WO2010113940A1 - 電気化学デバイス電極バインダー用組成物、電気化学デバイス用電極スラリー、及び電気化学デバイス用電極 - Google Patents
電気化学デバイス電極バインダー用組成物、電気化学デバイス用電極スラリー、及び電気化学デバイス用電極 Download PDFInfo
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- WO2010113940A1 WO2010113940A1 PCT/JP2010/055684 JP2010055684W WO2010113940A1 WO 2010113940 A1 WO2010113940 A1 WO 2010113940A1 JP 2010055684 W JP2010055684 W JP 2010055684W WO 2010113940 A1 WO2010113940 A1 WO 2010113940A1
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- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical class CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005359 phenoxyalkyl group Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- 235000019275 potassium ascorbate Nutrition 0.000 description 1
- 229940017794 potassium ascorbate Drugs 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- CONVKSGEGAVTMB-RXSVEWSESA-M potassium-L-ascorbate Chemical compound [K+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] CONVKSGEGAVTMB-RXSVEWSESA-M 0.000 description 1
- 230000002265 prevention Effects 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
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- 235000019250 sodium sorbate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 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
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-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
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USNDJVGIYZJHOD-UHFFFAOYSA-N tetrapotassium;dioxidophosphanyl phosphite Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])OP([O-])[O-] USNDJVGIYZJHOD-UHFFFAOYSA-N 0.000 description 1
- KRAHLZAGPKKBSW-UHFFFAOYSA-N tetrasodium;dioxidophosphanyl phosphite Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])OP([O-])[O-] KRAHLZAGPKKBSW-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- MDROHCXIEQHRRP-UHFFFAOYSA-N trisodium [hydroxy(oxido)phosphanyl] phosphite Chemical compound [Na+].[Na+].[Na+].OP([O-])OP([O-])[O-] MDROHCXIEQHRRP-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an electrochemical device electrode binder composition, an electrochemical device electrode slurry, an electrochemical device electrode, and an electrochemical device. More specifically, a composition for an electrochemical device electrode binder capable of producing an electrode having good adhesion to a current collector, producing a secondary battery having a low capacity drop during high-speed discharge and excellent cycle characteristics, and Electrode device electrode slurry, electrode for electrochemical device that can produce a secondary battery with low capacity loss due to high-speed discharge, excellent cycle characteristics, and good adhesion to the current collector, and this electrochemical The present invention relates to an electrochemical device using a device electrode.
- the binder functions to improve the adhesion between the electrode layer containing the active material and the current collector.
- binders using fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride have not always had sufficient adhesion to the current collector.
- battery characteristics such as charge / discharge cycle characteristics cannot be improved.
- the electrode plate using the fluororesin as a binder is not flexible, there is a problem that the electrode plate is likely to be cracked particularly during the manufacturing process of the wound battery, and a problem that the electrode plate is easily peeled off. was there.
- an SBR latex binder As a material for suppressing such a problem, an SBR latex binder has been conventionally used. Since the electrode plate using this binder is flexible and has high adhesion strength, problems such as peeling and cracking as described above are unlikely to occur. However, on the other hand, since the double bond derived from butadiene remains in the polymer, there is a problem that the binder is easily deteriorated due to an oxidation reaction caused by energization, and the battery characteristics including the charge / discharge cycle characteristics of the battery are also affected. There was a problem.
- Patent Document 2 a modified polymer in which a functional group such as a carboxyl group is introduced into a hydrogenated diene polymer is used as a binder for a lithium secondary battery (for example, see Patent Document 2). ).
- a functional group such as a carboxyl group
- Patent Document 2 even the binder disclosed in Patent Document 2 is not necessarily sufficient for improving the adhesion between the electrode layer and the current collector.
- a capacity drop due to high-speed discharge and a capacity drop due to repeated charge / discharge (cycle characteristics) are particularly remarkable.
- a polymer containing fluorine and an acrylic polymer having a functional group such as a carboxyl group are combined to improve capacity reduction due to high-speed discharge and capacity reduction due to repeated charge / discharge (cycle characteristics).
- An aqueous dispersion for example, refer to Patent Document 3
- a functional group-containing polymer containing a structural unit derived from at least one selected from the group consisting of an amide group-containing unsaturated monomer and a sulfonic acid group / amide group-containing unsaturated monomer A composition (see, for example, Patent Document 4) is disclosed.
- the aqueous dispersion and polymer composition of the composite polymer disclosed in Patent Documents 3 and 4 do not have an unsaturated double bond in the polymer main chain, and thus have high resistance to oxidation reaction.
- the cohesive strength of (meth) acrylic acid polymers is low, and the strength of the polymer is not sufficient. For this reason, the adhesion of the obtained electrode plate is not sufficient, and the charge / discharge cycle characteristics of the battery have not been sufficiently improved.
- the present invention has been made in view of such problems of the prior art, and the problem is that an electrode having good adhesion to a current collector can be manufactured, and high-speed discharge can be achieved.
- An object of the present invention is to provide an electrochemical device electrode binder composition and an electrochemical device electrode slurry capable of producing a secondary battery with low capacity reduction and excellent cycle characteristics.
- the problem is to provide an electrode for an electrochemical device that is capable of producing a secondary battery that has a low capacity loss during high-speed discharge, has excellent cycle characteristics, and has good adhesion to a current collector. It is in.
- the place made into the subject is providing the electrochemical device provided with this electrode for electrochemical devices.
- the present inventors have found that a fluorine-containing atomic polymer, and a polymer containing a structural unit derived from an aromatic vinyl monomer and a structural unit derived from a conjugated diene monomer.
- the present inventors have found that the above-mentioned problems can be achieved by containing polymer particles containing, and a dispersion medium, and have completed the present invention.
- electrochemical device electrode binder composition electrochemical device electrode slurry, electrochemical device electrode, and electrochemical device are provided.
- the polymer (A2) comprises (a1) 20 to 50 parts by mass of an aromatic vinyl compound, (a2) 25 to 60 parts by mass of a conjugated diene compound, and (a3) 5 of a (meth) acrylic acid ester compound. To 40 parts by mass and (a4) a monomer component containing 0.5 to 6 parts by mass of an ethylenically unsaturated carboxylic acid monomer (provided that the total of the monomer components is 100 parts by mass)
- the (A) polymer particle is obtained by emulsion polymerization of a monomer component containing the monomer constituting the (A2) polymer in the presence of the (A1) fluorine-containing atomic polymer.
- the composition for an electrochemical device electrode binder according to any one of [1] to [4] above.
- An electrode slurry for an electrochemical device containing the composition for an electrochemical device electrode binder according to any one of [1] to [5] and an electrode active material.
- An electrode for an electrochemical device comprising: a current collector; and an electrode layer formed by applying and drying the electrode slurry for an electrochemical device according to [6] on a surface of the current collector.
- composition for an electrochemical device electrode binder of the present invention can produce an electrode having good adhesion to a current collector, and can produce a secondary battery having excellent cycle characteristics with little capacity loss during high-speed discharge. There is an effect that there is.
- the electrode slurry for an electrochemical device of the present invention can produce an electrode having good adhesion to a current collector, and can produce a secondary battery excellent in cycle characteristics with little decrease in capacity during high-speed discharge. There is an effect.
- the electrode for an electrochemical device of the present invention can produce a secondary battery that is less likely to have a reduced capacity during high-speed discharge, has excellent cycle characteristics, and has the effect of having good adhesion to a current collector. .
- the electrochemical device of the present invention has an effect that it can be suitably used for a battery power source or the like of an electronic device that is required to be reduced in size and weight.
- Electrochemical device electrode binder composition The composition for an electrochemical device electrode binder of the present invention comprises (A1) a fluorine-containing atomic polymer, and (A2) a structural unit derived from an aromatic vinyl monomer and a structural unit derived from a conjugated diene monomer. (A) polymer particle containing the polymer to contain, and (B) a dispersion medium. The details will be described below.
