WO2015115201A1 - Electrode for electrochemical elements, and electrochemical element - Google Patents
Electrode for electrochemical elements, and electrochemical element Download PDFInfo
- Publication number
- WO2015115201A1 WO2015115201A1 PCT/JP2015/051005 JP2015051005W WO2015115201A1 WO 2015115201 A1 WO2015115201 A1 WO 2015115201A1 JP 2015051005 W JP2015051005 W JP 2015051005W WO 2015115201 A1 WO2015115201 A1 WO 2015115201A1
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- Prior art keywords
- electrode
- active material
- electrode active
- parts
- binder
- Prior art date
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- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910014195 BM-400B Inorganic materials 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RZEMOZGCDJJSLV-UHFFFAOYSA-N [S].CS(C)=O Chemical compound [S].CS(C)=O RZEMOZGCDJJSLV-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UBTITNUVKXQFBF-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCS(O)(=O)=O UBTITNUVKXQFBF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- AUCOQXJDRCYQCE-UHFFFAOYSA-N hepta-1,4-dien-3-one Chemical class CCC=CC(=O)C=C AUCOQXJDRCYQCE-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an electrode for an electrochemical element and an electrochemical element.
- Electrochemical elements such as lithium ion secondary batteries that are small and lightweight, have high energy density, and can be repeatedly charged and discharged are rapidly expanding their demands by taking advantage of their characteristics.
- Lithium ion secondary batteries are used in fields such as mobile phones, notebook personal computers, and electric vehicles because of their relatively high energy density.
- electrochemical elements are required to be further improved in accordance with expansion and development of applications, such as lowering resistance, increasing capacity, improving mechanical properties and productivity. Under such circumstances, there is a demand for a more productive manufacturing method for electrochemical element electrodes, and various improvements have been made regarding the manufacturing method capable of high-speed molding and the materials for electrochemical element electrodes suitable for the manufacturing method. Has been done.
- An electrode for an electrochemical element is usually formed by laminating an electrode active material layer formed by binding an electrode active material and a conductive material used as necessary with a binder on a current collector. is there.
- an intermediate layer such as an adhesive layer for improving adhesion and a rust prevention layer for rust prevention is also provided between the electrode active material layer and the current collector.
- Patent Document 1 discloses that a current collector made of copper that has been subjected to roughening treatment is subjected to rust prevention treatment, and then an electrode active material layer is formed using a slurry containing a negative electrode active material and a binder. .
- Patent Document 2 discloses that a conductive coating film formed by a conductive coating solution containing a polymer having a hydroxyl group and / or an amino acid and a conductive filler is formed on a current collector, and then an electrode active material and It is disclosed that an electrode active material layer is formed using a slurry containing a binder.
- An object of the present invention is to provide an electrode for an electrochemical element and an electrochemical element that are excellent in adhesion between a current collector and an electrode active material layer and that are excellent in durability.
- the present inventor has found that the above object can be achieved by specifying a specific combination of the material contained in the intermediate layer and the composition of the binder contained in the electrode active material layer. It came to be completed.
- the binder has an acid group-containing monomer unit of 0.1 to 10% by weight, and the content of the binder in the electrode active material layer is 0.1 to 20 with respect to 100 parts by weight of the electrode active material.
- Electrode for an electrochemical element that is part by weight (2) The electrode for an electrochemical element according to (1), wherein the cationic compound has a number average molecular weight of 10,000 to 2,000,000.
- An electrochemical element comprising the electrode for an electrochemical element according to any one of (1) to (4), a separator, and an electrolytic solution, (6)
- an electrode for an electrochemical element and an electrochemical element that are excellent in the adhesion between the current collector and the electrode active material layer, and further excellent in durability.
- the electrode for an electrochemical device of the present invention is an electrode for an electrochemical device in which an electrode active material layer containing an electrode active material and a binder is formed on a current collector, and the electrode for the electrochemical device is cationic on the current collector.
- An anchor layer containing a compound, the binder has an acid group-containing monomer unit of 0.1 to 10% by weight, and the binder content in the electrode active material layer is 100 parts by weight of the electrode active material. The amount is 0.1 to 20 parts by weight.
- the electrode for an electrochemical device of the present invention can be obtained by forming an anchor layer on a current collector and further forming an electrode active material layer on the current collector on which the anchor layer is formed.
- the material of the current collector is, for example, metal, carbon, conductive polymer, etc., and metal is preferably used.
- As the current collector metal aluminum, platinum, nickel, tantalum, titanium, stainless steel, copper, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance.
- the thickness of the current collector is preferably 5 to 100 ⁇ m, more preferably 8 to 70 ⁇ m, and still more preferably 10 to 50 ⁇ m.
- the electrode for an electrochemical element of the present invention includes an anchor layer.
- the anchor layer includes a cationic compound.
- a primary amine compound As the cationic compound contained in the anchor layer, a primary amine compound, a secondary amine compound (imino group-containing compound), a tertiary amine compound, a compound modified with a cationizing agent, or the like can be used. Of these, an imino group-containing compound and a compound modified with a cationizing agent are preferable.
- An imino group-containing compound is a compound having an imino group, and the nitrogen atom of the imino group may be bonded to the same carbon atom by a double bond, or may be bonded to a separate carbon atom by a single bond. May be.
- the imino group-containing compound a low molecular imino group-containing compound or a high molecular imino group-containing compound may be used.
- the low molecular imino group-containing compound include chain imino group-containing compounds such as dimethylamine, diethylamine, and dipropylamine; cyclic imino group-containing compounds such as ethyleneimine, propyleneimine, pyrrolidine, piperidine, and piperazine. It is done.
- polymer imino group-containing compound examples include polyethyleneimine; polyethyleneimine derivatives such as poly N-hydroxylethyleneimine and carboxymethylated polyethyleneimine / sodium salt; polypropyleneimine; polyN-2-dihydroxypropyleneimine And the like, and the like, and the like.
- a polymer imino group-containing compound is preferable, and polyethyleneimine is more preferable.
- an imino group containing compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- Examples of the compound modified with a cationizing agent include cationized cellulose and the like obtained by modifying a cellulose compound such as hydroxyethyl cellulose and carboxymethyl cellulose with a cationizing agent.
- the number average molecular weight of the cationic compound is preferably 100 to 2,000,000, and more preferably 10,000 to 2,000,000.
- the number average molecular weight of the cationic compound can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- the method for forming the anchor layer is not particularly limited, but the anchor layer is formed by applying a coating solution for an anchor layer in which a cationic compound is dispersed or dissolved in a solvent such as water on a current collector and drying it. be able to. Further, the concentration can be appropriately adjusted according to the coating method of the cationic compound in the anchor layer coating solution.
- the method for applying the anchor layer coating solution is not particularly limited.
- the anchor layer is formed on the current collector by a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a die coating method, a brush coating, or the like. Further, after forming an adhesive layer on the release paper, it may be transferred to a current collector.
- examples of the method for drying the anchor layer coating solution coated on the current collector include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. Can be mentioned. Of these, a drying method using hot air and a drying method using irradiation with far infrared rays are preferable.
- the drying temperature and the drying time are preferably a temperature and a time at which the solvent in the current collector coating adhesive coating solution coated on the current collector can be completely removed.
- the drying temperature is usually 50 to 300 ° C., preferably 80 ° C. ⁇ 250 ° C.
- the drying time is usually 2 hours or less, preferably 5 seconds to 30 minutes.
- the thickness of the anchor layer is preferably 0.01 ⁇ m or more and less than 10 ⁇ m, more preferably 0.01 ⁇ m or more and 2 ⁇ m, from the viewpoint of obtaining an electrode having good adhesion to the electrode active material layer described later and low resistance. Less than, more preferably 0.01 ⁇ m or more and less than 1 ⁇ m.
- the electrode for an electrochemical element of the present invention includes an electrode active material layer, and the electrode active material layer includes an electrode active material, a binder, a thickener used as necessary, and a conductive additive.
- the binder content in the electrode active material layer is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the electrode active material. It is.
- the electrode active material layer is formed by applying and drying an electrode slurry containing an electrode active material, a binder, a thickener used as necessary, and a conductive auxiliary agent on the anchor layer of the current collector on which the anchor layer is formed. Is formed.
- the method for applying the electrode slurry onto the anchor layer formed on the current collector is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a comma direct coating, a slide die coating, and a brush coating method.
- the drying method include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
- the drying time is usually 1 to 60 minutes, and the drying temperature is usually 40 to 180 ° C.
- the electrode active material layer may be formed by repeating application and drying of the electrode slurry a plurality of times.
- the electrode slurry can be obtained by mixing an electrode active material, a binder, a thickener and a conductive aid used as necessary, and a solvent such as water.
- the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
- a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
- the electrode active material (positive electrode active material) of the positive electrode for the lithium ion secondary battery includes a metal oxide capable of reversibly doping and dedoping lithium ions. It is done. Examples of the metal oxide include lithium cobaltate, lithium nickelate, lithium manganate, and lithium iron phosphate.
- the positive electrode active material illustrated above may be used independently according to a use, and may be used in mixture of multiple types.
- the negative electrode active material (negative electrode active material) as the counter electrode of the positive electrode for a lithium ion secondary battery
- low crystalline carbon non-graphitizable carbon, non-graphitizable carbon, pyrolytic carbon, etc.
- Crystalline carbon graphite (natural graphite, artificial graphite)
- alloy materials such as tin and silicon, oxides such as silicon oxide, tin oxide, and lithium titanate.
- the negative electrode active material illustrated above may be used independently according to a use suitably, and may be used in mixture of multiple types.
- the shape of the electrode active material of the electrode for a lithium ion secondary battery is preferably a granulated particle.
- a higher-density electrode can be formed during electrode molding.
