JPWO2019013102A1 - Binder composition for electrochemical device functional layer, composition for electrochemical device functional layer, functional layer for electrochemical device, and electrochemical device - Google Patents
Binder composition for electrochemical device functional layer, composition for electrochemical device functional layer, functional layer for electrochemical device, and electrochemical device Download PDFInfo
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- JPWO2019013102A1 JPWO2019013102A1 JP2019529101A JP2019529101A JPWO2019013102A1 JP WO2019013102 A1 JPWO2019013102 A1 JP WO2019013102A1 JP 2019529101 A JP2019529101 A JP 2019529101A JP 2019529101 A JP2019529101 A JP 2019529101A JP WO2019013102 A1 JPWO2019013102 A1 JP WO2019013102A1
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- soluble polymer
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- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose 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
- 239000004927 clay Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- BSCJIBOZTKGXQP-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCO BSCJIBOZTKGXQP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride 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
- 239000007774 positive electrode material Substances 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004804 winding Methods 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/52—Separators
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含有する水溶性重合体を含む、電気化学素子機能層用バインダー組成物である。A binder composition for an electrochemical device functional layer, comprising a water-soluble polymer containing a hydroxyl group-containing monomer unit in an amount of 15.000% by mass or more and 90.000% by mass or less.
Description
本発明は、電気化学素子機能層用バインダー組成物、電気化学素子機能層用組成物、電気化学素子用機能層、及び電気化学素子に関するものである。 The present invention relates to a binder composition for an electrochemical device functional layer, a composition for an electrochemical device functional layer, a functional layer for an electrochemical device, and an electrochemical device.
リチウムイオン二次電池、電気二重層キャパシタ、及びリチウムイオンキャパシタなどの電気化学素子は、小型で軽量、且つ、エネルギー密度が高く、更に繰り返し充放電が可能という特性があり、幅広い用途に使用されている。そして電気化学素子は、一般に、外装体と、外装体内に収容された電極アッセンブリとを備える。電極アッセンブリは、複数の電極、及びこれら電極を隔離して短絡を防止するセパレータの積層体である。 Electrochemical devices such as lithium-ion secondary batteries, electric double-layer capacitors, and lithium-ion capacitors are small and lightweight, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. There is. The electrochemical device generally includes an outer casing and an electrode assembly housed in the outer casing. The electrode assembly is a laminate of a plurality of electrodes and a separator that isolates the electrodes and prevents a short circuit.
ここで、電気化学素子の部材としては、当該部材に所望の機能を発揮させるために配合された成分を含んでなる機能層を備える部材が使用されている。例えば、電気化学素子が二次電池である場合には、正極と負極とを隔離して正極と負極との間の短絡を防ぐセパレータなどの部材に、機能層として、耐熱性や強度の向上を目的とした多孔膜層、及び電池部材間の接着性の向上を目的とした接着層などが設けられている。また、電気化学素子が二次電池である場合には、集電体上に電極活物質を含む電極合材層を備える電極基材の上に、さらに上述の多孔膜層や接着層を備える電極が使用されている。 Here, as the member of the electrochemical element, a member having a functional layer containing a component blended for exhibiting a desired function in the member is used. For example, when the electrochemical element is a secondary battery, a member such as a separator that separates the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode is used as a functional layer to improve heat resistance and strength. A porous film layer for the purpose, an adhesive layer for improving the adhesiveness between the battery members, and the like are provided. Further, when the electrochemical element is a secondary battery, an electrode further including the above-mentioned porous membrane layer or adhesive layer on the electrode base material including the electrode mixture layer containing the electrode active material on the current collector. Is used.
そして、電気化学素子の更なる性能向上を達成すべく、機能層の形成に用いる組成物の改良が従来から試みられている。例えば、特許文献１では、２つ以上の水酸基を有する単量体単位を０．０５質量％以上５質量％以下含む粒子状重合体、及び増粘剤として機能し得る水溶性重合体等の任意成分を含む非水系二次電池多孔膜用バインダー組成物が提案されている。また、特許文献２では、酸化チタン等のフィラーと、（メタ）アクリルアミド単量体単位を４０質量％以上含有する水溶性重合体とを含む保護膜用スラリーが提案されている。 Then, in order to further improve the performance of the electrochemical device, attempts have been made to improve the composition used for forming the functional layer. For example, in Patent Document 1, a particulate polymer containing 0.05% by mass or more and 5% by mass or less of a monomer unit having two or more hydroxyl groups, and a water-soluble polymer capable of functioning as a thickener are optional. A binder composition for a non-aqueous secondary battery porous membrane containing components has been proposed. Further, Patent Document 2 proposes a protective film slurry containing a filler such as titanium oxide and a water-soluble polymer containing 40% by mass or more of a (meth) acrylamide monomer unit.
ここで、近年、耐熱性及びレート特性の双方の面で優れる電気化学素子を提供することが必要とされている。しかしながら、上記従来の技術では、得られる保護膜及び多孔膜といった機能層を備える電気化学素子のレート特性を高めるという点で改善の余地があった。また、上記従来の技術では、かかる機能層を備える電気化学素子の耐熱性を高めるという点においても、改善の余地があった。このため、上記従来の技術では、得られる電気化学素子の耐熱性及びレート特性の双方をバランスよく向上させうる機能層を提供するという点で改善の余地があった。 Here, in recent years, it has been required to provide an electrochemical element excellent in both heat resistance and rate characteristics. However, in the above-mentioned conventional technique, there is room for improvement in that the rate characteristics of the electrochemical device provided with the functional layers such as the protective film and the porous film obtained can be improved. Further, in the above-mentioned conventional technique, there is room for improvement in terms of increasing the heat resistance of the electrochemical device including such a functional layer. Therefore, the above-mentioned conventional technique has room for improvement in that it provides a functional layer capable of improving both the heat resistance and rate characteristics of the obtained electrochemical device in a well-balanced manner.
そこで、本発明は、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用バインダー組成物を提供することを目的とする。
また、本発明は、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用組成物を提供することを目的とする。
そして、本発明は、電気化学素子の耐熱性及びレート特性を向上させ得る電気化学素子用機能層を提供することを目的とする。
さらに、本発明は、耐熱性及びレート特性の高い電気化学素子を提供することを目的とする。Therefore, an object of the present invention is to provide a binder composition for an electrochemical device functional layer capable of forming a functional layer capable of improving the heat resistance and rate characteristics of the electrochemical device.
Another object of the present invention is to provide a composition for an electrochemical device functional layer capable of forming a functional layer capable of improving the heat resistance and rate characteristics of the electrochemical device.
And an object of the present invention is to provide a functional layer for electrochemical devices which can improve heat resistance and rate characteristics of an electrochemical device.
Another object of the present invention is to provide an electrochemical device having high heat resistance and high rate characteristics.