- the polymer particles include (A1) a fluorine-containing atomic polymer, and (A2) a polymer containing a structural unit derived from an aromatic vinyl monomer and a structural unit derived from a conjugated diene monomer (hereinafter referred to as “polymer”). , “(A2) polymer”).
- (A) polymer particles are contained in a state in which (A1) fluorine-containing atomic polymer and (A2) polymer are phase-separated, or in a state in which a local deviation occurs in the composition ratio. Is not included.
- the “polymer particle” means one dispersion unit when the polymer is uniformly dispersed in a dispersion medium, and its size can be measured by a light scattering method or an electron microscope measurement. is there.
- the fluorine-containing atom polymer is not particularly limited as long as it is a polymer containing fluorine atoms.
- a polymer having a structural unit derived from vinylidene fluoride, propylene hexafluoride, vinyl fluoride, tetrafluoroethylene, perfluoroalkyl vinyl ether, or fluoroalkyl (meth) acrylate is preferable.
- the proportion of structural units derived from vinylidene fluoride contained in the fluorine-containing atomic polymer is preferably 70 to 95% by mass, more preferably 80 to 90% by mass, and 85 to 90% by mass is particularly preferred.
- the proportion of the structural unit derived from vinylidene fluoride is 70 to 95% by mass, the compatibility between the (A1) fluorine-containing atomic polymer and the monomer component constituting the (A2) polymer is good, Moreover, since the crystallinity of the (A1) fluorine-containing atomic polymer becomes appropriate, it is preferable in that (A) polymer particles composed of a composite polymer are easily obtained.
- the proportion of structural units derived from propylene hexafluoride contained in the fluorine-containing atomic polymer is preferably 5 to 30% by mass, more preferably 10 to 20% by mass. It is particularly preferable that the content be ⁇ 15% by mass.
- the proportion of the structural unit derived from hexafluoropropylene is 5 to 30% by mass, the crystallinity of the (A1) fluorine-containing atomic polymer is high, and (A1) the fluorine-containing atomic polymer and the (A2) polymer are Since the compatibility with the constituent monomer component is improved, (A) polymer particles composed of a composite polymer are preferable in that it is easy to obtain.
- the structural unit of the fluorine-containing atom polymer may have a structural unit derived from another unsaturated monomer other than the monomer containing a fluorine atom.
- unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n.
- Polyvalent (meth) acrylic acid such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Esters; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and divinylbenzene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halide compounds such as vinyl chloride and vinylidene chloride; butadiene, isoprene, chloroprene, etc.
- ethylene there are unsaturated monomers having a specific functional group.
- these other unsaturated monomers can be used individually by 1 type or in combination of 2 or more types.
- Examples of the functional group in the unsaturated monomer having the specific functional group described above include a carboxyl group, a carboxylic acid anhydride group, an amide group, an amino group, a cyano group, an epoxy group, a vinyl group, and a sulfonic acid group.
- a carboxyl group, an amide group, a cyano group, an epoxy group, and a sulfonic acid group are preferable.
- unsaturated monomers having a carboxyl group examples include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid Acids; free carboxyl group-containing alkyl esters and free carboxyl group-containing amides of the unsaturated polycarboxylic acids.
- Examples of the unsaturated monomer having a carboxylic acid anhydride group include acid anhydrides of the unsaturated polycarboxylic acid.
- Examples of the unsaturated monomer having an amide group include (meth) acrylamide, ⁇ -chloroacrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, and N-hydroxy.
- Unsaturated carboxylic acid amides such as diacetone acrylamide; N-dimethylaminomethyl (meth) acrylamide, N-2-aminoethyl (meth) acrylamide, N-2-methylaminoethyl (meth) acrylamide, N-2- Ethylaminoethyl (me ) Acrylamide, N-2-dimethylaminoethyl (meth) acrylamide, N-2-diethylaminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, N-3-methylaminopropyl (meth) acrylamide, N There are
- Examples of the unsaturated monomer having an amino group include aminomethyl (meth) acrylate, methylaminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and 2-methylamino.
- unsaturated monomers having a cyano group examples include unsaturated carboxylic nitriles such as (meth) acrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide; 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) ), Cyanoalkyl esters of unsaturated carboxylic acids such as acrylate and 3-cyanopropyl (meth) acrylate.
- Examples of the unsaturated monomer having an epoxy group include unsaturated group-containing glycidyl compounds such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether.
- Examples of the unsaturated monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid (salt), isoprenesulfonic acid (salt), methallyloxybenzenesulfonic acid (salt), Examples include allyloxybenzene sulfonic acid (salt), allyl sulfonic acid (salt), vinyl sulfonic acid (salt), methallyl sulfonic acid (salt), and 4-sulfobutyl methacrylate (salt).
- the proportion of structural units derived from other unsaturated monomers contained in the fluorine-containing atomic polymer is preferably 25% by mass or less, more preferably 10% by mass or less, It is particularly preferably 5% by mass or less.
- the proportion of structural units derived from other unsaturated monomers is 0 to 25% by mass, the compatibility between the (A1) fluorine-containing atomic polymer and the monomer component constituting the (A2) polymer is It is preferable in that it is good and it is easy to obtain (A) polymer particles composed of a composite polymer.
- the method for preparing the fluorine-containing atomic polymer is not particularly limited. For example, first, a mixed gas composed of vinylidene fluoride and propylene hexafluoride is obtained. Next, a polymerization initiator is added to the obtained mixed gas, and a polymerization reaction is performed under the conditions of a reaction temperature of 60 ° C. and a pressure of 1.96 MPa in the reaction system, thereby containing (A1) a fluorine-containing atomic polymer. Get latex. Thereafter, there is a method of drying the obtained latex.
- the aromatic vinyl unit is a structural unit obtained by polymerizing (a1) an aromatic vinyl compound.
- the (a1) aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, vinyltoluene, chlorostyrene and the like. Among these, styrene is preferable.
- the amount of the (a1) aromatic vinyl compound used is preferably 20 to 55 parts by weight, more preferably 30 to 50 parts by weight, and more preferably 35 to 45 parts by weight with respect to 100 parts by weight of the (A2) polymer. Part is particularly preferred.
- (A1) When the amount of the aromatic vinyl compound used is 20 to 55 parts by mass, the electrode plate has good adhesion because it interacts with graphite and conductive carbon appropriately. In addition, the glass transition temperature of the binder becomes an appropriate value, the electrode plate to be produced has an appropriate flexibility, and problems such as cracks occurring on the electrode plate surface during battery production are unlikely to occur.
- the conjugated diene unit is a structural unit obtained by polymerizing (a2) a conjugated diene compound.
- Examples of the (a2) conjugated diene compound include butadiene, isoprene, chloroprene, 2-chloro-1,3-butadiene and the like. Of these, butadiene is preferred.
- the amount of the (a2) conjugated diene compound used is preferably 25 to 65 parts by weight, more preferably 30 to 65 parts by weight, and more preferably 35 to 60 parts by weight with respect to 100 parts by weight of the (A2) polymer. It is particularly preferred that (A2) When the amount of the conjugated diene compound used is 25 to 65 parts by mass, the glass transition temperature of the binder is an appropriate value, the electrode plate to be produced has appropriate flexibility, and the surface of the electrode plate at the time of battery production Problems such as cracks are unlikely to occur. In addition, since the surface of the electrode to be produced has appropriate adhesiveness, process defects such as press contamination are unlikely to occur when the electrode is compressed by a roll press or the like. *
- (A2) polymer is a polymer containing the structural unit derived from (a3) (meth) acrylic acid ester compound and the structural unit derived from (a4) ethylenically unsaturated carboxylic acid monomer. Is preferred.
- ((A3) (meth) acrylic acid ester compound) (A3)
- (meth) acrylic acid ester compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Tert-butyl (meth) acrylate pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate;
- Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol ( Polyethylene glycol (meth) such as (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate Acrylate compounds;
- Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, 4- Butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl Cycloalkyl (meth) acrylates such as (meth) acrylate;
- the amount of the (a3) (meth) acrylic acid ester compound used is preferably 5 to 40 parts by weight, more preferably 7 to 30 parts by weight, based on 100 parts by weight of the (A2) polymer. It is particularly preferable that the amount be ⁇ 20 parts by mass.