- the volume average particle diameter of the electrode active material of the electrode for a lithium ion secondary battery is usually 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, more preferably 0.8 to 30 ⁇ m for both the positive electrode and the negative electrode.
- Examples of the negative electrode active material preferably used when the electrochemical element is a lithium ion capacitor include low crystalline carbon (amorphous carbon such as graphitizable carbon, non-graphitizable carbon, and pyrolytic carbon). ), Graphite (natural graphite, artificial graphite) and the like, and negative electrode active materials formed of carbon.
- the positive electrode active material when the electrochemical element is a lithium ion capacitor
- any material can be used as long as it can reversibly carry lithium ions and anions such as tetrafluoroborate.
- an allotrope of carbon can be preferably used.
- Specific examples of the allotrope of carbon include activated carbon, polyacene (PAS), carbon whisker, carbon nanotube, and graphite.
- the binder used in the present invention is a component for adhering electrode active materials to each other, and is usually used in the form of a solution or dispersion in which polymer particles having binding properties are dissolved or dispersed in a solvent such as water.
- binder used in the present invention examples include diene polymers and acrylic polymers.
- the diene polymer is a polymer containing monomer units obtained by polymerizing conjugated dienes such as butadiene and isoprene.
- the proportion of monomer units obtained by polymerizing conjugated diene in the diene polymer is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.
- Examples of the polymer include homopolymers of conjugated dienes such as polybutadiene and polyisoprene; and copolymers of monomers that are copolymerizable with conjugated dienes.
- Examples of the copolymerizable monomer include ⁇ , ⁇ -unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; styrene, chlorostyrene, vinyltoluene, and t-butyl.
- Styrene monomers such as styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene and divinyl benzene; olefins such as ethylene and propylene; vinyl chloride and vinylidene chloride Halogen atom-containing monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl Vinyl ketones such as ketone, butyl vinyl ketone, hexyl vinyl ketone, and isopropenyl vinyl ketone; and heterocyclic ring-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine, and vinyl imidazole.
- the acrylic polymer is a polymer containing a monomer unit obtained by polymerizing an acrylic ester and / or a methacrylic ester.
- the proportion of monomer units obtained by polymerizing acrylic acid ester and / or methacrylic acid ester in the acrylic polymer is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.
- Examples of the polymer include homopolymers of acrylic acid esters and / or methacrylic acid esters, and copolymers with monomers copolymerizable therewith.
- Examples of the copolymerizable monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; two or more carbons such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate.
- unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid
- two or more carbons such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate.
- Carboxylates having carbon double bonds including styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene, Styrenic monomers such as divinylbenzene; Amide monomers such as acrylamide, N-methylolacrylamide, and acrylamide-2-methylpropanesulfonic acid; ⁇ , ⁇ -insoluble such as acrylonitrile and methacrylonitrile Nitrile compounds; olefins such as ethylene and propylene; diene monomers such as butadiene and isoprene; monomers containing halogen atoms such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Vinyl esters such as methyl vinyl
- styrene-butadiene copolymer acrylonitrile-butadiene copolymer, and acrylic polymer are preferable because of excellent adhesion, and styrene-butadiene copolymer and acrylic polymer are more preferable.
- the binder used in the present invention further contains an acid group-containing monomer unit.
- the acid group-containing monomer that leads to the acid group-containing monomer unit include: —COOH group (carboxyl group); —SO 3 H group (sulfonic acid group); —PO 3 H 2 group and —PO (OH ) (OR) groups (wherein R represents a hydrocarbon group) or the like; monomers having an acid group such as;
- Examples of the monomer having a carboxyl group include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and derivatives thereof.
- Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, and isocrotonic acid.
- Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and methylmaleic acid.
- Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride and the like.
- Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide-2. -Methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, 2- (N-acryloyl) amino-2-methyl-1,3-propane-disulfonic acid and the like.
- “(meth) acryl” means “acryl” or “methacryl”.
- Examples of the monomer having a phosphoric acid group such as —PO 3 H 2 group and —PO (OH) (OR) group (R represents a hydrocarbon group) include, for example, phosphoric acid-2- (meth) acryloyloxy Examples thereof include ethyl, phosphoric acid methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl.
- “(meth) acryloyl” means “acryloyl” or “methacryloyl”.
- the salt of the monomer mentioned above can also be used as an acid group-containing monomer.
- the acid group-containing monomer one type may be used alone, or two or more types may be used in combination at any ratio.
- different types of monomers containing the same type of acidic group may be used in combination.
- monomers containing different types of acidic groups may be used in combination.
- the content of the acid group-containing monomer unit in the binder used in the present invention is 0.1 to 10% by weight, preferably 0.2 to 9% by weight, more preferably 0.3 to 8% by weight.
- the electrode active material layer of the present invention may contain a thickener as necessary.
- thickeners include cellulosic polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; ) Polyvinyl alcohols such as polyvinyl alcohol, copolymers of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or copolymers of maleic acid or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified Examples thereof include polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, acrylonitrile-butadiene copolymer hydride, and the like. Among these, it is preferable to use carboxymethylcellulose, ammonium salt of carboxymethylcellulose, and alkali metal salt.
- the content of the thickener in the electrode active material layer is preferably within a range not affecting the battery characteristics, and is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 0.2 parts by weight with respect to 100 parts by weight of the electrode active material.
- the amount is 4 parts by weight, more preferably 0.3 to 3 parts by weight.
- the electrode active material layer of the present invention may contain a conductive additive as necessary.
- the conductive auxiliary agent is not particularly limited as long as it is a conductive material, but a conductive particulate material is preferable.
- conductive carbon black such as furnace black, acetylene black, and ketjen black
- natural And graphite such as graphite and artificial graphite
- carbon fibers such as polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and vapor grown carbon fiber.
- the average particle diameter when the conductive assistant is a particulate material is not particularly limited, but is preferably smaller than the average particle diameter of the electrode active material, from the viewpoint of expressing sufficient conductivity with a smaller amount of use.
- the thickness is preferably 0.001 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and still more preferably 0.1 to 1 ⁇ m.
- Electrochemical element Examples of usage of the electrode for an electrochemical element of the present invention include a lithium ion secondary battery and a lithium ion capacitor using such an electrode, and a lithium ion secondary battery is preferable.
- a lithium ion secondary battery uses an electrode for an electrochemical element obtained as described above as at least one of a positive electrode and a negative electrode, and further includes a separator and an electrolytic solution.
- a polyolefin resin such as polyethylene or polypropylene
- a microporous film or nonwoven fabric containing an aromatic polyamide resin a porous resin coat containing an inorganic ceramic powder, or the like
- a porous resin coat containing an inorganic ceramic powder, or the like can be used.
- the thickness of the separator is preferably 0.5 to 40 ⁇ m, more preferably from the viewpoint of reducing resistance due to the separator in the lithium ion secondary battery and excellent workability when manufacturing the lithium ion secondary battery.
- the thickness is 1 to 30 ⁇ m, more preferably 1 to 25 ⁇ m.
- the electrolytic solution is not particularly limited.
- a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used.
- the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more.
- the amount of the supporting electrolyte is usually 1 wt. % Or more, preferably 5 wt. % Or more, and usually 30 wt. % Or less, preferably 20 wt. % Or less. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered, and the charging characteristics and discharging characteristics of the battery are degraded.
- the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
- Alkyl carbonates such as carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds are used.
- dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These can be used alone or in admixture of two or more. Moreover, it is also possible to use an electrolyte containing an additive.
- the additive is preferably a carbonate compound such as vinylene carbonate (VC).
- electrolytic solutions include gel polymer electrolytes in which a polymer electrolyte such as polyethylene oxide or polyacrylonitrile is impregnated with an electrolytic solution, lithium sulfide, LiI, Li 3 N, Li 2 SP—P 2 S 5 glass ceramic, etc.
- An inorganic solid electrolyte can be mentioned.
- a lithium ion secondary battery is obtained by stacking a negative electrode and a positive electrode through a separator, winding this according to the shape of the battery, folding it into a battery container, pouring the electrolyte into the battery container and sealing it. It is done. Further, if necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
- the shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
- an electrode for an electrochemical element and an electrochemical element that are excellent in the adhesion between the current collector and the electrode active material layer, and further excellent in durability.
- Adhesiveness (1-1) Peel strength
- the electrodes for lithium ion secondary batteries produced in the examples and comparative examples were cut into rectangles having a length of 100 mm and a width of 10 mm to form test pieces with the electrode active material layer surface facing down.
- the measurement was performed three times, the average value was obtained and this was taken as the peel strength, and the results are shown in Tables 1 and 2. The higher the peel strength, the greater the binding force of the electrode active material layer to the anchor layer, that is, the higher the adhesion strength.
- the cationic compound was dissolved in dimethylformamide to prepare a 1% solution.
- GPC measurement was performed using polystyrene as a standard substance, and using a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide as a developing solvent.
- the GPC measuring device is HLC-8220GPC (manufactured by Tosoh Corporation), the detector is HLC-8320GPC RI detector (manufactured by Tosoh Corporation), the measuring column is TSKgel SuperHZM-M (manufactured by Tosoh Corporation), and the measurement temperature is measured. Measurement was performed at 40 ° C., a developing solvent flow rate of 0.6 mL / min, and a sample injection amount of 20 ⁇ l.
- Example 1 Manufacture of anchor layer
- Polyethyleneimine (Epomin, Nippon Shokubai Co., Ltd., number average molecular weight 700,000, 30% solid content aqueous solution) is discharged from a die onto a 12 ⁇ m thick copper current collector as a cationic compound, at a molding speed of 30 m / min.
- the current collector was applied on one side and dried at 120 ° C. for 5 minutes to form an anchor layer having a thickness of 0.5 ⁇ m.