本発明者らは、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者らは、ヒドロキシル基含有単量体単位の含有比率が特定の範囲内である水溶性重合体を含むバインダー組成物を用いることで、得られる機能層のイオン伝導性及び耐熱性を高めることができることを新たに見出し、本発明を完成させた。 The inventors of the present invention have made earnest studies for the purpose of solving the above problems. Then, the present inventors have used the binder composition containing the water-soluble polymer in which the content ratio of the hydroxyl group-containing monomer unit is within a specific range, whereby the ion conductivity and heat resistance of the functional layer obtained are obtained. The present invention has been completed and the present invention has been completed.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の電気化学素子機能層用バインダー組成物は、水溶性重合体を含む電気化学素子機能層用バインダー組成物であって、前記水溶性重合体が、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含むことを特徴とする。このように、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む水溶性重合体をバインダー組成物に含有させることで、電気化学素子の耐熱性及びレート特性を向上させうる機能層を提供することができる。
ここで、本明細書において、「水溶性重合体」とは、温度５０℃において重合体０．５ｇを１００ｇの水に溶解した際に、不溶解分が１０．０質量％未満となる重合体を意味する。
また、本明細書において、「単量体単位を含む」とは、「その単量体を用いて得た重合体中に単量体由来の繰り返し単位が含まれている」ことを意味する。また、本明細書において、水溶性重合体中における単量体単位の含有割合は、水溶性重合体に含有される全単量体単位の量を１００質量％とした場合に、当該単量体単位の占める含有割合を意味する。
さらにまた、本発明において、各単量体単位の含有割合（質量％）は、1Ｈ−ＮＭＲなどの核磁気共鳴（ＮＭＲ）法を用いて測定することができる。That is, the present invention is intended to advantageously solve the above problems, and the binder composition for an electrochemical device functional layer of the present invention is a binder composition for an electrochemical device functional layer containing a water-soluble polymer. The water-soluble polymer contains a hydroxyl group-containing monomer unit in a ratio of 15.000 mass% or more and 90.000 mass% or less. As described above, the heat resistance and the rate of the electrochemical device can be improved by incorporating the water-soluble polymer containing the hydroxyl group-containing monomer unit in the proportion of 15,000% by mass or more and 90.000% by mass or less into the binder composition. A functional layer capable of improving characteristics can be provided.
Here, in the present specification, the “water-soluble polymer” means a polymer having an insoluble content of less than 10.0% by mass when 0.5 g of the polymer is dissolved in 100 g of water at a temperature of 50 ° C. Means
In addition, in the present specification, “including a monomer unit” means that “a polymer obtained by using the monomer contains a repeating unit derived from a monomer”. Further, in the present specification, the content ratio of the monomer units in the water-soluble polymer is such that the amount of all the monomer units contained in the water-soluble polymer is 100% by mass. It means the content ratio of the unit.
Furthermore, in the present invention, the content ratio (% by mass) of each monomer unit can be measured by using a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
ここで、本発明の電気化学素子機能層用バインダー組成物において、前記水溶性重合体のガラス転移温度が−１０℃以上１００℃以下であることが好ましい。水溶性重合体のガラス転移温度が上記範囲内であるバインダー組成物を用いれば、得られる機能層の接着性を向上させることができる。
本明細書において、「水溶性重合体のガラス転移温度」は、ＪＩＳ Ｋ７１２１に準拠して測定することができる。Here, in the binder composition for an electrochemical device functional layer of the present invention, the glass transition temperature of the water-soluble polymer is preferably −10 ° C. or higher and 100 ° C. or lower. By using a binder composition in which the glass transition temperature of the water-soluble polymer is within the above range, the adhesiveness of the resulting functional layer can be improved.
In the present specification, the “glass transition temperature of the water-soluble polymer” can be measured according to JIS K7121.
また、本発明の電気化学素子機能層用バインダー組成物において、前記水溶性重合体が、さらに多官能エチレン性不飽和カルボン酸エステル単量体単位を、０．００１質量％以上１０．０００質量％以下の割合で含むことが好ましい。上記多官能単量体単位を０．００１質量％以上１０．０００質量％以下の割合で含有する水溶性重合体を含むバインダー組成物を用いれば、得られる機能層の接着性を一層向上させることができる。さらに、かかる機能層を備える電気化学素子の耐熱性及びレート特性を一層向上させることができる。 Further, in the binder composition for an electrochemical device functional layer of the present invention, the water-soluble polymer further contains a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in an amount of 0.001% by mass or more and 10.000% by mass or more. It is preferable to contain the following proportions. Use of a binder composition containing a water-soluble polymer containing the polyfunctional monomer unit in a proportion of 0.001% by mass or more and 10.000% by mass or less can further improve the adhesiveness of the resulting functional layer. You can Furthermore, the heat resistance and rate characteristics of the electrochemical device provided with such a functional layer can be further improved.
また、本発明の電気化学素子機能層用バインダー組成物において、前記水溶性重合体が、さらにエチレン性不飽和カルボン酸単量体単位を０．５００質量％以上５０．０００質量％以下の割合で含むことが好ましい。エチレン性不飽和カルボン酸単量体単位を０．５００質量％以上５０．０００質量％以下の割合で含有する水溶性重合体を含むバインダー組成物を用いれば、得られる機能層の接着性を一層向上させることができる。さらに、かかる機能層を備える電気化学素子のレート特性を一層向上させることができる。 In the binder composition for an electrochemical device functional layer of the present invention, the water-soluble polymer further contains an ethylenically unsaturated carboxylic acid monomer unit in a proportion of 0.500% by mass or more and 50.000% by mass or less. It is preferable to include. If a binder composition containing a water-soluble polymer containing an ethylenically unsaturated carboxylic acid monomer unit in a proportion of 0.500% by mass or more and 50.000% by mass or less is used, the adhesiveness of the resulting functional layer is further improved. Can be improved. Furthermore, the rate characteristics of the electrochemical device provided with such a functional layer can be further improved.
また、本発明の電気化学素子機能層用バインダー組成物において、前記水溶性重合体が、さらに（メタ）アクリルアミド単量体単位を５．０００質量％以上６５．０００質量％以下の割合で含むことが好ましい。（メタ）アクリルアミド単量体単位を５．０００質量％以上６５．０００質量％以下の割合で含有する水溶性重合体を含むバインダー組成物を用いれば、電気化学素子のレート特性を一層向上させうる機能層を形成することができる。
なお、本明細書において「（メタ）アクリル」とは、「アクリル」又は「メタクリル」を意味する。Further, in the binder composition for an electrochemical device functional layer of the present invention, the water-soluble polymer further contains a (meth) acrylamide monomer unit in a ratio of 5.000% by mass to 65.000% by mass. Is preferred. Use of a binder composition containing a water-soluble polymer containing a (meth) acrylamide monomer unit in a proportion of 5.000% by mass or more and 65,000% by mass or less can further improve the rate characteristics of the electrochemical device. A functional layer can be formed.