- (A3) When the amount of the (meth) acrylic acid ester compound used is 5 to 40 parts by mass, the affinity with the electrolytic solution is good and the internal resistance of the battery is hardly increased excessively. Moreover, since it does not swell excessively with respect to the electrolytic solution, the adhesion of the electrode plate is lowered after injection of the electrolytic solution, and problems such as electrode plate peeling are unlikely to occur.
- (A4) ethylenically unsaturated carboxylic acid monomer (A4)
- examples of the ethylenically unsaturated carboxylic acid monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated monomers such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid. Saturated polycarboxylic acids; acid anhydrides of the unsaturated polycarboxylic acids.
- the amount of the (a4) ethylenically unsaturated carboxylic acid monomer used is preferably 0.5 to 6 parts by mass and preferably 1 to 5 parts by mass with respect to 100 parts by mass of the (A2) polymer. More preferred is 1.5 to 4.5 parts by mass.
- A4 When the amount of the ethylenically unsaturated carboxylic acid monomer used is 0.5 to 6 parts by mass, the dispersion stability of the binder is good, and problems such as generation of aggregates during electrode slurry preparation, Problems such as the slurry thickening with time are less likely to occur.
- the polymer (A2) is more preferably a polymer containing a structural unit derived from (a5) a vinyl cyanide compound.
- Vinyl cyanide compound examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like. Among these, acrylonitrile and methacrylonitrile are preferable.
- the amount of the vinyl cyanide compound used is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the polymer (A2). It is particularly preferred.
- the amount of the vinyl cyanide compound used is 1 to 30 parts by mass, the battery internal resistance is unlikely to increase excessively because of its good affinity with the electrolyte. Moreover, since it does not swell excessively with respect to the electrolytic solution, the adhesion of the electrode plate is lowered after the electrolytic solution is injected, and problems such as electrode plate peeling are unlikely to occur.
- the polymer may be a polymer containing a structural unit derived from another monomer other than the structural units described above.
- examples of other monomers include vinyl ester monomers, halogenated vinyl monomers, unsaturated monomers having a specific functional group, and the like exemplified as the other unsaturated monomers described above. .
- the amount of other monomers used is preferably 10 parts by weight or less, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer (A2). It is particularly preferred that When the amount of other monomers used is 0 to 10 parts by mass, the adhesion of the electrode plate is unlikely to decrease.
- the amount of (A1) fluorine-containing atom polymer used is preferably 3 to 70 parts by mass with respect to a total of 100 parts by mass of (A1) fluorine-containing atom polymer and (A2) polymer. More preferably, it is part by mass. (A1) When the amount of the fluorine-containing atomic polymer used is 3 to 70 parts by mass, chemical resistance, electrochemical stability, and electrode plate adhesion are improved.
- (Composite polymer) In (A) polymer particles, a plurality of polymers including (A1) fluorine-containing atomic polymer and (A2) polymer form a single particle (that is, composed of a composite polymer). Is preferred.
- the polymer particles (A) constituted by such a composite polymer are not formed from a single polymer (including a block polymer), but two or more types of polymers are composed of single particles. Forming. When two or more types of polymers are mixed to form particles, it is very difficult to uniformly mix due to differences in specific gravity of the polymers, particle surface tension, surface polarity, etc. When used as a single particle, such a problem is solved.
- the method for preparing the polymer particles is not particularly limited. In the presence of (A1) fluorine-containing atom polymer, (A2) a monomer component containing a monomer constituting the polymer is used. A method prepared by emulsion polymerization is preferred. As such a preparation method, for example, there is a method described in Japanese Patent Publication No. 4-55441.
- (A1) a fluorine-containing atomic polymer is prepared as described above, and then (A2) a monomer that constitutes the polymer is included using (A1) the fluorine-containing atomic polymer as a seed. What is necessary is just to emulsion-polymerize a monomer component.
- the (A) polymer particles thus prepared usually constitute a composite polymer by combining (A1) a fluorine-containing atom polymer and (A2) polymer.
- Such a composite polymer is preferable because it can produce a secondary battery with less capacity reduction during high-speed discharge, further excellent cycle characteristics, and better adhesion to the current collector.
- the toluene insoluble content contained in this composite polymer is usually 20% by mass or more, and preferably 30 to 90% by mass.
- the composition for an electrochemical device electrode binder prepared using the polymer particles (A) composed of this composite polymer When used, it is preferable in that the polymer flow is less likely to occur in the drying step after coating and the electrode active material is not easily covered excessively, so that the conductivity of the electrode is inhibited and overvoltage is unlikely to occur. Further, it is also preferable in that the durability against the electrolytic solution is less likely to decrease, and the electrode active material is less likely to be detached from the current collector.
- Emulsion polymerization is not particularly limited and can be performed under normal emulsion polymerization conditions.
- an emulsifier, a polymerization initiator, a chain transfer agent, and optionally a chelating agent, a pH adjuster, a solvent, etc. are added to an aqueous medium, and polymerization is carried out at a temperature of 30 to 90 ° C. for 1 to 30 hours.
- the monomer component containing the monomer constituting the polymer (A2) may be added to the reaction vessel all at once, may be added separately, or may be added continuously. .
- emulsifiers examples include an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
- these emulsifiers can be used individually by 1 type or in combination of 2 or more types.
- anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, aliphatic sulfonates, and polyethylene glycol alkyl ether sulfates.
- nonionic surfactants include alkyl ester type, alkyl ether type, and alkyl phenyl ether type polyethylene glycols.
- amphoteric surfactants include those having a carboxylate, sulfate, sulfonate, and phosphate ester salt as the anion moiety, and those having an amine salt and quaternary ammonium salt as the cation moiety. it can.
- betaines such as lauryl betaine and stearyl betaine
- amino acid type compounds such as lauryl- ⁇ -alanine, stearyl- ⁇ -alanine, lauryl di (aminoethyl) glycine, octyldi (aminoethyl) glycine, and the like.
- betaines such as lauryl betaine and stearyl betaine
- amino acid type compounds such as lauryl- ⁇ -alanine, stearyl- ⁇ -alanine, lauryl di (aminoethyl) glycine, octyldi (aminoethyl) glycine, and the like.
- betaines such as lauryl betaine and stearyl betaine
- amino acid type compounds such as lauryl- ⁇ -alanine, stearyl- ⁇ -alanine, lauryl di (aminoethyl) glycine, octyl
- the amount of the emulsifier used can be reduced.
- the amount of the emulsifier liberated in the active material paste can be reduced, a composition for an electrochemical device electrode binder with less foaming and excellent adhesion can be obtained.
- the reactive emulsifier include an emulsifier having, in one molecule, an ethylenically unsaturated group as a radical reactive group, a polyoxyalkylene group, a sulfone group or a sulfuric acid group as a hydrophilic group, and an alkyl group as a hydrophobic group. Can do.
- the use amount of the emulsifier is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the monomer component including the monomer constituting the polymer (A2).
- polymerization initiator examples include water-soluble polymerization initiators represented by persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, and the like.
- Oil-soluble polymerization initiators typified by hydroperoxides can be used. These water-soluble polymerization initiators and oil-soluble polymerization initiators are used in an amount of 0.01 to 10 masses per 100 mass parts of the monomer component containing the monomer constituting the polymer (A2). Part.
- redox polymerization initiators and the like based on a combination of a polymerization initiator and a reducing agent can be used alone or in combination of two or more.
- the reducing agent include ersorbic acid, sodium sorbate, potassium sorbate, ascorbic acid, sodium ascorbate, potassium ascorbate, saccharides, longgarit (sodium formaldehyde sulfoxylate), sodium bisulfite, potassium bisulfite, sodium sulfite.