- the reaction was stopped by cooling to obtain a mixture containing particulate negative electrode binder (styrene-butadiene copolymer (SBR)).
- SBR styrene-butadiene copolymer
- the unreacted monomer is removed by heating under reduced pressure, and then cooled to 30 ° C or lower.
- An aqueous dispersion containing the desired particulate negative electrode binder was obtained.
- the negative electrode slurry obtained above was applied with a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material before pressing.
- the negative electrode original fabric before pressing was rolled with a roll press to obtain a negative electrode for a lithium ion secondary battery after pressing (hereinafter, also referred to as “negative electrode”) having a negative electrode composition layer thickness of 80 ⁇ m.
- LiCoO 2 LiCoO 2
- PVDF polyvinylidene fluoride
- KF-1100 polyvinylidene fluoride
- N-methylpyrrolidone 6 parts of acetylene black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) and 20 parts of N-methylpyrrolidone were added and mixed with a planetary mixer to obtain a positive electrode slurry.
- This positive electrode slurry is applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 30 minutes, and then roll-pressed to form a positive electrode for a lithium ion secondary battery having a thickness of 60 ⁇ m (hereinafter, referred to as “positive electrode”). )
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut out to 55 ⁇ 5.5 cm 2 .
- Example 2 Production of anchor layer, production of negative electrode slurry, production of negative electrode in the same manner as in Example 1 except that the amount of itaconic acid was 0.2 parts and the amount of styrene was 63.8 parts in the production of the negative electrode binder. And the lithium ion secondary battery was manufactured.
- Example 3 In the production of the negative electrode binder, the anchor layer was produced in the same manner as in Example 1 except that the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 9.5 parts, and the amount of styrene was 59.5 parts. The production of slurry for negative electrode, the production of negative electrode and the production of lithium ion secondary battery were carried out.
- Example 4 In the production of the negative electrode slurry, the production of the anchor layer, the production of the negative electrode, and the lithium ion secondary were the same as in Example 1 except that the amount of the particulate negative electrode binder used was 0.2 parts in terms of solid content. The battery was manufactured.
- Example 5 In the production of the negative electrode slurry, the anchor layer, the negative electrode, and the lithium ion secondary battery were produced in the same manner as in Example 1 except that the amount of the particulate binder was 18 parts in terms of solid content. .
- Example 6 In the production of the negative electrode binder, in the same manner as in Example 1, except that sodium styrenesulfonate (hereinafter sometimes referred to as “NaSS”) was used instead of itaconic acid, production of the anchor layer and production of the negative electrode slurry were performed. The negative electrode and the lithium ion secondary battery were manufactured.
- NaSS sodium styrenesulfonate
- Example 7 In the production of the binder for the negative electrode, except that methyl-2-methacryloyloxyethyl phosphate was used instead of itaconic acid, the production of the anchor layer, the production of the slurry for the negative electrode, the production of the negative electrode, and lithium were performed in the same manner as in Example 1. An ion secondary battery was manufactured.
- Example 8 In the production of the anchor layer, as in Example 1, except that carboxymethylated polyethyleneimine sodium salt (number average molecular weight 50000, solid content concentration 3% aqueous solution) was used as the cationic compound instead of polyethyleneimine. Production of a slurry, production of a negative electrode, and production of a lithium ion secondary battery were performed.
- carboxymethylated polyethyleneimine sodium salt number average molecular weight 50000, solid content concentration 3% aqueous solution
- Example 9 In the production of the anchor layer, as in Example 1, except that cationized cellulose (poise C-60H, number average molecular weight 600000, solid content concentration 3% aqueous solution) was used instead of polyethyleneimine as the cationic compound. Production of a slurry, production of a negative electrode, and production of a lithium ion secondary battery were performed.
- cationized cellulose poise C-60H, number average molecular weight 600000, solid content concentration 3% aqueous solution
- Example 10 Manufacture of anchor layer
- Polyethyleneimine epomine, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 700,000, 30% solid content aqueous solution
- the current collector was applied on one side and dried at 120 ° C. for 5 minutes to form an anchor layer having a thickness of 0.5 ⁇ m.
- the reaction was stopped by cooling to obtain a mixture containing particulate positive electrode binder (acrylic polymer (ACL)).
- ACL acrylic polymer
- the unreacted monomer is removed by heating under reduced pressure, and then cooled to 30 ° C or lower.
- an aqueous dispersion containing a desired positive electrode binder was obtained.
- the above-mentioned mixed solution was charged with 3 parts of the positive electrode binder (solid content standard) produced above and ion-exchanged water, adjusted to a final solid content concentration of 54%, and further mixed for 10 minutes. This was defoamed under reduced pressure to obtain a positive electrode slurry having good fluidity.
- the positive electrode slurry was applied onto the aluminum current collector having the anchor layer with a comma coater so that the film thickness after drying was about 150 ⁇ m and dried. This drying was performed by transporting the aluminum foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Then, it heat-processed for 2 minutes at 120 degreeC, and obtained the positive electrode.
- the positive electrode raw material before pressing was rolled by a roll press to obtain a positive electrode after pressing with a positive electrode active material layer having a thickness of 80 ⁇ m.
- ion exchange water was added so as to have a solid content concentration of 50%, and mixed and dispersed to obtain a negative electrode slurry, which was applied to a copper foil having a thickness of 18 ⁇ m and dried at 120 ° C. for 30 minutes. Thereafter, roll pressing was performed to obtain a negative electrode having a thickness of 50 ⁇ m.
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut out to 55 ⁇ 5.5 cm 2 .
- the anchor layer was produced in the same manner as in Example 1, except that the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 11.0 parts, and the amount of styrene was 58 parts. Slurry production, negative electrode production and lithium ion secondary battery production were carried out.
- Example 2 In the production of the negative electrode slurry, the production of the anchor layer, the production of the negative electrode, and the lithium ion secondary battery was the same as in Example 1 except that the amount of the particulate negative electrode binder used was 22 parts in terms of solid content. Manufactured.
- Example 3 In the production of the negative electrode binder, the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 11.0 parts, and the amount of styrene was 58 parts.
- An anchor layer, a negative electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the amount was 22 parts in terms of solid content.
- Example 4 In the production of the negative electrode binder, the anchor layer was produced in the same manner as in Example 1, except that itaconic acid was not used and the amount of 1,3-butadiene was 34 parts and the amount of styrene was 65 parts. , Negative electrode, and lithium ion secondary battery.
- the anchor layer slurry was discharged from a die onto a 12 ⁇ m thick copper current collector, applied to one side of the current collector at a molding speed of 30 m / min, and dried at 120 ° C. for 5 minutes to obtain a thickness of 0 An anchor layer of 0.5 ⁇ m was formed. Except for using a copper current collector having an anchor layer containing the conductive filler, a negative electrode slurry, a negative electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1.
- an electrode for an electrochemical device in which an electrode active material layer containing an electrode active material and a binder is formed on a current collector, the cationic current on the current collector
- An anchor layer containing a compound, the binder has an acid group-containing monomer unit of 0.1 to 10% by weight, and the binder content in the electrode active material layer is 100 parts by weight of the electrode active material.
- the adhesion of the electrode for an electrochemical element which is 0.1 to 20 parts by weight, was good, and the durability and low-temperature characteristics of a lithium ion secondary battery using this electrode for an electrochemical element were good. .
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Abstract
Description
本発明の目的は、集電体と電極活物質層との密着力に優れ、さらに耐久性に優れた電気化学素子用電極及び電気化学素子を提供することである。 However, the electrode for an electrochemical element described in Patent Document 1 does not have sufficient adhesion between the current collector and the electrode active material layer. In addition, the electrochemical device including the electrode for an electrochemical device described in Patent Document 2 has not been sufficiently durable.
An object of the present invention is to provide an electrode for an electrochemical element and an electrochemical element that are excellent in adhesion between a current collector and an electrode active material layer and that are excellent in durability.
(1) 集電体上に、電極活物質およびバインダーを含む電極活物質層が形成されてなる電気化学素子用電極であって、前記集電体上に、カチオン性化合物を含むアンカー層を有し、前記バインダーは酸基含有単量体単位を0.1~10重量%有し、前記電極活物質層中の前記バインダーの含有割合が電極活物質100重量部に対して0.1~20重量部である、電気化学素子用電極、
(2) 前記カチオン性化合物の数平均分子量が、10000~2000000である(1)記載の電気化学素子用電極、
(3) 前記アンカー層の厚みが、0.01μm以上1μm未満である(1)または(2)記載の電気化学素子用電極、
(4) 前記酸基含有単量体単位が、カルボキシル基、スルホン酸基、リン酸基のいずれかを含む(1)~(3)のいずれかに記載の電気化学素子用電極、
(5) (1)~(4)のいずれかに記載の電気化学素子用電極、セパレーターおよび電解液を含む電気化学素子、
(6) 前記電気化学素子が、リチウムイオン二次電池である(5)記載の電気化学素子、
が提供される。 That is, according to the present invention,
(1) An electrode for an electrochemical element in which an electrode active material layer containing an electrode active material and a binder is formed on a current collector, and an anchor layer containing a cationic compound is provided on the current collector. The binder has an acid group-containing monomer unit of 0.1 to 10% by weight, and the content of the binder in the electrode active material layer is 0.1 to 20 with respect to 100 parts by weight of the electrode active material. Electrode for an electrochemical element that is part by weight,
(2) The electrode for an electrochemical element according to (1), wherein the cationic compound has a number average molecular weight of 10,000 to 2,000,000.
(3) The electrode for an electrochemical element according to (1) or (2), wherein the anchor layer has a thickness of 0.01 μm or more and less than 1 μm.