In addition, in this specification, "(meth) acryl" means "acryl" or "methacryl."
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の電気化学素子機能層用組成物は、上述した何れかの電気化学素子機能層用バインダー組成物を含むことが好ましい。機能層用組成物が本発明のバインダー組成物を含んでいれば、かかる機能層用組成物を用いて形成される機能層を備える電気化学素子の耐熱性及びレート特性を一層向上させることができる。 Further, the present invention is intended to advantageously solve the above problems, the composition for electrochemical device functional layer of the present invention, any one of the binder composition for electrochemical device functional layer described above. It is preferable to include. When the composition for functional layer contains the binder composition of the present invention, it is possible to further improve the heat resistance and rate characteristics of the electrochemical device having the functional layer formed by using the composition for functional layer. ..
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の電気化学素子用機能層は、上述した電気化学素子機能層用組成物を用いて形成されたことを特徴とする。上述した本発明の電気化学素子機能層用組成物から形成された機能層を備える電気化学素子は、耐熱性が高く、レート特性に優れる。 Further, the present invention has an object to advantageously solve the above problems, and the functional layer for electrochemical device of the present invention is formed using the composition for electrochemical device functional layer described above. Is characterized by. An electrochemical device including a functional layer formed from the composition for an electrochemical device functional layer of the present invention described above has high heat resistance and excellent rate characteristics.
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の電気化学素子は、上述した電気化学素子用機能層を備えることを特徴とする。上述した機能層を備える電気化学素子は、耐熱性が高く、レート特性に優れる。 Moreover, this invention aims at solving the said subject advantageously, and the electrochemical element of this invention is equipped with the functional layer for electrochemical elements mentioned above, It is characterized by the above-mentioned. The electrochemical device including the above-mentioned functional layer has high heat resistance and excellent rate characteristics.
本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用バインダー組成物を提供することができる。
また、本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用組成物を提供することができる。
そして、本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る電気化学素子用機能層を提供することができる。
さらに、本発明によれば、耐熱性及びレート特性の高い電気化学素子を提供することができる。ADVANTAGE OF THE INVENTION According to this invention, the binder composition for electrochemical element functional layers which can form the functional layer which can improve the heat resistance and rate characteristic of an electrochemical element can be provided.
Further, according to the present invention, it is possible to provide a composition for an electrochemical device functional layer capable of forming a functional layer capable of improving the heat resistance and rate characteristics of the electrochemical device.
Then, according to the present invention, it is possible to provide a functional layer for an electrochemical device capable of improving the heat resistance and rate characteristics of the electrochemical device.
Furthermore, according to the present invention, it is possible to provide an electrochemical element having high heat resistance and high rate characteristics.
以下、本発明の実施形態について詳細に説明する。ここで、本発明の電気化学素子機能層用バインダー組成物及び本発明の電気化学素子機能層用組成物は、電気化学素子内において、電気化学素子に含まれる部材の補強若しくは接着などの機能を担う、任意の機能層（例えば、多孔膜層、保護層、及び接着層）の形成に用いることができる。さらに、本発明の電気化学素子用機能層は、本発明の電気化学素子機能層用組成物を用いて形成される。そして、本発明の電気化学素子は、本発明の電気化学素子用機能層を備える。 Hereinafter, embodiments of the present invention will be described in detail. Here, the binder composition for an electrochemical device functional layer of the present invention and the composition for an electrochemical device functional layer of the present invention have functions such as reinforcement or adhesion of members included in the electrochemical device in the electrochemical device. It can be used for forming any of the functional layers (for example, the porous membrane layer, the protective layer, and the adhesive layer) to be carried. Further, the functional layer for electrochemical device of the present invention is formed using the composition for electrochemical device functional layer of the present invention. The electrochemical device of the present invention comprises the functional layer for electrochemical device of the present invention.
（電気化学素子機能層用バインダー組成物）
本発明のバインダー組成物は、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む水溶性重合体を含む組成物である。なお、本発明のバインダー組成物は、上記水溶性重合体以外に、粒子状重合体、及びその他の成分を含有していてもよい。(Binder composition for electrochemical device functional layer)
The binder composition of the present invention is a composition containing a water-soluble polymer containing a hydroxyl group-containing monomer unit in a ratio of 15.000 mass% or more and 90.000 mass% or less. The binder composition of the present invention may contain a particulate polymer and other components in addition to the above water-soluble polymer.
そして、本発明のバインダー組成物は、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む水溶性重合体を含むので、得られる機能層を備える電気化学素子の耐熱性及びレート特性を高めることができる。その理由は明らかではないが、上記組成の水溶性重合体の有するポリマー構造に起因すると推察される。かかる特定の水溶性重合体の有するポリマー構造によれば、機能層におけるイオン伝導性が高まりうる。これにより、かかる機能層を備える電気化学素子の内部抵抗を低減して、電気化学素子のレート特性を高めることが可能となりうる。また、本発明のバインダー組成物を用いて形成した機能層は、そのポリマー構造に起因して耐熱性に優れると推定され、かかる機能層を備える電気化学素子が、高温環境下におかれた場合に、微小内部短絡が発生することを効果的に抑制して、電気化学素子の耐熱安定性を向上させることが可能となりうる。よって、本発明のバインダー組成物を用いて形成した機能層を電気化学素子に備えることで、電気化学素子に優れたレート特性及び耐熱性を付与することが可能となる。 Since the binder composition of the present invention contains a water-soluble polymer containing a hydroxyl group-containing monomer unit in a ratio of 15.000% by mass or more and 90.000% by mass or less, an electrochemical including a functional layer obtained is obtained. The heat resistance and rate characteristics of the device can be improved. The reason for this is not clear, but it is presumed that it is due to the polymer structure of the water-soluble polymer having the above composition. The polymer structure of the specific water-soluble polymer can increase the ionic conductivity in the functional layer. Thereby, it may be possible to reduce the internal resistance of the electrochemical device including such a functional layer and improve the rate characteristics of the electrochemical device. In addition, the functional layer formed using the binder composition of the present invention is presumed to have excellent heat resistance due to its polymer structure, and an electrochemical element including such a functional layer is placed in a high temperature environment. In addition, it may be possible to effectively suppress the occurrence of a minute internal short circuit and improve the heat resistance stability of the electrochemical device. Therefore, by providing the electrochemical device with the functional layer formed using the binder composition of the present invention, it becomes possible to impart excellent rate characteristics and heat resistance to the electrochemical device.