- Sulfites such as potassium sulfite, sodium pyrosulfite, potassium hydrogen sulfite, sodium pyrosulfite, pyrosulfite such as potassium pyrosulfite, sodium thiosulfate, potassium thiosulfate, phosphorous acid, sodium phosphite, potassium phosphite, Phosphorous acid salts such as sodium hydrogen phosphite and potassium hydrogen phosphite, pyrophosphorous acid such as pyrophosphorous acid, sodium pyrophosphite, potassium pyrophosphite, sodium hydrogen pyrophosphite, potassium hydrogen pyrophosphite Salt, there is a mercaptan.
- the amount of these reducing agents used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer component containing the monomer constituting the (A2) polymer.
- Specific methods for adding the polymerization initiator and the reducing agent include, for example, a method in which both are added simultaneously and continuously from separate supply pipes into the polymerization reactor, and polymerization in which the polymerization initiator is present in excess of the reducing agent.
- There are a method of continuously adding a reducing agent into the system a method of continuously adding a polymerization initiator into a polymerization system in which the reducing agent is present in excess of the polymerization initiator, and the like.
- the equivalence ratio between the polymerization initiator and the reducing agent is preferably 100/1 to 1/100.
- an oxidation-reduction catalyst can be further added to the polymerization system to carry out emulsion polymerization.
- chain transfer agents examples include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan; dimethylxanthogen disulfide, diethylxanthogen disulfide Xanthogen disulfides such as diisopropylxanthogen disulfide; thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide; halogenated hydrocarbons such as chloroform, carbon tetrachloride, ethylene bromide; pentaphenylethane, Hydrocarbons such as ⁇ -methylstyrene
- chain transfer agents can be used individually by 1 type or in combination of 2 or more types.
- chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethylethylenediaminetriacetic acid.
- Solvents include small amounts of methyl ethyl ketone, acetone, trichlorotrifluoroethane, methyl isobutyl ketone, dimethyl sulfoxide, toluene, dibutyl phthalate, etc., as long as workability, disaster prevention safety, environmental safety, and production stability are not impaired. Can be used.
- the usage-amount of a solvent is 20 mass parts or less normally with respect to 100 mass parts of monomer components containing the monomer which comprises the (A2) polymer.
- the number average particle diameter of polymer particles measured by a light scattering method is preferably 100 to 300 nm, more preferably 120 to 280 nm, and particularly preferably 150 to 250 nm. When the number average particle diameter is within this range, the dispersion stability of the binder is good, and (A) the number of polymer particles, that is, the number of adhesion points is sufficiently large, which is preferable because high adhesion can be imparted. .
- (B) Dispersion medium As the dispersion medium, when water is used, or when (A) the polymer particles are obtained by emulsion polymerization as described above, the aqueous dispersion medium at the time of polymerization is used as it is, or it is used after being concentrated. can do. Moreover, it can substitute and use the organic dispersion medium suitable for an electrode active material as needed. There are no particular limitations on the organic dispersion medium used, and aromatic hydrocarbon compounds, non-aromatic hydrocarbon compounds, oxygen-containing hydrocarbon compounds, chlorine-containing hydrocarbon compounds, nitrogen-containing hydrocarbon compounds, sulfur-containing hydrocarbon compounds, etc. Is mentioned.
- organic dispersion medium examples include toluene, N-methylpyrrolidone (NMP), methyl isobutyl ketone (MIBK), cyclohexanone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and the like.
- the method of substitution with an organic dispersion medium is not particularly limited.
- the concentration of the polymer particles (A) in the composition for an electrochemical device electrode binder can be appropriately set so that the viscosity range is easy to handle depending on the type of the (B) dispersion medium used.
- the (B) dispersion medium is water, it is usually 20 to 55% by mass.
- the concentration is within this range, the composition of the electrochemical device electrode binder composition does not become excessively high, and handling in a blending process such as metering is easy.
- the solid content of the electrode slurry is difficult to decrease, and this is preferable because an electrode having a desired thickness can be easily produced.
- “in terms of solid content” means (B) a composition for an electrochemical device electrode binder that does not contain a dispersion medium.
- composition for an electrochemical device electrode binder of the present invention can be suitably used as a binder for a secondary battery electrode, a binder for a capacitor electrode, etc., taking advantage of its characteristics.
- Electrode slurry for electrochemical devices Next, an embodiment of the electrode slurry for electrochemical devices of the present invention will be described.
- the electrode slurry for electrochemical devices of this embodiment contains the composition for electrochemical device electrode binders, and an electrode active material.
- the electrode slurry for electrochemical devices of this embodiment can be prepared by mixing the composition for electrochemical device electrode binders and an electrode active material with various additives added as needed. .
- Electrochemical device electrode binder composition The composition for an electrochemical device electrode binder is described in “I. Composition for Electrochemical Device Electrode Binder”.
- the electrode slurry for an electrochemical device of this embodiment contains 0.1 to 10 parts by mass of the composition for an electrochemical device electrode binder in terms of solid content with respect to 100 parts by mass of the electrode active material.
- the content is preferably 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass.
- adhesion is good.
- the internal resistance does not increase excessively and does not affect battery characteristics.
- various kneaders, bead mills, high-pressure homogenizers, etc. can be used for mixing the composition for an electrochemical device electrode binder and the electrode active material.
- Electrode active material As an electrode active material contained in the electrode slurry for an electrochemical device of the present embodiment, a hydrogen storage alloy powder is suitably used in an aqueous battery such as a nickel metal hydride battery. More specifically, a material in which a part of Ni is substituted with an element such as Mn, Al, Co or the like based on MmNi 5 is preferably used. “Mm” represents misch metal which is a mixture of rare earth elements.
- the electrode active material is preferably a powder having a particle diameter of 3 to 400 ⁇ m and having passed through 100 mesh.
- a non-aqueous battery for example, MnO 2 , MoO 3 , V 2 O 5 , V 6 O 13 , Fe 2 O 3 , Fe 3 O 4 , Li (1-x) CoO 2 , Li (1-x ) NiO 2 , Li x Co y Sn z O 2 , Li (1-x) Co (1-y) Ni y O 2 , TiS 2 , TiS 3 , MoS 3 , FeS 2 , CuF 2 , NiF 2, etc.
- Carbon materials such as carbon fluoride, graphite, vapor-grown carbon fiber and / or pulverized product thereof, PAN-based carbon fiber and / or pulverized product thereof, pitch-based carbon fiber and / or pulverized product thereof; polyacetylene, poly- Examples thereof include conductive polymers such as p-phenylene.
- Li (1-x) CoO 2 Li (1-x) NiO 2 , Li x Co y Sn z O 2 , Li (1-x) Co (1-y) Ni y O 2, etc.
- a composite oxide it is preferable because both positive and negative electrodes can be assembled in a discharged state.
- Examples of the negative electrode active material include carbon such as carbon fluoride, graphite, vapor-grown carbon fiber and / or pulverized product thereof, PAN-based carbon fiber and / or pulverized product thereof, pitch-based carbon fiber and / or pulverized product thereof.
- Preferred examples include materials, conductive polymers such as polyacetylene and poly-p-phenylene, and amorphous compounds composed of compounds such as tin oxide and fluorine.
- a graphite material such as natural graphite, artificial graphite, or graphitized mesophase carbon having a high graphitization degree is used, a battery having good charge / discharge cycle characteristics and high capacity can be obtained.
- the average particle size of the carbonaceous material is reduced current efficiency, reduced paste stability, increased interparticle resistance within the resulting electrode coating film, etc.
- it is preferably 0.1 to 50 ⁇ m, more preferably 1 to 45 ⁇ m, and particularly preferably 3 to 40 ⁇ m.
- activated carbon or polyacene organic semiconductor can be used.
- additives added to the electrode slurry for an electrochemical device of the present embodiment as necessary include (B) a viscosity adjusting polymer that can be dissolved in the dispersion medium used, conductive carbon such as graphite, and metal powder.