(4) The electrode for an electrochemical element according to any one of (1) to (3), wherein the acid group-containing monomer unit contains any of a carboxyl group, a sulfonic acid group, and a phosphoric acid group,
(5) An electrochemical element comprising the electrode for an electrochemical element according to any one of (1) to (4), a separator, and an electrolytic solution,
(6) The electrochemical device according to (5), wherein the electrochemical device is a lithium ion secondary battery,
Is provided.
本発明の電気化学素子用電極は、集電体上にアンカー層を形成し、さらにアンカー層が形成された集電体上に電極活物質層を形成することにより得られる。 (Electrodes for electrochemical devices)
The electrode for an electrochemical device of the present invention can be obtained by forming an anchor layer on a current collector and further forming an electrode active material layer on the current collector on which the anchor layer is formed.
集電体の厚みは、好ましくは5~100μm、より好ましくは8~70μm、さらに好ましくは10~50μmである。 The material of the current collector is, for example, metal, carbon, conductive polymer, etc., and metal is preferably used. As the current collector metal, aluminum, platinum, nickel, tantalum, titanium, stainless steel, copper, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance.
The thickness of the current collector is preferably 5 to 100 μm, more preferably 8 to 70 μm, and still more preferably 10 to 50 μm.
本発明の電気化学素子用電極は、アンカー層を含む。アンカー層は、カチオン性化合物を含む。 (Anchor layer)
The electrode for an electrochemical element of the present invention includes an anchor layer. The anchor layer includes a cationic compound.
アンカー層に含まれるカチオン性化合物としては、一級アミン化合物、二級アミン化合物(イミノ基含有化合物)、三級アミン化合物、カチオン化剤により修飾された化合物等を用いることができる。なかでも、イミノ基含有化合物、カチオン化剤により修飾された化合物が好ましい。 (Cationic compound)
As the cationic compound contained in the anchor layer, a primary amine compound, a secondary amine compound (imino group-containing compound), a tertiary amine compound, a compound modified with a cationizing agent, or the like can be used. Of these, an imino group-containing compound and a compound modified with a cationizing agent are preferable.
カチオン性化合物の数平均分子量は、100~2000000であることが好ましく、10000~2000000であることがより好ましい。
なお、カチオン性化合物の数平均分子量は、例えば、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー(GPC)により測定できる。 Examples of the compound modified with a cationizing agent include cationized cellulose and the like obtained by modifying a cellulose compound such as hydroxyethyl cellulose and carboxymethyl cellulose with a cationizing agent.
The number average molecular weight of the cationic compound is preferably 100 to 2,000,000, and more preferably 10,000 to 2,000,000.
The number average molecular weight of the cationic compound can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard substance.
本発明の電気化学素子用電極は、電極活物質層を含み、電極活物質層は、電極活物質、バインダー、必要に応じて用いられる増粘剤及び導電助剤を含む。また、電極活物質層におけるバインダーの含有量は電極活物質100重量部に対して、0.1~20重量部、好ましくは0.2~15重量部、より好ましくは0.3~10重量部である。 (Electrode active material layer)
The electrode for an electrochemical element of the present invention includes an electrode active material layer, and the electrode active material layer includes an electrode active material, a binder, a thickener used as necessary, and a conductive additive. The binder content in the electrode active material layer is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the electrode active material. It is.
電気化学素子がリチウムイオン二次電池である場合の、リチウムイオン二次電池用正極の電極活物質(正極活物質)としては、リチウムイオンを可逆的にドープ・脱ドープ可能な金属酸化物が挙げられる。かかる金属酸化物としては、例えば、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、燐酸鉄リチウム等を挙げることができる。なお、上記にて例示した正極活物質は適宜用途に応じて単独で使用してもよく、複数種混合して使用してもよい。 (Electrode active material)
In the case where the electrochemical device is a lithium ion secondary battery, the electrode active material (positive electrode active material) of the positive electrode for the lithium ion secondary battery includes a metal oxide capable of reversibly doping and dedoping lithium ions. It is done. Examples of the metal oxide include lithium cobaltate, lithium nickelate, lithium manganate, and lithium iron phosphate. In addition, the positive electrode active material illustrated above may be used independently according to a use, and may be used in mixture of multiple types.
本発明に用いるバインダーは、電極活物質同士を接着するための成分であり、通常結着性を有する重合体粒子が水等の溶媒に溶解または分散された溶液または分散液の状態で用いられる。 (binder)
The binder used in the present invention is a component for adhering electrode active materials to each other, and is usually used in the form of a solution or dispersion in which polymer particles having binding properties are dissolved or dispersed in a solvent such as water.
ジエン系重合体とは、ブタジエン、イソプレンなどの共役ジエンを重合してなる単量体単位を含む重合体である。ジエン系重合体中の共役ジエンを重合してなる単量体単位の割合は通常40重量%以上、好ましくは50重量%以上、より好ましくは60重量%以上である。重合体としては、ポリブタジエンやポリイソプレンなどの共役ジエンの単独重合体;共役ジエンと共重合可能な単量体との共重合体が挙げられる。前記共重合可能な単量体としては、アクリロニトリル、メタクリロニトリルなどのα,β-不飽和ニトリル化合物;アクリル酸、メタクリル酸などの不飽和カルボン酸類;スチレン、クロロスチレン、ビニルトルエン、t-ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α-メチルスチレン、ジビニルベンゼン等のスチレン系単量体;エチレン、プロピレン等のオレフィン類;塩化ビニル、塩化ビニリデン等のハロゲン原子含有単量体; 酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類;メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類;メチルビニルケトン、エチルビニルケトン、ブチルビニルケトン、ヘキシルビニルケトン、イソプロペニルビニルケトン等のビニルケトン類; N-ビニルピロリドン、ビニルピリジン、ビニルイミダゾール等の複素環含有ビニル化合物が挙げられる。 (Diene polymer)
The diene polymer is a polymer containing monomer units obtained by polymerizing conjugated dienes such as butadiene and isoprene. The proportion of monomer units obtained by polymerizing conjugated diene in the diene polymer is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more. Examples of the polymer include homopolymers of conjugated dienes such as polybutadiene and polyisoprene; and copolymers of monomers that are copolymerizable with conjugated dienes. Examples of the copolymerizable monomer include α, β-unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; styrene, chlorostyrene, vinyltoluene, and t-butyl. Styrene monomers such as styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, α-methyl styrene and divinyl benzene; olefins such as ethylene and propylene; vinyl chloride and vinylidene chloride Halogen atom-containing monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl Vinyl ketones such as ketone, butyl vinyl ketone, hexyl vinyl ketone, and isopropenyl vinyl ketone; and heterocyclic ring-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine, and vinyl imidazole.
アクリル系重合体とは、アクリル酸エステルおよび/またはメタクリル酸エステルを重合してなる単量体単位を含む重合体である。アクリル系重合体中のアクリル酸エステルおよび/またはメタクリル酸エステルを重合してなる単量体単位の割合は、通常40重量%以上、好ましくは50重量%以上、より好ましくは60重量%以上である。重合体としては、アクリル酸エステル及び/又はメタクリル酸エステルの単独重合体、これと共重合可能な単量体との共重合体が挙げられる。前記共重合可能な単量体としては、アクリル酸、メタクリル酸、イタコン酸、フマル酸などの不飽和カルボン酸類;エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレートなどの2つ以上の炭素-炭素二重結合を有するカルボン酸エステル類;スチレン、クロロスチレン、ビニルトルエン、t-ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α-メチルスチレン、ジビニルベンゼン等のスチレン系単量体;アクリルアミド、N-メチロールアクリルアミド、アクリルアミド-2-メチルプロパンスルホン酸などのアミド系単量体;アクリロニトリル、メタクリロニトリルなどのα,β-不飽和ニトリル化合物;エチレン、プロピレン等のオレフィン類;ブタジエン、イソプレン等のジエン系単量体;塩化ビニル、塩化ビニリデン等のハロゲン原子含有単量体; 酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類;メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類;メチルビニルケトン、エチルビニルケトン、ブチルビニルケトン、ヘキシルビニルケトン、イソプロペニルビニルケトン等のビニルケトン類; N-ビニルピロリドン、ビニルピリジン、ビニルイミダゾール等の複素環含有ビニル化合物が挙げられる。 (Acrylic polymer)
The acrylic polymer is a polymer containing a monomer unit obtained by polymerizing an acrylic ester and / or a methacrylic ester. The proportion of monomer units obtained by polymerizing acrylic acid ester and / or methacrylic acid ester in the acrylic polymer is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more. . Examples of the polymer include homopolymers of acrylic acid esters and / or methacrylic acid esters, and copolymers with monomers copolymerizable therewith. Examples of the copolymerizable monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; two or more carbons such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate. Carboxylates having carbon double bonds; styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, α-methyl styrene, Styrenic monomers such as divinylbenzene; Amide monomers such as acrylamide, N-methylolacrylamide, and acrylamide-2-methylpropanesulfonic acid; α, β-insoluble such as acrylonitrile and methacrylonitrile Nitrile compounds; olefins such as ethylene and propylene; diene monomers such as butadiene and isoprene; monomers containing halogen atoms such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Vinyl esters such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinyl Heterocycle-containing vinyl compounds such as pyridine and vinylimidazole can be mentioned.