＜水溶性重合体＞
水溶性重合体は、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む必要があり、さらに、多官能エチレン性不飽和カルボン酸エステル単量体単位、エチレン性不飽和カルボン酸単量体単位、及び（メタ）アクリルアミド単量体単位を含むことがさらに好ましい。<Water-soluble polymer>
The water-soluble polymer must contain a hydroxyl group-containing monomer unit in a ratio of 15.000% by mass or more and 90.000% by mass or less, and further, a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit, It is more preferable to contain an ethylenically unsaturated carboxylic acid monomer unit and a (meth) acrylamide monomer unit.
―水溶性重合体の組成―
［ヒドロキシル基含有単量体単位］
ヒドロキシル基含有単量体単位を形成し得るヒドロキシル基含有単量体としては、ヒドロキシル基を含有する単量体単位である限りにおいて特に限定されることなく、あらゆる単量体を用いることができる。中でも、ヒドロキシル基含有単量体単位としては、ヒドロキシル基の数、及び（−ＣＲ＝ＣＨ2）（ここでＲは水素またはアルキル基を表す）等のエチレン性不飽和結合（Ｃ＝Ｃ）の数が、分子中に各１つである単官能化合物であるヒドロキシル基含有ビニル単量体が好ましい。また、ヒドロキシル基含有ビニル単量体としては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシプロピルメタクリレート、Ｎ−ヒドロキシメチルアクリルアミド、Ｎ−ヒドロキシメチルメタクリルアミド、Ｎ−ヒドロキシエチルアクリルアミド、Ｎ−ヒドロキシエチルメタクリルアミドなどが挙げられる。これらは１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。中でも、得られる機能層の耐熱性及びイオン伝導性を高める観点から、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、及びＮ−ヒドロキシエチルアクリルアミドが好ましく、２−ヒドロキシエチルアクリレート（β−ヒドロキシエチルアクリレート）が特に好ましい。-Composition of water-soluble polymer-
[Hydroxyl group-containing monomer unit]
The hydroxyl group-containing monomer that can form the hydroxyl group-containing monomer unit is not particularly limited as long as it is a hydroxyl group-containing monomer unit, and any monomer can be used. Among them, as the hydroxyl group-containing monomer units, the number of hydroxyl groups, and (-CR = CH 2) (wherein R represents hydrogen or an alkyl group) ethylenically unsaturated bond such as (C = C) A hydroxyl group-containing vinyl monomer, which is a monofunctional compound having one each in the molecule, is preferable. Further, as the hydroxyl group-containing vinyl monomer, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide. , N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide and the like. These may be used alone or in combination of two or more at an arbitrary ratio. Among them, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and N-hydroxyethyl acrylamide are preferable, and 2-hydroxyethyl acrylate (β-hydroxyethyl acrylate), from the viewpoint of enhancing heat resistance and ionic conductivity of the obtained functional layer. ) Is particularly preferable.
水溶性重合体中におけるヒドロキシル基含有単量体単位の含有割合は、１９．０００質量％以上であることが好ましく、２５．０００質量％以上であることがより好ましく、７０．０００質量％以下であることが好ましく、５０．０００質量％以下であることがより好ましい。水溶性重合体中におけるヒドロキシル基含有単量体単位の含有割合を上記範囲内とすることで、得られる機能層の耐熱性及びイオン伝導性を一層高めることができる。従って、電気化学素子の耐熱性及びレート特性を向上させることができる。 The content ratio of the hydroxyl group-containing monomer unit in the water-soluble polymer is preferably 19.000 mass% or more, more preferably 25.000 mass% or more, and 70.000 mass% or less. It is preferable that the amount is 50.000% by mass or less. By setting the content ratio of the hydroxyl group-containing monomer unit in the water-soluble polymer within the above range, the heat resistance and ionic conductivity of the resulting functional layer can be further enhanced. Therefore, the heat resistance and rate characteristics of the electrochemical device can be improved.
［多官能エチレン性不飽和カルボン酸エステル単量体単位］
水溶性重合体中における多官能エチレン性不飽和カルボン酸エステル単量体単位は、多官能エチレン性不飽和カルボン酸エステル単量体を用いて形成することができる。多官能エチレン性不飽和カルボン酸エステル単量体としては、２つ以上のエチレン性不飽和結合を含むカルボン酸エステル単量体が挙げられる。より詳細には、多官能エチレン性不飽和カルボン酸エステル単量体は、一般式：−（ＣｍＨ２ｍＯ）ｎ−[式中、ｍは１以上の整数であり、ｎは１以上の整数である]で表されるオキシアルキレン構造及び２つ以上のエチレン性不飽和結合を有する多官能化合物（以下、「多官能化合物」とも称する）を用いて形成することができる。このような多官能化合物を水溶性重合体の重合に用いることで、水溶性重合体に適度な柔軟性を付与して基材と機能層との間の密着性を向上させることができる。また、水との親和性が高いオキシアルキレン構造の寄与により、水溶性重合体の重合が容易となる。加えて、イオン伝導性が確保され、得られる機能層のイオン伝導性を一層高めることができる。オキシアルキレン構造と２つ以上のエチレン性不飽和結合とを有する化合物は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。[Polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit]
The polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in the water-soluble polymer can be formed by using the polyfunctional ethylenically unsaturated carboxylic acid ester monomer. Examples of polyfunctional ethylenically unsaturated carboxylic acid ester monomers include carboxylic acid ester monomers containing two or more ethylenically unsaturated bonds. More particularly, the polyfunctional ethylenically unsaturated carboxylic acid ester monomers, the general formula :-( C m H 2m O) n - in [wherein, m is an integer of 1 or more, n represents 1 or more It is an integer] and can be formed using a polyfunctional compound having an oxyalkylene structure and two or more ethylenically unsaturated bonds (hereinafter, also referred to as “polyfunctional compound”). By using such a polyfunctional compound for the polymerization of the water-soluble polymer, it is possible to impart appropriate flexibility to the water-soluble polymer and improve the adhesion between the base material and the functional layer. Further, the contribution of the oxyalkylene structure having a high affinity for water facilitates the polymerization of the water-soluble polymer. In addition, ionic conductivity is secured, and the ionic conductivity of the resulting functional layer can be further enhanced. As the compound having an oxyalkylene structure and two or more ethylenically unsaturated bonds, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.
