電極。
- 前記金属酸化物が、チタン酸リチウムであることを特徴とする請求項8に記載の電極。
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WO2013047832A1 (ja) * | 2011-09-30 | 2013-04-04 | 日本ケミコン株式会社 | 金属酸化物とカーボンナノチューブとの複合体、その製造方法、この複合体を用いた電極及び電気化学素子 |
CN103907224A (zh) * | 2011-10-29 | 2014-07-02 | 日本贵弥功株式会社 | 片材状复合体、其制造方法、使用了该复合体的电极及电化学元件 |
EP2772967A4 (en) * | 2011-10-29 | 2015-05-20 | Nippon Chemicon | FILM-COMPOSITE COMPOSITE, METHOD OF MANUFACTURING THEREOF AND ELECTRODE AND ELECTROCHEMICAL ELEMENT WITH THIS COMPOSITE |
EP2772927A4 (en) * | 2011-10-29 | 2015-05-20 | Nippon Chemicon | SHEET-LIKE COMPOSITE, METHOD FOR MANUFACTURING SAME, ELECTRODE, AND ELECTROCHEMICAL ELEMENT USING SAME-LIKE COMPOSITE |
WO2014129540A1 (ja) * | 2013-02-20 | 2014-08-28 | 日本ケミコン株式会社 | 電極、その電極を用いた電気二重層キャパシタ、及び電極の製造方法 |
JPWO2014129540A1 (ja) * | 2013-02-20 | 2017-02-02 | 日本ケミコン株式会社 | 電極、その電極を用いた電気二重層キャパシタ、及び電極の製造方法 |
TWI620214B (zh) * | 2013-02-20 | 2018-04-01 | Nippon Chemicon | 電極、使用該電極的電雙層電容器及電極之製造方法 |
US9997301B2 (en) | 2013-02-20 | 2018-06-12 | Nippon Chemi-Con Corporation | Electrode, electric double-layer capacitor using the same, and manufacturing method of the electrode |
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CN102439671A (zh) | 2012-05-02 |
EP2405452A4 (en) | 2013-04-17 |
KR20110123799A (ko) | 2011-11-15 |
US20120132861A1 (en) | 2012-05-31 |
EP2405452A1 (en) | 2012-01-11 |
JP2010212309A (ja) | 2010-09-24 |
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