本発明に用いるバインダーは、さらに酸基含有単量体単位を含む。酸基含有単量体単位を導く酸基含有単量体としては、例えば、-COOH基(カルボキシル基);-SO3H基(スルホン酸基);-PO3H2基及び-PO(OH)(OR)基(Rは炭化水素基を表す)等のリン酸基;等の酸基を有する単量体が挙げられる。 (Acid group-containing monomer)
The binder used in the present invention further contains an acid group-containing monomer unit. Examples of the acid group-containing monomer that leads to the acid group-containing monomer unit include: —COOH group (carboxyl group); —SO 3 H group (sulfonic acid group); —PO 3 H 2 group and —PO (OH ) (OR) groups (wherein R represents a hydrocarbon group) or the like; monomers having an acid group such as;
また、上述した単量体の塩も、酸基含有単量体として用いうる。 Examples of the monomer having a phosphoric acid group such as —PO 3 H 2 group and —PO (OH) (OR) group (R represents a hydrocarbon group) include, for example, phosphoric acid-2- (meth) acryloyloxy Examples thereof include ethyl, phosphoric acid methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl. In the present invention, “(meth) acryloyl” means “acryloyl” or “methacryloyl”.
Moreover, the salt of the monomer mentioned above can also be used as an acid group-containing monomer.
本発明の電極活物質層は、必要に応じて増粘剤を含んでもよい。増粘剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系ポリマーおよびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリ(メタ)アクリル酸およびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリビニルアルコール、アクリル酸又はアクリル酸塩とビニルアルコールの共重合体、無水マレイン酸又はマレイン酸もしくはフマル酸とビニルアルコールの共重合体などのポリビニルアルコール類;ポリエチレングリコール、ポリエチレンオキシド、ポリビニルピロリドン、変性ポリアクリル酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプン、アクリロニトリル-ブタジエン共重合体水素化物などが挙げられる。これらのなかでも、カルボキシメチルセルロース及びカルボキシメチルセルロースのアンモニウム塩並びにアルカリ金属塩を用いることが好ましい。なお、本発明において、「(変性)ポリ」は「未変性ポリ」又は「変性ポリ」を意味する。 (Thickener)
The electrode active material layer of the present invention may contain a thickener as necessary. Examples of thickeners include cellulosic polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; ) Polyvinyl alcohols such as polyvinyl alcohol, copolymers of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or copolymers of maleic acid or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified Examples thereof include polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, acrylonitrile-butadiene copolymer hydride, and the like. Among these, it is preferable to use carboxymethylcellulose, ammonium salt of carboxymethylcellulose, and alkali metal salt. In the present invention, “(modified) poly” means “unmodified poly” or “modified poly”.
本発明の電極活物質層は、必要に応じて導電助剤を含有していてもよい。導電助剤としては、導電性を有する材料であれば特に限定されないが、導電性を有する粒子状の材料が好ましく、たとえば、ファーネスブラック、アセチレンブラック、及びケッチェンブラック等の導電性カーボンブラック;天然黒鉛、人造黒鉛等の黒鉛;ポリアクリロニトリル系炭素繊維、ピッチ系炭素繊維、気相法炭素繊維等の炭素繊維;が挙げられる。導電助剤が粒子状の材料である場合の平均粒子径は、特に限定されないが、電極活物質の平均粒子径よりも小さいものが好ましく、より少ない使用量で十分な導電性を発現させる観点から、好ましくは0.001~10μm、より好ましくは0.05~5μm、さらに好ましくは0.1~1μmである。 (Conductive aid)
The electrode active material layer of the present invention may contain a conductive additive as necessary. The conductive auxiliary agent is not particularly limited as long as it is a conductive material, but a conductive particulate material is preferable. For example, conductive carbon black such as furnace black, acetylene black, and ketjen black; natural And graphite such as graphite and artificial graphite; and carbon fibers such as polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and vapor grown carbon fiber. The average particle diameter when the conductive assistant is a particulate material is not particularly limited, but is preferably smaller than the average particle diameter of the electrode active material, from the viewpoint of expressing sufficient conductivity with a smaller amount of use. The thickness is preferably 0.001 to 10 μm, more preferably 0.05 to 5 μm, and still more preferably 0.1 to 1 μm.
本発明の電気化学素子用電極の使用態様としては、かかる電極を用いたリチウムイオン二次電池、リチウムイオンキャパシタなどが挙げられ、リチウムイオン二次電池が好適である。たとえばリチウムイオン二次電池は、上述のようにして得られる電気化学素子用電極を正極および負極の少なくとも一方に用い、さらにセパレーターおよび電解液を備える。 (Electrochemical element)
Examples of usage of the electrode for an electrochemical element of the present invention include a lithium ion secondary battery and a lithium ion capacitor using such an electrode, and a lithium ion secondary battery is preferable. For example, a lithium ion secondary battery uses an electrode for an electrochemical element obtained as described above as at least one of a positive electrode and a negative electrode, and further includes a separator and an electrolytic solution.
電解液は、特に限定されないが、例えば、非水系の溶媒に支持電解質としてリチウム塩を溶解したものが使用できる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどのリチウム塩が挙げられる。特に溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liは好適に用いられる。これらは、単独、または2種以上を混合して用いることができる。支持電解質の量は、電解液に対して、通常1wt.%以上、好ましくは5wt.%以上、また通常は30wt.%以下、好ましくは20wt.%以下である。支持電解質の量が少なすぎても多すぎてもイオン導電度は低下し電池の充電特性、放電特性が低下する。 (Electrolyte)
The electrolytic solution is not particularly limited. For example, a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used. Examples of the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts. In particular, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more. The amount of the supporting electrolyte is usually 1 wt. % Or more, preferably 5 wt. % Or more, and usually 30 wt. % Or less, preferably 20 wt. % Or less. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered, and the charging characteristics and discharging characteristics of the battery are degraded.
(1-1)ピール強度
実施例および比較例で製造したリチウムイオン二次電池用電極を長さ100mm、幅10mmの長方形に切り出して試験片とし、電極活物質層面を下にして電極活物質層表面にセロハンテープ(JIS Z1522に規定されるもの)を貼り付け、アンカー層を有する集電体の一端を垂直方向に引張り速度50mm/分で引張って剥がしたときの応力を測定した(なお、セロハンテープは試験台に固定されている。)。測定を3回行い、その平均値を求めてこれをピール強度とし、結果を表1及び表2に示した。ピール強度が大きいほど電極活物質層のアンカー層への結着力が大きい、すなわち密着強度が大きいことを示す。 (1) Adhesiveness (1-1) Peel strength The electrodes for lithium ion secondary batteries produced in the examples and comparative examples were cut into rectangles having a length of 100 mm and a width of 10 mm to form test pieces with the electrode active material layer surface facing down. Measure the stress when cellophane tape (as defined in JIS Z1522) is applied to the surface of the electrode active material layer, and one end of the current collector having the anchor layer is pulled in the vertical direction at a pulling speed of 50 mm / min. (The cellophane tape is fixed to the test stand.) The measurement was performed three times, the average value was obtained and this was taken as the peel strength, and the results are shown in Tables 1 and 2. The higher the peel strength, the greater the binding force of the electrode active material layer to the anchor layer, that is, the higher the adhesion strength.
(2-1)高温サイクル特性測定後のピール強度
(2-2)の評価後、800mAhの捲回型セルのリチウムイオン二次電池を解体し、60℃、24時間、真空乾燥した。その後、リチウムイオン二次電池用電極を長さ100mm、幅10mmの長方形に切り出して試験片とし、電極活物質層面を下にして電極活物質層表面にセロハンテープ(JIS Z1522に規定されるもの)を貼り付け、アンカー層を有する集電体の一端を垂直方向に引張り速度50mm/分で引張って剥がしたときの応力を測定した(なお、セロハンテープは試験台に固定されている。)。測定を3回行い、その平均値を求めてこれをピール強度とし、結果を表1及び表2に示した。ピール強度が大きいほど電極活物質層のアンカー層への結着力が大きい、すなわち密着強度が大きいことを示す。 (2) Durability (2-1) Peel strength after measurement of high-temperature cycle characteristics After evaluation of (2-2), the 800-mAh wound cell lithium ion secondary battery was disassembled and vacuumed at 60 ° C. for 24 hours. Dried. Thereafter, the electrode for the lithium ion secondary battery is cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece, and a cellophane tape (as defined in JIS Z1522) is formed on the surface of the electrode active material layer with the electrode active material layer side down. The one end of the current collector having the anchor layer was pulled in the vertical direction and pulled at a pulling speed of 50 mm / min, and the stress was measured (note that the cellophane tape was fixed to the test stand). The measurement was performed three times, the average value was obtained and this was taken as the peel strength, and the results are shown in Tables 1 and 2. The higher the peel strength, the greater the binding force of the electrode active material layer to the anchor layer, that is, the higher the adhesion strength.
実施例および比較例において作製した800mAh捲回型セルのリチウムイオン二次電池を、25℃の環境下で24時間静置させた後に、25℃の環境下で、4.2V、0.1Cの充電、3.0V、0.1Cの放電にて充放電の操作を行い、初期容量C0を測定した。さらに、60℃環境下で、充放電を繰り返し、1000サイクル後の容量C1を測定した。高温サイクル特性は、ΔC=C1/C0×100(%)で示す容量維持率にて評価し、結果を表1及び表2に示した。この値が高いほど寿命特性に優れることを示す。 (2-2) High-temperature cycle characteristics After the lithium ion secondary battery of the 800 mAh wound-type cell produced in the examples and comparative examples was allowed to stand for 24 hours in an environment at 25 ° C, Charge / discharge operation was performed by charging at 4.2 V and 0.1 C and discharging at 3.0 V and 0.1 C, and the initial capacity C 0 was measured. Furthermore, charging / discharging was repeated under an environment of 60 ° C., and the capacity C 1 after 1000 cycles was measured. The high-temperature cycle characteristics were evaluated by the capacity retention rate represented by ΔC = C 1 / C 0 × 100 (%), and the results are shown in Tables 1 and 2. It shows that it is excellent in a lifetime characteristic, so that this value is high.