ここで、多官能化合物としては、例えば、上記一般式中における、オキシアルキレン構造の繰り返し数を表す「ｎ」が２以上であるポリオキシアルキレン構造を有するものが好ましい。具体的には、多官能化合物としては、特に限定されることなく、下記の化合物（Ｉ）〜（Ｖ）が挙げられる
なお、本発明において、「（メタ）アクリレート」とは、アクリレート及び／またはメタクリレートを指す。
（Ｉ）下記一般式：
（ＩＩ）下記一般式：
（ＩＩＩ）下記一般式：
（ＩＶ）下記一般式：
（Ｖ）下記一般式：
(I) The following general formula:
(II) The following general formula:
(III) The following general formula:
(IV) The following general formula:
(V) The following general formula:
なお、重合を容易にする観点からは、多官能化合物のエチレン性不飽和結合の数（官能数）は、２以上６以下であることが好ましく、２以上４以下であることが更に好ましい。さらに、多官能化合物は、得られる機能層と基材との間の密着性を一層向上させる観点、及び得られる機能層のイオン伝導性を一層向上させる観点から、２〜６官能のアクリレートであることが好ましく、２〜４官能のアクリレートであることが更に好ましい。 From the viewpoint of facilitating the polymerization, the number of ethylenically unsaturated bonds (functional number) of the polyfunctional compound is preferably 2 or more and 6 or less, and more preferably 2 or more and 4 or less. Furthermore, the polyfunctional compound is a 2- to 6-functional acrylate from the viewpoint of further improving the adhesion between the functional layer obtained and the substrate, and from the viewpoint of further improving the ion conductivity of the functional layer obtained. It is preferable that the acrylate is a bifunctional to tetrafunctional acrylate.
更に、多官能化合物が有するオキシアルキレン構造（−（ＣｍＨ２ｍＯ）ｎ−）の整数ｍは、２０以下であることが好ましく、１５以下であることが更に好ましく、１０以下であることが特に好ましく、２以上であることが好ましい。
また、多官能化合物が有するオキシアルキレン構造（−（ＣｍＨ２ｍＯ）ｎ−）の整数ｎは、２０以下であることが好ましく、１５以下であることが更に好ましく、１０以下であることが特に好ましく、２以上であることが好ましく、３以上であることが更に好ましく、４以上であることが特に好ましい。なお、多官能化合物が分子内に複数のオキシアルキレン構造（−（ＣｍＨ２ｍＯ）ｎ−）を有する場合には、複数のオキシアルキレン構造の整数ｎの平均値が上記範囲内に含まれることが好ましく、全てのオキシアルキレン構造の整数ｎが上記範囲内に含まれることが更に好ましい。Further, an oxyalkylene structure polyfunctional compound having (- (C m H 2m O ) n -) integer m of preferably 20 or less, still more preferably 15 or less, not more than 10 Particularly preferred is 2 or more.
The oxyalkylene structure polyfunctional compound having (- (C m H 2m O ) n -) integer n is preferably 20 or less, still more preferably 15 or less, not more than 10 Particularly preferred is 2 or more, more preferred is 3 or more, and particularly preferred is 4 or more. Incidentally, the polyfunctional compound is more in the molecule oxyalkylene structure (- (C m H 2m O ) n -) in the case where a has an average value of integer n of a plurality of oxyalkylene structure is included within the scope It is preferable that the integer n of all oxyalkylene structures be included in the above range.
水溶性重合体中における多官能エチレン性不飽和カルボン酸エステル単量体単位の含有割合は、０．００１質量％以上であることが好ましく、１０．０００質量％以下であることが好ましく、５．０００質量％以下であることがより好ましく、１．０００質量％以下であることがさらに好ましく、０．５００質量％以下であることがさらに好ましく、０．２００質量％以下であることが特に好ましい。水溶性重合体中における上記多官能単量体単位の含有割合を上記下限値以上とすることで、得られる機能層に適度な柔軟性を付与して基材との間の密着性を向上させうるとともに、得られる機能層のイオンとの親和性を高めてイオン伝導性を一層向上させることができる。また、水溶性重合体中における上記多官能単量体単位の含有割合を上記上限値以下とすることで、水溶性重合体が過度に剛直になることを抑制して、得られる機能層と基材との間の密着性を高めるとともに、得られる機能層のイオン伝導性を高めることができる。さらには、水溶性重合体中における上記多官能単量体単位の含有割合を上記上限値以下とすることで、得られる機能層の耐熱性を高めることができる。 4. The content ratio of the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in the water-soluble polymer is preferably 0.001 mass% or more, and preferably 10.000 mass% or less. The amount is more preferably 000% by mass or less, still more preferably 1.000% by mass or less, further preferably 0.500% by mass or less, and particularly preferably 0.200% by mass or less. By adjusting the content ratio of the polyfunctional monomer unit in the water-soluble polymer to the above lower limit or more, it is possible to impart appropriate flexibility to the obtained functional layer and improve the adhesion with the substrate. At the same time, the affinity of the resulting functional layer with ions can be increased to further improve the ion conductivity. Further, by controlling the content ratio of the polyfunctional monomer unit in the water-soluble polymer to be the upper limit or less, it is possible to prevent the water-soluble polymer from becoming excessively rigid, and to obtain the functional layer and the group. It is possible to enhance the adhesion between the material and the material and to enhance the ion conductivity of the obtained functional layer. Furthermore, by setting the content ratio of the polyfunctional monomer unit in the water-soluble polymer to the upper limit value or less, the heat resistance of the obtained functional layer can be increased.
［エチレン性不飽和カルボン酸単量体単位］
エチレン性不飽和カルボン酸単量体単位を形成し得るエチレン性不飽和カルボン酸単量体としては、ヒドロキシル基を有さないエチレン性不飽和カルボン酸単量体が挙げられる。例えば、エチレン性不飽和カルボン酸単量体としては、エチレン性不飽和モノカルボン酸及びその誘導体、エチレン性不飽和ジカルボン酸及びその酸無水物並びにそれらの誘導体などが挙げられる。なお、エチレン性不飽和カルボン酸単量体は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。[Ethylene unsaturated carboxylic acid monomer unit]
Examples of the ethylenically unsaturated carboxylic acid monomer capable of forming the ethylenically unsaturated carboxylic acid monomer unit include an ethylenically unsaturated carboxylic acid monomer having no hydroxyl group. Examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and its derivative, ethylenically unsaturated dicarboxylic acid and its acid anhydride, and their derivatives. The ethylenically unsaturated carboxylic acid monomer may be used alone or in combination of two or more kinds at an arbitrary ratio.
ここで、エチレン性不飽和モノカルボン酸の例としては、アクリル酸、メタクリル酸、クロトン酸などが挙げられる。
また、エチレン性不飽和モノカルボン酸の誘導体の例としては、２−エチルアクリル酸、イソクロトン酸、α−アセトキシアクリル酸、β−ｔｒａｎｓ−アリールオキシアクリル酸、α−クロロ−β−Ｅ−メトキシアクリル酸、β−ジアミノアクリル酸などが挙げられる。
また、エチレン性不飽和ジカルボン酸の例としては、マレイン酸、フマル酸、イタコン酸などが挙げられる。
また、エチレン性不飽和ジカルボン酸の酸無水物の例としては、無水マレイン酸、ジアクリル酸無水物、メチル無水マレイン酸、ジメチル無水マレイン酸などが挙げられる。
そして、エチレン性不飽和ジカルボン酸の誘導体の例としては、メチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸、などが挙げられる。Here, examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like.