- a conductive material such as can be added.
- the viscosity adjusting polymer that can be dissolved in the dispersion medium (B) to be used include ethylene vinyl alcohol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylamide, and the case where the (B) dispersion medium to be used is NMP. Examples thereof include methyl methacrylate and polyvinylidene fluoride.
- Electrodes for electrochemical devices Next, an embodiment of the electrode for an electrochemical device of the present invention will be described.
- the electrode for an electrochemical device of the present embodiment includes a current collector and an electrode layer formed by applying and drying an electrode slurry for an electrochemical device on the surface of the current collector.
- Examples of current collectors include water-based batteries and water-based capacitors, such as Ni mesh, Ni-plated punching metal, expanded metal, wire mesh, foam metal, and reticulated metal fiber sintered body.
- Examples of current collectors include water-based batteries and water-based capacitors, such as Ni mesh, Ni-plated punching metal, expanded metal, wire mesh, foam metal, and reticulated metal fiber sintered body.
- members such as aluminum foil and copper foil, can be mentioned as a suitable example, for example.
- Electrode layer The electrode layer is formed by applying the electrode slurry for electrochemical devices described in “II. Electrode device electrode slurry” to a predetermined thickness on at least one surface of the current collector, and then heating the electrode layer. , Formed by drying. If such an electrode layer is formed, the electrode for an electrochemical device of the present embodiment can be obtained.
- a method of applying the electrode slurry for an electrochemical device on the surface of the current collector a method using any coater head such as a reverse roll method, a comma bar method, a gravure method, an air knife method, or the like can be employed.
- a method of heating and drying the electrode slurry for an electrochemical device coated on the surface of the current collector for example, a method of leaving it to stand for natural drying, a blower dryer, a hot air dryer, an infrared heater Alternatively, a drying method using a far infrared heater or the like can be employed.
- the drying temperature is usually preferably 20 to 250 ° C., more preferably 130 to 170 ° C.
- the drying time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.
- the electrode for an electrochemical device of the present embodiment can be suitably used as an electrode for any one of an aqueous battery and a non-aqueous battery.
- a nickel-hydrogen battery electrode can be used as an aqueous battery, and an alkaline secondary battery electrode, a lithium ion battery electrode, an electric double layer capacitor electrode, an electrode for a lithium ion capacitor, or the like can be exhibited as a non-aqueous battery.
- the non-aqueous electrolyte solution one in which an electrolyte is dissolved in a non-aqueous solvent is usually used.
- the electrolyte for example, LiClO 4, LiBF 4, LiAsF 6, CF 3 SO 3 Li, LiPF 6, LiI, LiAlCl 4, NaClO 4, NaBF 4, NaI, (n-Bu) 4 NClO 4, (N-Bu) 4 NBF 4 , KPF 6 and the like can be mentioned.
- non-aqueous solvent used in the electrolytic solution examples include ethers, ketones, lactones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, Phosphate ester compounds and sulfolane compounds can be used.
- ethers, ketones, nitriles, chlorinated hydrocarbons, carbonates, and sulfolane compounds are preferable.
- tetrahydrofuran 2-methyltetrahydrofuran, 1,4-dioxane, anisole, monoglyme, diglyme, triglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1, 2-dichloroethane, ⁇ -butyrolactone, dimethoxyethane, methyl formate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, sulfolane, 3-methylsulfolane, trimethyl phosphate, or triethyl phosphate, or these And the like.
- a 5N or higher potassium hydroxide aqueous solution is usually used as an electrolytic solution for an aqueous battery.
- a battery is configured using parts such as a separator, a terminal, and an insulating plate.
- the structure of the battery is not particularly limited, but the positive electrode, the negative electrode, and, if necessary, a paper type battery having a single layer or multiple layers of the separator, or the positive electrode, the negative electrode, and if necessary, the separator is rolled. Examples thereof include a cylindrical battery wound in a shape.
- the secondary battery manufactured using the electrochemical device electrode of the present embodiment can be suitably used for, for example, AV equipment, OA equipment, communication equipment, and the like.
- Electrochemical device The electrochemical device of the present invention comprises the electrode for an electrochemical device described in “III. Electrode for Electrochemical Device”. Electrodes for electrochemical devices are capable of manufacturing secondary batteries with low capacity loss during high-speed discharge and excellent cycle characteristics, and have good adhesion to the current collector. It can be suitably used for a power supply battery of a recent electronic device that is required.
- Electrode adhesion (N / 2 cm) A test piece having a width of 2 cm and a length of 12 cm was cut out from the secondary battery electrode, and the electrode layer side surface of the test piece was attached to an aluminum plate using a double-sided tape. It was. In addition, an 18 mm wide tape ("Cello Tape (registered trademark)" (manufactured by Nichiban Co., Ltd.)) (specified in JIS Z1522) is attached to the surface of the current collector of the test piece, and the tape is taped at a speed of 50 mm / min in the 90 ° direction. The strength (N / 2 cm) when the film was peeled was measured 6 times, and the average value was calculated as the peel strength (N / 2 cm). In addition, it can be evaluated that the larger the peel strength value, the higher the adhesion strength between the current collector and the electrode layer, and the more difficult the electrode layer peels from the current collector.
- Charging over 2.5 hours with constant current (1C) -constant voltage (4.2V) method and discharging with constant current (1C) method repeated 50 cycles for the discharge capacity of the third cycle The ratio (%) of the discharge capacity of the eyes was measured and used as an index of cycle characteristics.
- Example 1 In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.1 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite, ⁇ -methylstyrene dimer 2 parts, 0.1 part of dodecyl mercaptan, 1st stage monomer component shown in Table 1, and 10 parts of (A1) fluorine-containing atomic polymer (in terms of solid content) are charged all at once, and the temperature is raised to 70 ° C. The polymerization reaction was carried out for 2 hours.
- (A1) fluorine-containing atomic polymer in terms of solid content
- the second-stage monomer component shown in Table 1 was added over 6 hours while maintaining the reaction temperature at 70 ° C. When 3 hours had elapsed from the start of addition of the second-stage monomer component, 0.5 part of ⁇ -methylstyrene dimer and 0.1 part of dodecyl mercaptan were further added. After the addition of the second-stage monomer component was completed, the temperature was raised to 80 ° C. and further reacted for 2 hours. After the completion of the polymerization reaction, the pH of the latex is adjusted to 7.5, the residual monomer is treated by steam distillation, and then concentrated to 50% solids under reduced pressure, thereby forming an electrochemical device electrode binder composition (1). Got.
- the number average particle diameter of the obtained composition for electrochemical device electrode binder (1) was 200 nm.
- the obtained binder composition (1) is diluted with water so that the solid content concentration is about 0.04%, and an appropriate amount is dropped onto a copper collodion mesh, and exposed to osmium vapor for 20 minutes to osmium staining. Then, the sample for observation was prepared by air-drying overnight. When this sample was observed with a transmission electron microscope (trade name “H-7650”, manufactured by Hitachi High-Technologies Corporation), the (A1) fluorine-containing atomic polymer and the (A2) polymer were composed of a composite polymer. It was confirmed that
- Example 2 and 3 Except having set it as the composition shown in Table 1, it carried out similarly to Example 1, and obtained the composition (2) and (3) for electrochemical device electrode binders.
- the number average particle diameter of the obtained composition for electrochemical device electrode binders (2) and (3) was 150 nm and 220 nm, respectively.
- each binder composition was observed with the transmission electron microscope in the same manner as in Example 1, it was found that (A1) the fluorine-containing atomic polymer and (A2) polymer were composed of a composite polymer. confirmed.
- composition for an electrochemical device electrode binder (5) was obtained by adjusting the pH to 7.0 with a 1% NaOH aqueous solution.
- the number average particle diameter of the obtained composition for electrochemical device electrode binder (5) was 140 nm.
- the temperature was raised to 80 ° C., after stirring for further 3 hours, cooled to room temperature, the pH was adjusted to 7.0 with 10% NH 4 OH aqueous solution.