実施例および比較例において作製した800mAh捲回型セルのリチウムイオン二次電池を、25℃の環境下で24時間静置させた後に、25℃の環境下で、4.2V、0.1Cの充電、3.0V、0.1Cの放電にて充放電の操作を行った後、捲回型セルを流動パラフィンに浸漬し、その体積V0を測定した。さらに、60℃環境下で、充放電を繰り返し、1000サイクル後の捲回型セルを流動パラフィンに浸漬し、その体積V1を測定した。高温サイクル特性前後でのセル体積変化ΔV(%)=(V1-V0)/V0×100にて評価し、結果を表1及び表2に示した。この値が小さいほどガス発生抑制に優れていることを示す。 (2-3) Cell volume change before and after the cycle The lithium ion secondary battery of the 800 mAh wound type cell produced in the examples and comparative examples was allowed to stand for 24 hours in an environment of 25 ° C. Under the environment, after charging / discharging operation by charging at 4.2V, 0.1C, discharging at 3.0V, 0.1C, the wound type cell was immersed in liquid paraffin, and the volume V 0 was set. It was measured. Furthermore, charging and discharging were repeated under an environment of 60 ° C., the wound cell after 1000 cycles was immersed in liquid paraffin, and its volume V 1 was measured. The cell volume change ΔV (%) before and after the high-temperature cycle characteristics was evaluated at (V 1 −V 0 ) / V 0 × 100, and the results are shown in Tables 1 and 2. The smaller this value, the better the gas generation suppression.
(3-1)低温出力特性
実施例および比較例において作製した800mAh捲回型のリチウムイオン二次電池を、25℃の環境下で24時間静置させた後に、25℃の環境下で、4.2V、0.1C、5時間の充電の操作を行い、その時の電圧V0を測定した。その後、-10℃環境下で、1Cの放電レートにて放電の操作を行い、放電開始15秒後の電圧V1を測定した。低温特性は、ΔV=V0-V1で示す電圧変化にて評価し、結果を表1及び表2に示した。この値が小さいほど低温特性に優れることを示す。 (3) Low temperature characteristics (3-1) Low temperature output characteristics The 800 mAh wound type lithium ion secondary battery produced in the examples and comparative examples was allowed to stand for 24 hours in an environment of 25 ° C, Under the environment, 4.2 V, 0.1 C, and 5 hours of charging were performed, and the voltage V 0 at that time was measured. Thereafter, a discharge operation was performed at a discharge rate of 1 C in an environment of −10 ° C., and the voltage V 1 15 seconds after the start of discharge was measured. The low temperature characteristics were evaluated by a voltage change represented by ΔV = V 0 −V 1 , and the results are shown in Tables 1 and 2. It shows that it is excellent in a low temperature characteristic, so that this value is small.
カチオン性化合物を、ジメチルホルムアミドに溶解して1%溶液を調製した。これを測定サンプルとして、標準物質にポリスチレンを用い、展開溶媒に、ジメチルホルムアミドの10体積%水溶液に0.85g/mlの硝酸ナトリウムを溶解させた溶液を用いたGPC測定を行った。
なお、GPC測定装置は、HLC-8220GPC(東ソー社製)、検出器は、HLC-8320GPC RI検出器(東ソー社製)、測定カラムは、TSKgel SuperHZM-M(東ソー社製)を用い、測定温度40℃、展開溶媒流速0.6mL/min、サンプル注入量20μlで測定を行った。 (Measurement of number average molecular weight)
The cationic compound was dissolved in dimethylformamide to prepare a 1% solution. Using this as a measurement sample, GPC measurement was performed using polystyrene as a standard substance, and using a solution obtained by dissolving 0.85 g / ml sodium nitrate in a 10% by volume aqueous solution of dimethylformamide as a developing solvent.
The GPC measuring device is HLC-8220GPC (manufactured by Tosoh Corporation), the detector is HLC-8320GPC RI detector (manufactured by Tosoh Corporation), the measuring column is TSKgel SuperHZM-M (manufactured by Tosoh Corporation), and the measurement temperature is measured. Measurement was performed at 40 ° C., a developing solvent flow rate of 0.6 mL / min, and a sample injection amount of 20 μl.
(アンカー層の製造)
厚さ12μmの銅集電体にダイより、カチオン性化合物としてポリエチレンイミン(エポミン、日本触媒社製、数平均分子量700000、固形分濃度30%水溶液)を吐出し、30m/分の成形速度で、前記集電体の片面に塗布し、120℃で5分間乾燥して、厚さ0.5μmのアンカー層を形成した。 Example 1
(Manufacture of anchor layer)
Polyethyleneimine (Epomin, Nippon Shokubai Co., Ltd., number average molecular weight 700,000, 30% solid content aqueous solution) is discharged from a die onto a 12 μm thick copper current collector as a cationic compound, at a molding speed of 30 m / min. The current collector was applied on one side and dried at 120 ° C. for 5 minutes to form an anchor layer having a thickness of 0.5 μm.
攪拌機付き5MPa耐圧容器に、1,3-ブタジエン(以下、「BD」ということがある。)33部、イタコン酸3.5部、スチレン(以下、「ST」ということがある。)62.5部、2-ヒドロキシエチルアクリレート(以下、「β-HEA」ということがある。)1部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム0.4部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、50℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、粒子状の負極用バインダー(スチレン-ブタジエン共重合体(SBR))を含む混合物を得た。上記粒子状の負極用バインダーを含む混合物に、5%水酸化ナトリウム水溶液を添加して、pH8に調整後、加熱減圧蒸留によって未反応単量体の除去を行った後、30℃以下まで冷却し、所望の粒子状の負極用バインダーを含む水分散液を得た。 (Manufacture of binder for negative electrode)
In a 5 MPa pressure vessel equipped with a stirrer, 33 parts of 1,3-butadiene (hereinafter sometimes referred to as “BD”), 3.5 parts of itaconic acid, and 62.5 of styrene (hereinafter sometimes referred to as “ST”). 1 part, 2-hydroxyethyl acrylate (hereinafter sometimes referred to as “β-HEA”), 0.4 part sodium dodecylbenzenesulfonate as an emulsifier, 150 parts ion-exchanged water, and potassium persulfate as a polymerization initiator 0 .5 parts was added, and after sufficiently stirring, the mixture was heated to 50 ° C. to initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing particulate negative electrode binder (styrene-butadiene copolymer (SBR)). After adding 5% aqueous sodium hydroxide solution to the mixture containing the particulate negative electrode binder and adjusting to pH 8, the unreacted monomer is removed by heating under reduced pressure, and then cooled to 30 ° C or lower. An aqueous dispersion containing the desired particulate negative electrode binder was obtained.
人造黒鉛(平均粒子径:15.6μm)100部、増粘剤としてカルボキシメチルセルロースナトリウム塩(日本製紙社製「MAC350HC」;以下、「CMC-Na塩」ということがある。)の2%水溶液を固形分相当で1部、イオン交換水で固形分濃度68%に調製した後、25℃60分間混合した。さらにイオン交換水で固形分濃度62%に調製した後、さらに25℃15分間混合した。上記混合液に、上記粒子状の負極用バインダーを固形分相当量で1.5部、及びイオン交換水を入れ、最終固形分濃度52%となるように調整し、さらに10分間混合した。これを減圧下で脱泡処理して流動性の良い負極用スラリーを得た。 (Manufacture of negative electrode slurry)
100 parts of artificial graphite (average particle size: 15.6 μm), a 2% aqueous solution of carboxymethylcellulose sodium salt (“MAC350HC” manufactured by Nippon Paper Industries Co., Ltd .; hereinafter sometimes referred to as “CMC-Na salt”) as a thickener. The solid content was 1 part, and the solid content concentration was adjusted to 68% with ion-exchanged water, followed by mixing at 25 ° C. for 60 minutes. Further, the solid content was adjusted to 62% with ion-exchanged water, and further mixed at 25 ° C. for 15 minutes. In the mixed solution, 1.5 parts of the particulate negative electrode binder in an amount corresponding to the solid content and ion-exchanged water were added, adjusted to a final solid content concentration of 52%, and further mixed for 10 minutes. This was defoamed under reduced pressure to obtain a negative electrode slurry having good fluidity.
前記アンカー層を有する銅集電体上に、上記で得られた負極用スラリーを、コンマコーターで、乾燥後の膜厚が150μm程度になるように塗布し、乾燥させた。この乾燥は、銅箔を0.5m/分の速度で60℃のオーブン内を2分間かけて搬送することにより行った。その後、120℃にて2分間加熱処理してプレス前の負極原反を得た。このプレス前の負極原反をロールプレスで圧延して、負極組成物層の厚みが80μmのプレス後のリチウムイオン二次電池用負極(以下、「負極」ということがある。)を得た。 (Manufacture of negative electrodes for lithium ion secondary batteries)
On the copper current collector having the anchor layer, the negative electrode slurry obtained above was applied with a comma coater so that the film thickness after drying was about 150 μm, and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material before pressing. The negative electrode original fabric before pressing was rolled with a roll press to obtain a negative electrode for a lithium ion secondary battery after pressing (hereinafter, also referred to as “negative electrode”) having a negative electrode composition layer thickness of 80 μm.