Examples of the ethylenically unsaturated monocarboxylic acid derivative include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacryl. Examples thereof include acids and β-diaminoacrylic acid.
Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, diacrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride and the like.
Examples of the ethylenically unsaturated dicarboxylic acid derivative include methyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, and the like.
上述した中でも、エチレン性不飽和カルボン酸単量体としては、分子中にエチレン性不飽和結合（Ｃ＝Ｃ）を１つ有する単官能エチレン性不飽和カルボン酸単量体が好ましい。また、エチレン性不飽和カルボン酸単量体としては、得られる機能層のイオン伝導性を向上させる観点、及び得られる機能層と基材との間の密着性を向上させる観点から、エチレン性不飽和モノカルボン酸及びエチレン性不飽和ジカルボン酸が好ましく、アクリル酸、メタクリル酸及びイタコン酸がより好ましく、アクリル酸及びメタクリル酸が更に好ましい。 Among the above, the ethylenically unsaturated carboxylic acid monomer is preferably a monofunctional ethylenically unsaturated carboxylic acid monomer having one ethylenically unsaturated bond (C = C) in the molecule. Further, as the ethylenically unsaturated carboxylic acid monomer, from the viewpoint of improving the ionic conductivity of the obtained functional layer and the viewpoint of improving the adhesion between the obtained functional layer and the substrate, the ethylenic unsaturated carboxylic acid monomer is used. Saturated monocarboxylic acids and ethylenically unsaturated dicarboxylic acids are preferred, acrylic acid, methacrylic acid and itaconic acid are more preferred, and acrylic acid and methacrylic acid are even more preferred.
水溶性重合体中におけるエチレン性不飽和カルボン酸単量体単位の含有割合は、０．５０００質量％以上であることが好ましく、１．０００質量％以上であることがより好ましく、５．０００質量％以上であることがさらに好ましく、１０．０００質量％以上であることがさらにより好ましく、５０．０００質量％以下であることが好ましく、４０．０００質量％以下であることがより好ましく、３５．０００質量％以下であることがさらに好ましい。水溶性重合体中におけるエチレン性不飽和カルボン酸単量体単位の含有割合を上記範囲内とすることで、得られる機能層のイオン伝導性、及び得られる機能層と基材との間の密着性を向上させることができる。 The content ratio of the ethylenically unsaturated carboxylic acid monomer unit in the water-soluble polymer is preferably 0.5000 mass% or more, more preferably 1.000 mass% or more, and 5.000 mass. % Or more, more preferably 10.000% by mass or more, further preferably 50.000% by mass or less, more preferably 40.000% by mass or less, 35. It is more preferable that the content is 000% by mass or less. By setting the content ratio of the ethylenically unsaturated carboxylic acid monomer unit in the water-soluble polymer within the above range, the ion conductivity of the obtained functional layer, and the adhesion between the obtained functional layer and the base material It is possible to improve the sex.
［（メタ）アクリルアミド単量体単位］
（メタ）アクリルアミド単量体単位を形成し得る（メタ）アクリルアミド単量体としては、アクリルアミド、メタクリルアミド、ジメトキシアクリルアミド、ジメトキシメタクリルアミド、ジメチルアクリルアミド、及びジメチルメタクリルアミドが挙げられる。中でも、得られる機能層のイオン伝導性を向上させる観点から、アクリルアミド、ジメトキシアクリルアミド、及びジメチルアクリルアミドが好ましく、アクリルアミドが特に好ましい。なお、ヒドロキシル基を有するアクリルアミド単量体は、ヒドロキシル基含有単量体に含まれる。[(Meth) acrylamide monomer unit]
Examples of the (meth) acrylamide monomer capable of forming the (meth) acrylamide monomer unit include acrylamide, methacrylamide, dimethoxyacrylamide, dimethoxymethacrylamide, dimethylacrylamide, and dimethylmethacrylamide. Among them, acrylamide, dimethoxyacrylamide, and dimethylacrylamide are preferable, and acrylamide is particularly preferable, from the viewpoint of improving the ion conductivity of the obtained functional layer. The acrylamide monomer having a hydroxyl group is included in the hydroxyl group-containing monomer.
水溶性重合体における（メタ）アクリルアミド単量体単位の含有割合は、５．０００質量％以上であることが好ましく、１０．０００質量％以上であることがより好ましく、１５．０００質量％以上であることがさらに好ましく、２０．０００質量％以上であることがさらにより好ましく、６５．０００質量％以下であることが好ましく、５０．０００質量％以下であることがより好ましく、４０．０００質量％以下であることがさらに好ましい。水溶性重合体における（メタ）アクリルアミド単量体単位の含有割合が上記範囲内であれば、得られる機能層のイオン伝導性を向上させることができる。 The content ratio of the (meth) acrylamide monomer unit in the water-soluble polymer is preferably 5.000 mass% or more, more preferably 10.000 mass% or more, and 15.000 mass% or more. It is more preferable that it is 20.000 mass% or more, still more preferably 65.000 mass% or less, more preferably 50.000 mass% or less, and 40.000 mass%. The following is more preferable. When the content ratio of the (meth) acrylamide monomer unit in the water-soluble polymer is within the above range, the ion conductivity of the obtained functional layer can be improved.
［その他の単量体単位］
水溶性重合体は、本発明の効果を損なわない限りにおいて、上述したような単量体単位以外の他の単量体単位を含んでいても良い。かかる単量体単位としては、例えば、酢酸ビニル単量体単位、アクリロニトリル単量体単位、スチレン単量体単位、ブタジエン単量体単位、及びイソプレン単量体単位等が挙げられる。水溶性重合体が他の単量体単位を含有する場合には、それらの単量体単位の含有割合は１０．０００質量％以下であることが好ましい。[Other monomer units]
The water-soluble polymer may contain a monomer unit other than the above-mentioned monomer unit as long as the effect of the present invention is not impaired. Examples of such monomer units include vinyl acetate monomer units, acrylonitrile monomer units, styrene monomer units, butadiene monomer units, and isoprene monomer units. When the water-soluble polymer contains other monomer units, the content ratio of those monomer units is preferably 10.000% by mass or less.