- the composition for electrochemical device electrode binder (6) was obtained by concentrating under reduced pressure and adjusting solid content to 40%.
- the number average particle diameter of the composition (6) for electrochemical device electrode binder obtained was 100 nm.
- Comparative Example 4 By mixing the binder composition for electrochemical device electrodes (4) obtained in Comparative Example 1 and the latex of the (A1) fluorine-containing atomic polymer so that the mass ratio is 90/10 (in terms of solid content). A composition (7) for an electrochemical device electrode binder was obtained. The number average particle diameter of the composition (7) for electrochemical device electrode binder obtained was 140 nm. In addition, since the film which dried the composition for electrochemical device electrode binders (7) becomes cloudy, it is estimated that the (A1) fluorine-containing atomic polymer and the (A2) polymer are causing phase separation. .
- Electrochemical device electrode binder compositions (1) to (7) or polyvinylidene fluoride (PVdF) obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were used for electrochemical devices as shown below. Electrodes were manufactured, and electrode adhesion evaluation and cycle characteristics were measured using them.
- the electrode slurry for electrochemical devices was prepared by stirring and mixing for 1.5 minutes.
- the prepared electrode slurry for electrochemical devices was uniformly applied to the surface of the current collector made of copper foil by a doctor blade method so that the film thickness after drying was 100 ⁇ m, and was dried at 120 ° C. for 20 minutes.
- the lithium ion battery negative electrode (negative electrode for electrochemical devices) was obtained by pressing with a roll press so that the density of the obtained electrode layer was 1.8 g / cm 3 .
- PVdF When PVdF is used as the negative electrode binder instead of the electrochemical device electrode binder composition, 4 parts of PVdF (in terms of solid content) is added to the biaxial planetary mixer, and 100 parts of graphite is used as the negative electrode active material. 80 parts of N-methylpyrrolidone (hereinafter also referred to as “NMP”) was added (in terms of solid content) and stirred at 60 rpm for 1 hour. Then, after further adding 20 parts of NMP, using the above stirring defoamer, electrode slurry was prepared by stirring and mixing at 200 rpm for 2 minutes, 1800 rpm for 5 minutes, and under vacuum at 1800 rpm for 1.5 minutes did.
- NMP N-methylpyrrolidone
- the prepared electrode slurry was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 150 ⁇ m, followed by drying at 120 ° C. for 20 minutes. Then, the lithium ion battery negative electrode was obtained by pressing with a roll press machine so that the density of the electrode layer obtained may be 1.8 g / cm 3 .
- a device electrode slurry was prepared.
- the prepared electrode slurry for an electrochemical device was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 90 ⁇ m, and was dried at 120 ° C. for 20 minutes.
- the lithium ion battery positive electrode positive electrode for electrochemical devices was obtained by pressing with a roll press so that the density of the obtained electrode layer was 3.5 g / cm 3 .
- PVdF is used as the positive electrode binder instead of the electrochemical device electrode binder composition
- 4 parts of PVdF (in terms of solid content) is added to the biaxial planetary mixer, and lithium iron phosphate is used as the positive electrode active material.
- 100 parts (in terms of solid content), 5 parts (in terms of solid content) of acetylene black as a conductive agent, and 25 parts of NMP were added and stirred at 60 rpm for 1 hour.
- an electrode slurry was prepared by stirring and mixing at 200 rpm for 2 minutes, 1800 rpm for 5 minutes, and under vacuum at 1800 rpm for 1.5 minutes using the stirring deaerator. did.
- the prepared electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 90 ⁇ m, and was dried at 120 ° C. for 20 minutes. Then, the lithium ion battery positive electrode was obtained by pressing with a roll press so that the density of the electrode layer obtained may be 3.8 g / cm 3 .
- Example 4 A battery electrode was produced using the composition for an electrochemical device electrode binder obtained in Example 1, a secondary battery was produced using them, and the evaluation was performed. As a result, the adhesion at the positive electrode was 0.54 N / 2 cm, and the evaluation of flexibility was “ ⁇ ”. The adhesion at the negative electrode was 0.39 N / 2 cm, and the evaluation of flexibility was “ ⁇ ”. Furthermore, the cycle characteristics were 90%.
- Example 5 to 6 Comparative Examples 5 to 9