正極活物質としてLiCoO2(以下、「LCO」ということがある。)92部に、正極用バインダーとしてポリフッ化ビニリデン(PVDF;クレハ化学社製「KF-1100」)を固形分量が2部となるように加え、さらに、アセチレンブラック(電気化学工業社製「HS-100」)を6部、N-メチルピロリドン20部を加えて、プラネタリーミキサーで混合して正極用スラリーを得た。この正極用スラリーを厚さ18μmのアルミニウム箔に塗布し、120℃で30分乾燥した後、ロールプレスして厚さ60μmのリチウムイオン二次電池用正極(以下、「正極」ということがある。)を得た。 (Production of slurry for positive electrode and positive electrode for lithium ion secondary battery)
92 parts of LiCoO 2 (hereinafter also referred to as “LCO”) as the positive electrode active material and 2 parts of solid content of polyvinylidene fluoride (PVDF; “KF-1100” manufactured by Kureha Chemical Co., Ltd.) as the positive electrode binder In addition, 6 parts of acetylene black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) and 20 parts of N-methylpyrrolidone were added and mixed with a planetary mixer to obtain a positive electrode slurry. This positive electrode slurry is applied to an aluminum foil having a thickness of 18 μm, dried at 120 ° C. for 30 minutes, and then roll-pressed to form a positive electrode for a lithium ion secondary battery having a thickness of 60 μm (hereinafter, referred to as “positive electrode”). )
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、55×5.5cm2に切り抜いた。 (Preparation of separator)
A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by dry method, porosity 55%) was cut out to 55 × 5.5 cm 2 .
上記で得られたプレス後の正極を49×5cm2に切り出し、その上に55×5.5cm2に切り出したセパレーターを配置した。さらに、得られたプレス後の負極を、50×5.2cm2に切り出し、これをセパレーター上に、負極活物質層側の表面がセパレーターに向かい合うよう配置した。これを捲回機により、捲回し、捲回体を得た。この捲回体を60℃、0.5MPaでプレスし、扁平体とし、電池の外装として、アルミ包材外装で包み、電解液(溶媒:EC/DEC/VC=68.5/30/1.5体積比、電解質:濃度1MのLiPF6)を空気が残らないように注入し、さらに、アルミ包材の開口を密封するために、150℃のヒートシールをしてアルミ外装を閉口し、800mAhの捲回型リチウムイオン二次電池を製造した。 (Manufacture of lithium ion secondary batteries)
Cut out positive electrode after pressing obtained above in 49 × 5 cm 2, were placed separator was cut into 55 × 5.5cm 2 thereon. Furthermore, the obtained negative electrode after pressing was cut out to 50 × 5.2 cm 2 , and this was arranged on the separator so that the surface on the negative electrode active material layer side faces the separator. This was wound with a winding machine to obtain a wound body. The wound body is pressed at 60 ° C. and 0.5 MPa to form a flat body, and is wrapped with an aluminum packaging exterior as a battery exterior, and an electrolytic solution (solvent: EC / DEC / VC = 68.5 / 30/1. 5 volume ratio, electrolyte: 1M LiPF 6 ) was injected so as not to leave air, and in order to seal the opening of the aluminum packaging material, heat sealing at 150 ° C. was performed to close the aluminum exterior, and 800 mAh A wound type lithium ion secondary battery was manufactured.
負極用バインダーの製造において、イタコン酸の量を0.2部、スチレンの量を63.8部とした以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Example 2)
Production of anchor layer, production of negative electrode slurry, production of negative electrode in the same manner as in Example 1 except that the amount of itaconic acid was 0.2 parts and the amount of styrene was 63.8 parts in the production of the negative electrode binder. And the lithium ion secondary battery was manufactured.
負極用バインダーの製造において、1,3-ブタジエンの量を30部、イタコン酸の量9.5部、スチレンの量を59.5部とした以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 Example 3
In the production of the negative electrode binder, the anchor layer was produced in the same manner as in Example 1 except that the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 9.5 parts, and the amount of styrene was 59.5 parts. The production of slurry for negative electrode, the production of negative electrode and the production of lithium ion secondary battery were carried out.
負極用スラリーの製造において、用いる粒子状の負極用バインダーの量を固形分相当量で0.2部とした以外は、実施例1と同様にアンカー層の製造、負極の製造及びリチウムイオン二次電池の製造を行った。 Example 4
In the production of the negative electrode slurry, the production of the anchor layer, the production of the negative electrode, and the lithium ion secondary were the same as in Example 1 except that the amount of the particulate negative electrode binder used was 0.2 parts in terms of solid content. The battery was manufactured.
負極用スラリーの製造において、粒子状バインダーの量を固形分相当量で18部とした以外は、実施例1と同様にアンカー層の製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Example 5)
In the production of the negative electrode slurry, the anchor layer, the negative electrode, and the lithium ion secondary battery were produced in the same manner as in Example 1 except that the amount of the particulate binder was 18 parts in terms of solid content. .
負極用バインダーの製造において、イタコン酸に代えてスチレンスルホン酸ナトリウム(以下、「NaSS」ということがある。)を用いた以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Example 6)
In the production of the negative electrode binder, in the same manner as in Example 1, except that sodium styrenesulfonate (hereinafter sometimes referred to as “NaSS”) was used instead of itaconic acid, production of the anchor layer and production of the negative electrode slurry were performed. The negative electrode and the lithium ion secondary battery were manufactured.
負極用バインダーの製造において、イタコン酸に代えてリン酸メチル-2-メタアクリロイルオキシエチルを用いた以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Example 7)
In the production of the binder for the negative electrode, except that methyl-2-methacryloyloxyethyl phosphate was used instead of itaconic acid, the production of the anchor layer, the production of the slurry for the negative electrode, the production of the negative electrode, and lithium were performed in the same manner as in Example 1. An ion secondary battery was manufactured.
アンカー層の製造において、カチオン性化合物としてポリエチレンイミンに代えてカルボキシメチル化ポリエチレンイミン・ナトリウム塩(数平均分子量50000、固形分濃度3%水溶液)を用いた以外は、実施例1と同様に負極用スラリーの製造、負極の製造おおよびリチウムイオン二次電池の製造を行った。 (Example 8)
In the production of the anchor layer, as in Example 1, except that carboxymethylated polyethyleneimine sodium salt (number average molecular weight 50000, solid content concentration 3% aqueous solution) was used as the cationic compound instead of polyethyleneimine. Production of a slurry, production of a negative electrode, and production of a lithium ion secondary battery were performed.
アンカー層の製造において、カチオン性化合物としてポリエチレンイミンに代えてカチオン化セルロース(ポイズC-60H、数平均分子量600000、固形分濃度3%水溶液)を用いた以外は、実施例1と同様に負極用スラリーの製造、負極の製造おおよびリチウムイオン二次電池の製造を行った。 Example 9
In the production of the anchor layer, as in Example 1, except that cationized cellulose (poise C-60H, number average molecular weight 600000, solid content concentration 3% aqueous solution) was used instead of polyethyleneimine as the cationic compound. Production of a slurry, production of a negative electrode, and production of a lithium ion secondary battery were performed.
(アンカー層の製造)
厚さ18μmのアルミ集電体にダイより、カチオン性化合物としてポリエチレンイミン(エポミン、日本触媒社製、数平均分子量700000、固形分濃度30%水溶液)を吐出し、30m/分の成形速度で、前記集電体の片面に塗布し、120℃で5分間乾燥して、厚さ0.5μmのアンカー層を形成した。 (Example 10)
(Manufacture of anchor layer)
Polyethyleneimine (epomine, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 700,000, 30% solid content aqueous solution) is discharged from a die onto an aluminum current collector having a thickness of 18 μm as a cationic compound, and at a molding speed of 30 m / min. The current collector was applied on one side and dried at 120 ° C. for 5 minutes to form an anchor layer having a thickness of 0.5 μm.
攪拌機付き5MPa耐圧容器に、2-エチルヘキシルアクリレート(以下、「2-EHA」ということがある。)76部、イタコン酸4.0部、アクリロニトリル(以下、「AN」ということがある。)20部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム0.4部、イオン交換水150部及び重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、50℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、粒子状の正極用バインダー(アクリル系重合体(ACL))を含む混合物を得た。上記粒子状の正極用バインダーを含む混合物に、5%水酸化ナトリウム水溶液を添加して、pH8に調整後、加熱減圧蒸留によって未反応単量体の除去を行った後、30℃以下まで冷却し、所望の粒子状の正極用バインダーを含む水分散液を得た。 (Manufacture of binder for positive electrode)
In a 5 MPa pressure vessel equipped with a stirrer, 76 parts of 2-ethylhexyl acrylate (hereinafter sometimes referred to as “2-EHA”), 4.0 parts of itaconic acid, and 20 parts of acrylonitrile (hereinafter sometimes referred to as “AN”). Then, 0.4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water and 0.5 part of potassium persulfate as a polymerization initiator were stirred sufficiently, and then heated to 50 ° C. to initiate polymerization. . When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing particulate positive electrode binder (acrylic polymer (ACL)). After adding 5% aqueous sodium hydroxide solution to the mixture containing the particulate positive electrode binder and adjusting the pH to 8, the unreacted monomer is removed by heating under reduced pressure, and then cooled to 30 ° C or lower. Thus, an aqueous dispersion containing a desired positive electrode binder was obtained.
ディスパー付きのプラネタリーミキサーに、正極活物質としてLCOを100部、粘性付与剤としてCMC-Na塩(日本製紙社製「MAC350HC」)の2%水溶液を固形分相当で1部をそれぞれ加え、イオン交換水で固形分濃度60%に調整した後、25℃で60分混合した。次に、イオン交換水で固形分濃度57%に調整した後、さらに25℃で15分混合し混合液を得た。 (Production of positive electrode slurry)
To a planetary mixer with a disper, add 100 parts of LCO as a positive electrode active material and 1 part of a 2% aqueous solution of CMC-Na salt (“MAC350HC” manufactured by Nippon Paper Industries Co., Ltd.) as a viscosity-imparting agent. After adjusting the solid content concentration to 60% with exchange water, the mixture was mixed at 25 ° C. for 60 minutes. Next, after adjusting to 57% of solid content concentration with ion-exchange water, it mixed for 15 minutes at 25 degreeC, and the liquid mixture was obtained.