―水溶性重合体の性状―
［ガラス転移温度］
水溶性重合体のガラス転移温度が−１０℃以上であることが好ましく、０℃以上であることがより好ましく、１０℃以上であることがさらに好ましく、１００℃以下であることが好ましく、８０℃以下であることがより好ましく、６０℃以下であることがさらに好ましい。水溶性重合体のガラス転移温度が上記範囲内であれば、機能層の接着性を高めることで、得られる機能層と基材との間の密着性を一層高めることができる。-Properties of water-soluble polymer-
[Glass-transition temperature]
The glass transition temperature of the water-soluble polymer is preferably −10 ° C. or higher, more preferably 0 ° C. or higher, even more preferably 10 ° C. or higher, preferably 100 ° C. or lower, 80 ° C. The temperature is more preferably below, and even more preferably 60 ° C. or below. When the glass transition temperature of the water-soluble polymer is within the above range, the adhesiveness between the functional layer and the base material obtained can be further enhanced by enhancing the adhesiveness of the functional layer.
―水溶性重合体の調製方法―
水溶性重合体は、例えば、上述した各成分と任意の重合溶媒とを既知の方法で混合して得た単量体組成物を、任意の重合方法で重合させることで得られる。なお、上記単量体組成物を重合して得られる、水溶性重合体と重合溶媒とを含む溶液は、そのままバインダー組成物の調製に使用してもよいし、溶媒置換や任意の成分の添加などを行なった後にバインダー組成物の調製に使用してもよい。
ここで、水溶性重合体の重合方法としては、限定されることなく、例えば、水溶液重合法等の溶液重合法、スラリー重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法を用いてもよい。また、水溶性重合体の重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などの付加重合を用いることができる。そして、重合に使用される重合開始剤、重合促進剤、乳化剤、分散剤、連鎖移動剤などは、一般に用いられるものを使用することができ、その使用量も、一般に使用される量とすることができる。
中でも、溶媒の除去操作が不要であり、溶媒の安全性が高く、且つ、界面活性剤の混入の問題が無いことから、重合溶媒として水を使用した水溶液重合法が好ましい。-Method for preparing water-soluble polymer-
The water-soluble polymer can be obtained, for example, by polymerizing a monomer composition obtained by mixing the above-mentioned components and an arbitrary polymerization solvent by a known method by an arbitrary polymerization method. The solution containing the water-soluble polymer and the polymerization solvent, which is obtained by polymerizing the above-mentioned monomer composition, may be used as it is for the preparation of the binder composition, or may be subjected to solvent substitution or addition of any component. You may use it for preparation of a binder composition after performing etc.
Here, the polymerization method of the water-soluble polymer is not limited, and for example, any of solution polymerization methods such as aqueous solution polymerization method, slurry polymerization method, suspension polymerization method, bulk polymerization method, emulsion polymerization method and the like. Any method may be used. As the polymerization reaction of the water-soluble polymer, addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization can be used. And, as the polymerization initiator, the polymerization accelerator, the emulsifier, the dispersant, the chain transfer agent and the like used in the polymerization, those generally used can be used, and the amount thereof is also the amount generally used. You can
Among them, the aqueous solution polymerization method using water as a polymerization solvent is preferable because it does not require a solvent removing operation, has high solvent safety, and has no problem of mixing of a surfactant.
なお、重合溶媒として水を使用し、上述した単量体組成物を水中で重合して水溶性重合体を含む水溶液を調製する場合には、重合後に水溶液のｐＨを７以上９以下に調整することが好ましい。得られる水溶液を中和して上記範囲のｐＨに調整すれば、機能層用組成物の粘度安定性を良好にし易くなるからである。 When water is used as a polymerization solvent and the above-mentioned monomer composition is polymerized in water to prepare an aqueous solution containing a water-soluble polymer, the pH of the aqueous solution is adjusted to 7 or more and 9 or less after the polymerization. Preferably. This is because it is easy to improve the viscosity stability of the functional layer composition by neutralizing the resulting aqueous solution and adjusting the pH within the above range.
ここで、水溶性重合体の調製に用い得る重合開始剤としては、特に制限されることなく、既知の重合開始剤、例えば、過硫酸ナトリウム、過硫酸アンモニウム、過硫酸カリウムが挙げられる。中でも、過硫酸カリウムを用いることが好ましい。重合開始剤は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 Here, the polymerization initiator that can be used to prepare the water-soluble polymer is not particularly limited, and known polymerization initiators such as sodium persulfate, ammonium persulfate, and potassium persulfate can be used. Of these, potassium persulfate is preferably used. As the polymerization initiator, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.
また、重合促進剤としては、特に制限されることなく、既知の還元性の重合促進剤、例えば、テトラメチルエチレンジアミンを使用することができる。重合促進剤は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 The polymerization accelerator is not particularly limited, and known reducing polymerization accelerators such as tetramethylethylenediamine can be used. As the polymerization accelerator, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.
＜粒子状重合体＞
粒子状重合体は機能層中において接着能を発揮し得る成分である。そして、粒子状重合体は、機能層中にて粒子形状を維持したまま存在していてもよく、任意の非粒子形状を有して存在していてもよい。そして、粒子状重合体としては、特に限定されることなく、例えば、アクリル系重合体及び共役ジエン系重合体など電気化学素子の機能層にて接着成分として使用されうる任意の重合体を用いることができる。ここで、本発明の粒子状重合体とは、温度５０℃において重合体０．５ｇを１００ｇの水に溶解した際に、不溶解分が９０質量％以上となる重合体をいう。<Particulate polymer>
The particulate polymer is a component capable of exhibiting adhesiveness in the functional layer. The particulate polymer may be present in the functional layer while maintaining the particle shape, or may be present in an arbitrary non-particle shape. The particulate polymer is not particularly limited, and for example, any polymer that can be used as an adhesive component in the functional layer of the electrochemical device, such as an acrylic polymer and a conjugated diene polymer, can be used. You can Here, the particulate polymer of the present invention refers to a polymer having an insoluble content of 90% by mass or more when 0.5 g of the polymer is dissolved in 100 g of water at a temperature of 50 ° C.
なお、アクリル系重合体は、（メタ）アクリル酸エステル単量体単位を５０質量％以上の割合で含む重合体である。そして、アクリル系重合体は、（メタ）アクリル酸エステル単量体単位を形成し得る（メタ）アクリル酸エステル単量体と、かかる単量体と共重合可能な他の単量体とを任意の方法で重合して得ることができる。 The acrylic polymer is a polymer containing (meth) acrylic acid ester monomer units in a proportion of 50% by mass or more. The acrylic polymer may optionally contain a (meth) acrylic acid ester monomer capable of forming a (meth) acrylic acid ester monomer unit and another monomer copolymerizable with such a monomer. It can be obtained by polymerization by the method.