- Battery electrodes were produced using the composition for electrochemical device electrode binders or PVdF described in Table 2, secondary batteries were produced using them, and the evaluation was performed. The evaluation results are also shown in Table 2.
- the battery electrode produced using the composition for an electrochemical device electrode binder of the present invention has excellent cycle characteristics and flexibility, and also has good adhesion to the current collector.
- the cycle characteristics are inferior (Comparative Example 5).
- polyvinylidene fluoride is used as a binder, adhesiveness is remarkably inferior (Comparative Example 6).
- the binder composition which does not have the structural unit derived from a conjugated diene compound was used, it was inferior to adhesiveness (comparative example 7).
- a secondary battery that can be suitably used for AV equipment, OA equipment, communication equipment, etc., which has a low capacity drop during high-speed discharge and excellent cycle characteristics, is provided. can do.
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Abstract
Description
本発明の電気化学デバイス電極バインダー用組成物は、(A1)含フッ素原子重合体、並びに(A2)芳香族ビニル単量体に由来する構成単位及び共役ジエン系単量体に由来する構成単位を含む重合体、を含有する(A)重合体粒子と、(B)分散媒と、を含有するものである。以下、その詳細について説明する。
(A)重合体粒子は、(A1)含フッ素原子重合体、並びに(A2)芳香族ビニル単量体に由来する構成単位及び共役ジエン系単量体に由来する構成単位を含む重合体(以下、「(A2)重合体」ともいう)、を含有するものである。ここで、(A)重合体粒子は、(A1)含フッ素原子重合体と(A2)重合体が相分離を起こしている状態や、構成比率に局所的な偏りが生じた状態で含有するものは含まれない。なお、本明細書中「重合体粒子」とは、重合体を分散媒に均一に分散させたときの一つの分散単位をいい、光散乱法又は電子顕微鏡測定により大きさを測定可能なものである。
(i) (A1)含フッ素原子重合体:
(A1)含フッ素原子重合体は、フッ素原子を含有する重合体であれば特に限定されない。例えば、フッ化ビニリデン、六フッ化プロピレン、フッ化ビニル、テトラフルオロエチレン、パーフルオロアルキルビニルエーテル、フルオロアルキル(メタ)アクリレートに由来する構成単位を有する重合体がある。これらの中でも、フッ化ビニリデンと六フッ化プロピレンに由来する構成単位を有する重合体が好ましい。
(A2)重合体は、芳香族ビニル単量体に由来する構成単位(以下、「芳香族ビニル単位」ともいう)及び共役ジエン系単量体に由来する構成単位(以下、「共役ジエン単位」ともいう)を含む重合体である。
芳香族ビニル単位は、(a1)芳香族ビニル化合物を重合させた構造単位である。(a1)芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、p-メチルスチレン、ジビニルベンゼン、ビニルトルエン、クロルスチレン等がある。これらの中でも、スチレンが好ましい。
共役ジエン単位は、(a2)共役ジエン化合物を重合させた構造単位である。(a2)共役ジエン化合物としては、例えば、ブタジエン、イソプレン、クロロプレン、2-クロロ-1,3-ブタジエン等がある。これらの中でも、ブタジエンが好ましい。
(a3)(メタ)アクリル酸エステル化合物としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、アミル(メタ)アクリレート、イソアミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート等のアルキル(メタ)アクリレート類;
(a4)エチレン性不飽和カルボン酸単量体としては、例えば、(メタ)アクリル酸、クロトン酸等の不飽和モノカルボン酸類;マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸等の不飽和ポリカルボン酸類;前記不飽和ポリカルボン酸の酸無水物類等がある。
シアン化ビニル化合物としては、例えば、アクリロニトリル、メタクリロニトリル、α-クロルアクリロニトリル、α-エチルアクリロニトリル等がある。これらの中でも、アクリロニトリル、メタクリロニトリルが好ましい。
(A)重合体粒子は、(A1)含フッ素原子重合体と(A2)重合体とを含む複数の重合体が単一粒子を形成している(即ち、複合化重合体で構成されている)ことが好ましい。このような複合化重合体によって構成された(A)重合体粒子は、単一の重合体(ブロック重合体を含む)から形成されたものではなく、2種類以上の重合体が単一粒子を形成している。重合体を2種類以上混合して粒子を形成する場合、重合体の比重差、粒子表面張力、表面の極性の違い等により均一に混合することは非常に困難であるが、複数の重合体を一つの粒子として用いる場合には、このような問題が解消される。
(A)重合体粒子を調製する方法は特に限定されるものではないが、(A1)含フッ素原子重合体の存在下、(A2)重合体を構成する単量体を含む単量体成分を乳化重合して調製する方法が好ましい。このような調製方法としては、例えば、特公平4-55441号公報に記載の方法がある。
(数平均粒子径)
(A)重合体粒子の光散乱法により測定される数平均粒子径は、100~300nmであることが好ましく、120~280nmであることが更に好ましく、150~250nmであることが特に好ましい。数平均粒子径がこの範囲内にあると、バインダーの分散安定性が良好であり、且つ(A)重合体粒子の数、すなわち接着点の数が十分多く、高い密着性を付与できるために好ましい。
(B)分散媒としては、水を用いたり、(A)重合体粒子を前述のように乳化重合して得た場合には、重合時の水分散媒をそのまま用いたり、濃縮して用いたりすることができる。また、必要に応じて電極活物質に好適な有機系分散媒体に置換して用いることができる。使用する有機系分散媒体については特に限定されず、芳香族炭化水素化合物、非芳香族炭化水素化合物、含酸素炭化水素化合物、含塩素炭化水素化合物、含窒素炭化水素化合物、含硫黄炭化水素化合物等が挙げられる。
次に、本発明の電気化学デバイス用電極スラリーの一実施形態について説明する。本実施形態の電気化学デバイス用電極スラリーは、電気化学デバイス電極バインダー用組成物と、電極活物質とを含有するものである。なお、本実施形態の電気化学デバイス用電極スラリーは、電気化学デバイス電極バインダー用組成物と電極活物質とを、必要に応じて添加される各種添加剤とともに混合することにより、調製することができる。
電気化学デバイス電極バインダー用組成物は、「I.電気化学デバイス電極バインダー用組成物」にて記載したものである。
本実施形態の電気化学デバイス用電極スラリーに含有される電極活物質としては、水系電池、例えばニッケル水素電池では、水素吸蔵合金粉末が好適に用いられる。より具体的には、MmNi5をベースに、Niの一部をMn、Al、Co等の元素で置換したものが好適に用いられる。なお、「Mm」は、希土類の混合物であるミッシュメタルを表している。電極活物質は、その粒子径が3~400μmである、100メッシュを通過した粉末であることが好ましい。また、非水系電池においては、例えば、MnO2、MoO3、V2O5、V6O13、Fe2O3、Fe3O4、Li(1-x)CoO2、Li(1-x)NiO2、LixCoySnzO2、Li(1-x)Co(1-y)NiyO2、TiS2、TiS3、MoS3、FeS2、CuF2、NiF2等の無機化合物;フッ化カーボン、グラファイト、気相成長炭素繊維及び/又はその粉砕物、PAN系炭素繊維及び/又はその粉砕物、ピッチ系炭素繊維及び/又はその粉砕物等の炭素材料;ポリアセチレン、ポリ-p-フェニレン等の導電性高分子等を挙げることができる。特に、Li(1-x)CoO2、Li(1-x)NiO2、LixCoySnzO2、Li(1-x)Co(1-y)NiyO2等のリチウムイオン含有複合酸化物を用いた場合、正負極共に放電状態で組み立てることが可能となるために好ましい。
本実施形態の電気化学デバイス用電極スラリーに必要に応じて添加される各種添加剤としては、使用する(B)分散媒に溶解可能な粘度調整用ポリマーや、グラファイト等の導電性カーボン、金属粉末等の導電材等を添加することができる。使用する(B)分散媒に溶解可能な粘度調整用ポリマーとしては、使用する(B)分散媒がNMPである場合を例に挙げると、エチレンビニルアルコール、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、ポリメチルメタクリレート、ポリフッ化ビニリデン等を挙げることができる。
次に、本発明の電気化学デバイス用電極の一実施形態について説明する。本実施形態の電気化学デバイス用電極は、集電体と、電気化学デバイス用電極スラリーを集電体の表面上に塗布及び乾燥して形成した電極層と、を備えるものである。
集電体としては、水系電池、水系キャパシタでは、例えばNiメッシュ、Niメッキされたパンチングメタル、エキスパンドメタル、金網、発泡金属、網状金属繊維焼結体等がある。また、非水系電池、非水系キャパシタでは、例えばアルミ箔や銅箔等の部材を好適例として挙げることができる。