負極活物質として人造黒鉛(平均粒子径:24.5μm、黒鉛層間距離(X線回折法による(002)面の面間隔(d値):0.354nm)96部、スチレン-ブタジエン共重合ラテックス(BM-400B)を固形分換算量で3.0部、分散剤としてカルボキシメチルセルロースの1.5%水溶液(DN-800H:ダイセル化学工業社製)を固形分換算量で1.0部混合し、さらにイオン交換水を固形分濃度が50%となるように加え、混合分散して負極用スラリーを得た。この負極用スラリーを厚さ18μmの銅箔に塗布し、120℃で30分間乾燥した後、ロールプレスして厚さ50μmの負極を得た。 (Manufacture of negative electrode slurry and lithium ion secondary battery negative electrode)
Artificial graphite as the negative electrode active material (average particle size: 24.5 μm, graphite interlayer distance (interval of (002) plane by X-ray diffraction (d value): 9654 nm), 96 parts, styrene-butadiene copolymer latex ( BM-400B) in an amount of 3.0 parts in terms of solid content, and 1.5 parts of a 1.5% aqueous solution of carboxymethyl cellulose (DN-800H: manufactured by Daicel Chemical Industries) as a dispersant was mixed in an amount of 1.0 parts in terms of solid content. Further, ion exchange water was added so as to have a solid content concentration of 50%, and mixed and dispersed to obtain a negative electrode slurry, which was applied to a copper foil having a thickness of 18 μm and dried at 120 ° C. for 30 minutes. Thereafter, roll pressing was performed to obtain a negative electrode having a thickness of 50 μm.
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、55×5.5cm2に切り抜いた。 (Preparation of separator)
A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by dry method, porosity 55%) was cut out to 55 × 5.5 cm 2 .
上記で得られたプレス後の正極を49×5cm2に切り出し、その上に55×5.5cm2に切り出したセパレーターを配置した。さらに、得られたプレス後の負極を、50×5.2cm2に切り出し、これをセパレーター上に、負極活物質層側の表面がセパレーターに向かい合うよう配置した。これを捲回機により、捲回し、捲回体を得た。この捲回体を60℃、0.5MPaでプレスし、扁平体とし、電池の外装として、アルミ包材外装で包み、電解液(溶媒:EC/DEC/VC=68.5/30/1.5体積比、電解質:濃度1MのLiPF6)を空気が残らないように注入し、さらに、アルミ包材の開口を密封するために、150℃のヒートシールをしてアルミ外装を閉口し、800mAhの捲回型リチウムイオン二次電池を製造した。 (Manufacture of lithium ion secondary batteries)
Cut out positive electrode after pressing obtained above in 49 × 5 cm 2, were placed separator was cut into 55 × 5.5cm 2 thereon. Furthermore, the obtained negative electrode after pressing was cut out to 50 × 5.2 cm 2 , and this was arranged on the separator so that the surface on the negative electrode active material layer side faces the separator. This was wound with a winding machine to obtain a wound body. The wound body is pressed at 60 ° C. and 0.5 MPa to form a flat body, and is wrapped with an aluminum packaging exterior as a battery exterior, and an electrolytic solution (solvent: EC / DEC / VC = 68.5 / 30/1. 5 volume ratio, electrolyte: 1M LiPF 6 ) was injected so as not to leave air, and in order to seal the opening of the aluminum packaging material, heat sealing at 150 ° C. was performed to close the aluminum exterior, and 800 mAh A wound type lithium ion secondary battery was manufactured.
負極用バインダーの製造において、1,3-ブタジエンの量を30部、イタコン酸の量11.0部、スチレンの量を58部とした以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 1)
In the production of the negative electrode binder, the anchor layer was produced in the same manner as in Example 1, except that the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 11.0 parts, and the amount of styrene was 58 parts. Slurry production, negative electrode production and lithium ion secondary battery production were carried out.
負極用スラリーの製造において、用いる粒子状の負極用バインダーの量を固形分相当量で22部とした以外は、実施例1と同様にアンカー層の製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 2)
In the production of the negative electrode slurry, the production of the anchor layer, the production of the negative electrode, and the lithium ion secondary battery was the same as in Example 1 except that the amount of the particulate negative electrode binder used was 22 parts in terms of solid content. Manufactured.
負極用バインダーの製造において、1,3-ブタジエンの量を30部、イタコン酸の量11.0部、スチレンの量を58部とし、負極用スラリーの製造において、用いる粒子状の負極用バインダーの量を固形分相当量で22部とした以外は、実施例1と同様にアンカー層の製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 3)
In the production of the negative electrode binder, the amount of 1,3-butadiene was 30 parts, the amount of itaconic acid was 11.0 parts, and the amount of styrene was 58 parts. An anchor layer, a negative electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the amount was 22 parts in terms of solid content.
負極用バインダーの製造において、イタコン酸を用いずに、1,3-ブタジエンの量を34部、スチレンの量を65部とした以外は、実施例1と同様にアンカー層の製造、負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 4)
In the production of the negative electrode binder, the anchor layer was produced in the same manner as in Example 1, except that itaconic acid was not used and the amount of 1,3-butadiene was 34 parts and the amount of styrene was 65 parts. , Negative electrode, and lithium ion secondary battery.
アンカー層の製造において、カチオン性化合物を用いずにポリアクリル酸ナトリウム塩を用いた以外は、実施例1と同様に負極用スラリーの製造、負極の製造おおよびリチウムイオン二次電池の製造を行った。 (Comparative Example 5)
In the production of the anchor layer, except for using polyacrylic acid sodium salt without using a cationic compound, the production of the slurry for the negative electrode, the production of the negative electrode, and the production of the lithium ion secondary battery were performed in the same manner as in Example 1. It was.
(アンカー層の製造)
分散剤(ポリビニルアルコール)5部をイオン交換水80部に溶解させた水溶液に、導電性フィラーとしての炭素材料(黒鉛/カーボンブラック=80/20)100部を添加し、さらにカチオン性化合物としてポリエチレンイミン(エポミン、日本触媒社製、数平均分子量700000、固形分濃度30%水溶液)を固形分相当で2部添加したアンカー層用スラリーを作製した。厚さ12μmの銅集電体にダイより、アンカー層用スラリーを吐出し、30m/分の成形速度で、前記集電体の片面に塗布し、120℃で5分間乾燥して、厚さ0.5μmのアンカー層を形成した。
上記導電性フィラーを含むアンカー層を有する銅集電体を用いた以外は、実施例1と同様に負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 6)
(Manufacture of anchor layer)
100 parts of carbon material (graphite / carbon black = 80/20) as a conductive filler is added to an aqueous solution in which 5 parts of a dispersant (polyvinyl alcohol) is dissolved in 80 parts of ion-exchanged water, and polyethylene is added as a cationic compound. An anchor layer slurry was prepared by adding 2 parts of imine (epomine, manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 700,000, solid content concentration 30% aqueous solution) in an amount corresponding to the solid content. The anchor layer slurry was discharged from a die onto a 12 μm thick copper current collector, applied to one side of the current collector at a molding speed of 30 m / min, and dried at 120 ° C. for 5 minutes to obtain a thickness of 0 An anchor layer of 0.5 μm was formed.
Except for using a copper current collector having an anchor layer containing the conductive filler, a negative electrode slurry, a negative electrode, and a lithium ion secondary battery were manufactured in the same manner as in Example 1.
アンカー層の製造において、厚さ3μmのアンカー層を形成した以外は、比較例6と同様に負極用スラリーの製造、負極の製造及びリチウムイオン二次電池の製造を行った。 (Comparative Example 7)
In the production of the anchor layer, except for forming the anchor layer having a thickness of 3 μm, the production of the slurry for the negative electrode, the production of the negative electrode, and the production of the lithium ion secondary battery were performed in the same manner as in Comparative Example 6.
Claims (6)
- 集電体上に、電極活物質およびバインダーを含む電極活物質層が形成されてなる電気化学素子用電極であって、
前記集電体上に、カチオン性化合物を含むアンカー層を有し、
前記バインダーは酸基含有単量体単位を0.1~10重量%有し、前記電極活物質層中の前記バインダーの含有割合が電極活物質100重量部に対して0.1~20重量部である、電気化学素子用電極。 An electrode for an electrochemical element in which an electrode active material layer containing an electrode active material and a binder is formed on a current collector,
An anchor layer containing a cationic compound on the current collector;
The binder has an acid group-containing monomer unit of 0.1 to 10% by weight, and the binder content in the electrode active material layer is 0.1 to 20 parts by weight with respect to 100 parts by weight of the electrode active material. An electrode for an electrochemical element. - 前記カチオン性化合物の数平均分子量が、10000~2000000である請求項1記載の電気化学素子用電極。 The electrode for an electrochemical element according to claim 1, wherein the cationic compound has a number average molecular weight of 10,000 to 2,000,000.
- 前記アンカー層の厚みが、0.01μm以上1μm未満である請求項1または2記載の電気化学素子用電極。 The electrode for an electrochemical element according to claim 1 or 2, wherein the anchor layer has a thickness of 0.01 µm or more and less than 1 µm.
- 前記酸基含有単量体単位が、カルボキシル基、スルホン酸基、リン酸基のいずれかを含む請求項1~3のいずれか一項に記載の電気化学素子用電極。 The electrode for an electrochemical element according to any one of claims 1 to 3, wherein the acid group-containing monomer unit contains any of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
- 請求項1~4のいずれか一項に記載の電気化学素子用電極、セパレーターおよび電解液を含む電気化学素子。 An electrochemical element comprising the electrode for an electrochemical element according to any one of claims 1 to 4, a separator, and an electrolytic solution.
- 前記電気化学素子が、リチウムイオン二次電池である請求項5記載の電気化学素子。 The electrochemical device according to claim 5, wherein the electrochemical device is a lithium ion secondary battery.
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