電極層は、前述の集電体の少なくとも一方の表面上に、「II.電気化学デバイス用電極スラリー」にて記載した電気化学デバイス用電極スラリーを所定の厚みとなるように塗布した後、加熱、乾燥して形成したものである。このような電極層を形成すれば、本実施形態の電気化学デバイス用電極を得ることができる。集電体の表面上に電気化学デバイス用電極スラリーを塗布する方法としては、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法等の任意のコーターヘッドを用いる方法を採用することができる。
本発明の電気化学デバイスは、「III.電気化学デバイス用電極」に記載の電気化学デバイス用電極を備えるものである。電気化学デバイス用電極が、高速放電での容量低下が少なく、サイクル特性に優れる二次電池を製造可能であり、集電体との密着性が良好なものであるため、小型化・軽量化が要求される近年の電子機器の電源電池等に好適に使用することができる。
○;割れが見られない
△;塗工層の端部にのみ割れが見られる
×;塗工層全面に割れが見られる
電磁式撹拌機を備えた内容積約6Lのオートクレーブの内部を十分に窒素置換した後、脱酸素した純水2.5L、及び乳化剤としてパーフルオロデカン酸アンモニウム25gを仕込み、350rpmで撹拌しながら60℃まで昇温した。次いで、フッ化ビニリデン(VDF)70%、及び六フッ化プロピレン(HFP)30%からなる混合ガスを、内圧が20kg/cm2Gに達するまで仕込んだ。その後、重合開始剤としてジイソプロピルパーオキシジカーボネートを20%含有するフロン113溶液25gを、窒素ガスを使用して圧入し、重合を開始させた。重合中はVDF60.2%、及びHFP39.8%からなる混合ガスを逐次圧入して、圧力を20kg/cm2Gに維持した。また、重合の進行とともに重合速度が低下するため、3時間経過後に、先と同量の重合開始剤を、窒素ガスを使用して圧入し、更に3時間反応を継続させた。反応液を冷却するとともに撹拌を停止し、未反応単量体を放出して反応を停止させ、(A1)含フッ素原子重合体のラテックスAを得た。(A1)含フッ素原子重合体の数平均粒子径は120nmであった。また、19F-NMRから求めた各単量体の質量組成比はVdF/HFP=85/15であった。
攪拌機を備えた温度調節の可能なオートクレーブ中に、水200部、ドデシルベンゼンスルホン酸ナトリウム0.1部、過硫酸カリウム1.0部、重亜硫酸ナトリウム0.5部、α-メチルスチレンダイマー0.2部、ドデシルメルカプタン0.1部、表1に示した一段目単量体成分、及び(A1)含フッ素原子重合体10部(固形分換算)を一括して仕込み、70℃に昇温して2時間重合反応を行った。重合添加率が80%以上であることを確認した後、反応温度を70℃に維持したまま、表1に示した二段目単量体成分を6時間かけて添加した。尚、二段目単量体成分の添加開始から3時間経過した時点で、α-メチルスチレンダイマー0.5部、及びドデシルメルカプタン0.1部を更に添加した。二段目単量体成分の添加終了後、温度を80℃に昇温し、更に2時間反応させた。重合反応終了後、ラテックスのpHを7.5に調節し、残留モノマーを水蒸気蒸留で処理した後、減圧下で固形分50%まで濃縮することで、電気化学デバイス電極バインダー用組成物(1)を得た。得られた電気化学デバイス電極バインダー用組成物(1)の数平均粒子径は200nmであった。また、得られたバインダー組成物(1)を固形分濃度約0.04%になるように水で希釈して銅製のコロジオンメッシュに適量を滴下し、20分間オスミウムの蒸気に曝露してオスミウム染色を行った後、終夜風乾して観察用サンプルを作成した。このサンプルを透過型電子顕微鏡(商品名「H-7650」、日立ハイテクノロジーズ社製)で観察したところ、(A1)含フッ素原子重合体及び(A2)重合体が複合化重合体で構成されていることが確認された。
表1に示す組成としたこと以外は実施例1と同様にして電気化学デバイス電極バインダー用組成物(2)、(3)を得た。なお、得られた電気化学デバイス電極バインダー用組成物(2)、(3)の数平均粒子径は、それぞれ150nm、220nmであった。また、各バインダー組成物を実施例1と同様にして前記透過型電子顕微鏡で観察したところ、(A1)含フッ素原子重合体及び(A2)重合体が複合化重合体で構成されていることが確認された。
攪拌機を備えた温度調節の可能なオートクレーブ中に、水200部、ドデシルベンゼンスルホン酸ナトリウム0.1部、過硫酸カリウム1.0部、重亜硫酸ナトリウム0.5部、α-メチルスチレンダイマー0.2部、ドデシルメルカプタン0.1部、及び表1に示した一段目単量体成分を一括して仕込み、70℃に昇温し2時間重合反応させた。重合添加率が80%以上であることを確認した後、反応温度を70℃に維持したまま、表1に示す二段目単量体成分を6時間かけて添加した。尚、二段目単量体成分の添加開始から3時間経過した時点で、α-メチルスチレンダイマー0.5部及びドデシルメルカプタン0.1部を添加した。二段目単量体成分の添加終了後、温度を80℃に昇温し、更に2時間反応させた。重合反応終了後、ラテックスのpHを7.5に調節し、残留モノマーを水蒸気蒸留で処理した後、減圧下で固形分50%まで濃縮することで、電気化学デバイス電極バインダー用組成物(4)を得た。得られた電気化学デバイス電極バインダー用組成物(4)の数平均粒子径は180nmであった。
容量7Lのセパラブルフラスコの内部を十分に窒素置換した後、(A1)含フッ素原子重合体のラテックス150部(固形分換算)、及び乳化剤として2-(1-アリル)-4-ノニルフェノキシポリエチレングリコールスルフェートアンモニウム3部を仕込み、75℃に昇温した。次に、n-ブチルアクリレート60部、メチルメタクリレート36部、スチレンスルホン酸ナトリウム4部、及び適量の水を加え、75℃で30分撹拌した。その後、重合開始剤として過硫酸ナトリウム0.5部を加え、85~95℃で2時間重合を行った。冷却して反応を停止させ、1%NaOH水溶液にてpHを7.0に調整することで電気化学デバイス電極バインダー用組成物(5)を得た。得られた電気化学デバイス電極バインダー用組成物(5)の数平均粒子径は140nmであった。
容量7Lのセパラブルフラスコの内部を十分に窒素置換した後、水675部、10%ドデシル硫酸ナトリウム水溶液1.5部(固形分換算)、トリポリリン酸ナトリウム0.8部を投入し、攪拌しながら75℃まで昇温させた。重合開始剤として過硫酸アンモニウム2部を投入し、次いで、アクリル酸2-エチルヘキシル74部、アクリル酸ブチル20部、アクリロニトリル5部、及びエチレングリコールジメタクリレート1部からなる混合物を2時間かけて滴下した。滴下終了後80℃に昇温し、更に3時間攪拌を行った後、室温まで冷却し、10%NH4OH水溶液にてpHを7.0に調整した。減圧下で濃縮し、固形分を40%に調節することで電気化学デバイス電極バインダー用組成物(6)を得た。得られた電気化学デバイス電極バインダー用組成物(6)の数平均粒子径は100nmであった。
比較例1で得られた電気化学デバイス電極用バインダー組成物(4)と、(A1)含フッ素原子重合体のラテックスを質量比で90/10(固形分換算)となるように混合することで電気化学デバイス電極バインダー用組成物(7)を得た。得られた電気化学デバイス電極バインダー用組成物(7)の数平均粒子径は140nmであった。なお、電気化学デバイス電極バインダー用組成物(7)を乾燥させたフィルムは白濁することから、(A1)含フッ素原子重合体及び(A2)重合体が相分離を起こしていることが推定される。
実施例1で得られた電気化学デバイス電極バインダー用組成物を用いて電池電極を製造し、それらを用いて二次電池を作製し、その評価を行った。その結果、正極での密着性は0.54N/2cmであり、柔軟性の評価は「○」であった。また、負極での密着性は0.39N/2cmであり、柔軟性の評価は「○」であった。更に、サイクル特性は90%であった。
表2に記載した電気化学デバイス電極バインダー用組成物又はPVdFを用いて電池電極を製造し、それらを用いて二次電池を作製し、その評価を行った。評価結果を表2に併せて記載する。
Claims (8)
- (A1)含フッ素原子重合体、並びに
(A2)芳香族ビニル単量体に由来する構成単位及び共役ジエン系単量体に由来する構成単位を含む重合体、を含有する(A)重合体粒子と、
(B)分散媒と、を含有する電気化学デバイス電極バインダー用組成物。 - 光散乱法により測定される前記(A)重合体粒子の数平均粒子径が100~300nmである請求項1に記載の電気化学デバイス電極バインダー用組成物。
- 前記(A2)重合体が、
(a1)芳香族ビニル化合物を20~50質量部、
(a2)共役ジエン化合物を25~60質量部、
(a3)(メタ)アクリル酸エステル化合物を5~40質量部、及び
(a4)エチレン性不飽和カルボン酸単量体を0.5~6質量部、含む単量体成分(但し、単量体成分の合計を100質量部とする)を重合して得られるものである請求項1又は2に記載の電気化学デバイス電極バインダー用組成物。 - 前記(A)重合体粒子が、前記(A1)含フッ素原子重合体と前記(A2)重合体との複合化重合体で構成されている請求項1~3のいずれか一項に記載の電気化学デバイス電極バインダー組成物。
- 前記(A)重合体粒子が、前記(A1)含フッ素原子重合体の存在下、前記(A2)重合体を構成する単量体を含む単量体成分を乳化重合して得られるものである請求項1~4のいずれか一項に記載の電気化学デバイス電極バインダー用組成物。
- 請求項1~5のいずれか一項に記載の電気化学デバイス電極バインダー用組成物と、
電極活物質と、を含有する電気化学デバイス用電極スラリー。 - 集電体と、
前記集電体の表面上に請求項6に記載の電気化学デバイス用電極スラリーを塗布及び乾燥して形成した電極層と、を備える電気化学デバイス用電極。 - 請求項7に記載の電気化学デバイス用電極を備える電気化学デバイス。
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Also Published As
Publication number | Publication date |
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JP2014209503A (ja) | 2014-11-06 |
JP5854092B2 (ja) | 2016-02-09 |
JP5819190B2 (ja) | 2015-11-18 |
JP2015005523A (ja) | 2015-01-08 |
TW201043672A (en) | 2010-12-16 |
KR20120027126A (ko) | 2012-03-21 |
JPWO2010113940A1 (ja) | 2012-10-11 |
KR101630898B1 (ko) | 2016-06-15 |
JP2014222665A (ja) | 2014-11-27 |
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