アクリル系重合体の（メタ）アクリル酸エステル単量体単位を形成し得る（メタ）アクリル酸エステル単量体としては、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、ｔ−ブチルアクリレー卜、ペンチルアクリレート、ヘキシルアクリレート、ヘプチルアクリレート、オクチルアクリレート、２−エチルヘキシルアクリレート等のアクリル酸アルキルエステル；メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、ｔ−ブチルメタクリレート、ペンチルメタクリレート、ヘキシルメタクリレート、ヘプチルメタクリレート、オクチルメタクリレート、２−エチルヘキシルメタクリレート等のメタクリル酸アルキルエステル；などが挙げられる。これらは、１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。これらの中でも、（メタ）アクリル酸エステル単量体としては、メチルメタクリレート及びｎ−ブチルアクリレートが好ましい。 Examples of the (meth) acrylic acid ester monomer capable of forming the (meth) acrylic acid ester monomer unit of the acrylic polymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Acrylic acid alkyl esters such as t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t -Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid alkyl esters such as acrylate; and the like. These may be used alone or in combination of two or more. Among these, methyl methacrylate and n-butyl acrylate are preferable as the (meth) acrylic acid ester monomer.
アクリル系重合体の調製に用いるその他の単量体としては、上記（メタ）アクリル酸エステル単量体と共重合可能であるとともに、また、本発明の効果を損なわない限りにおいて特に限定されることなく、水溶性重合体のエチレン性不飽和カルボン酸単量体単位を形成し得る水溶性重合体のエチレン性不飽和カルボン酸単量体と同様の単量体や、多官能エチレン性不飽和カルボン酸エステル単量体単位を形成し得る多官能化合物を挙げることができる。 Other monomers used for the preparation of the acrylic polymer are copolymerizable with the above (meth) acrylic acid ester monomer and are particularly limited as long as the effects of the present invention are not impaired. The same monomer as the ethylenically unsaturated carboxylic acid monomer of the water-soluble polymer capable of forming an ethylenically unsaturated carboxylic acid monomer unit of the water-soluble polymer, or a polyfunctional ethylenically unsaturated carboxylic acid monomer. Mention may be made of polyfunctional compounds capable of forming acid ester monomer units.
共役ジエン系重合体としては、特に限定されることなく、スチレン−ブタジエン共重合体（ＳＢＲ）などの芳香族ビニル単量体単位及び脂肪族共役ジエン単量体単位を含む共重合体、ブタジエンゴム（ＢＲ）、イソプレンゴム、アクリルゴム（ＮＢＲ）（アクリロニトリル単位及びブタジエン単位を含む共重合体）、並びに、それらの水素化物などが挙げられる。なお、共役ジエン系重合体は、共役ジエン系単量体単位を１０質量％超の割合で含む重合体である。 The conjugated diene polymer is not particularly limited, and a copolymer containing an aromatic vinyl monomer unit such as a styrene-butadiene copolymer (SBR) and an aliphatic conjugated diene monomer unit, butadiene rubber. (BR), isoprene rubber, acrylic rubber (NBR) (a copolymer containing an acrylonitrile unit and a butadiene unit), and hydrides thereof. The conjugated diene polymer is a polymer containing a conjugated diene monomer unit in a proportion of more than 10% by mass.
そして、これらの粒子状重合体の重合方法としては、特に限定されることなく、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などを挙げることができる。また、重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などの付加重合を挙げることができる。そして、重合に使用され得る重合溶媒、乳化剤、分散剤、重合開始剤、連鎖移動剤などは、一般的なものを使用することができ、その使用量も、一般に使用される量とすることができる。 The method for polymerizing these particulate polymers is not particularly limited, and examples thereof include a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method. Examples of the polymerization reaction include addition polymerization such as ionic polymerization, radical polymerization and living radical polymerization. Then, as the polymerization solvent, emulsifier, dispersant, polymerization initiator, chain transfer agent, etc. that can be used in the polymerization, general ones can be used, and the amount thereof can also be a commonly used amount. it can.
＜溶媒＞
本発明のバインダー組成物に含まれ得る溶媒または分散媒としては、上述した水溶性重合体及び任意の粒子状重合体を溶解または分散可能な既知の溶媒または分散媒を用いることができる。中でも、溶媒または分散媒としては、水を用いることが好ましい。なお、バインダー組成物の溶媒の少なくとも一部は、特に限定されることなく、水溶性重合体及び／または任意の粒子状重合体の調製に用いた重合溶媒とすることができる。<Solvent>
As the solvent or dispersion medium that can be contained in the binder composition of the present invention, a known solvent or dispersion medium that can dissolve or disperse the above-mentioned water-soluble polymer and any particulate polymer can be used. Above all, it is preferable to use water as the solvent or the dispersion medium. In addition, at least a part of the solvent of the binder composition is not particularly limited, and may be the polymerization solvent used for preparing the water-soluble polymer and / or any particulate polymer.
＜その他の成分＞
本発明のバインダー組成物は、上述した水溶性重合体以外の他の水溶性の重合体を更に含んでいてもよい。バインダー組成物に含まれうる他の水溶性の重合体としては、例えば、増粘多糖類、アルギン酸、でんぷんなどの天然系高分子；カルボキシメチルセルロース（ＣＭＣ）などの半合成系高分子；ポリビニルピロリドン、架橋ポリアクリル酸及び非架橋ポリアクリル酸といったポリアクリル酸などの合成系高分子；を挙げることができる。<Other ingredients>
The binder composition of the present invention may further contain a water-soluble polymer other than the above-mentioned water-soluble polymer. Examples of other water-soluble polymers that can be contained in the binder composition include natural polymers such as thickening polysaccharides, alginic acid and starch; semi-synthetic polymers such as carboxymethyl cellulose (CMC); polyvinylpyrrolidone, Examples thereof include synthetic polymers such as polyacrylic acid such as crosslinked polyacrylic acid and non-crosslinked polyacrylic acid.
さらに、本発明のバインダー組成物が含みうるその他の成分としては、補強材、レベリング剤、粘度調整剤、電解液添加剤等の任意の添加剤が挙げられる。これらは、電気化学素子における電気化学的反応に影響を及ぼさないものであれば特に限られず、公知のものを使用することができる。また、これらの成分は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 Further, as the other components that can be contained in the binder composition of the present invention, optional additives such as a reinforcing material, a leveling agent, a viscosity modifier, and an electrolyte solution additive can be mentioned. These are not particularly limited as long as they do not affect the electrochemical reaction in the electrochemical element, and known ones can be used. Moreover, these components may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.
＜バインダー組成物の調製方法＞
そして、本発明のバインダー組成物は、上述した水溶性重合体並びに任意の粒子状重合体、溶媒及びその他の成分を、既知の方法で混合することにより調製することができる。具体的には、ボールミル、サンドミル、ビーズミル、顔料分散機、らい潰機、超音波分散機、ホモジナイザー、プラネタリーミキサー、フィルミックスなどの混合機を用いて上記各成分を混合することにより、バインダー組成物を調製することができる。
なお、水溶性重合体及び任意の粒子状重合体は、水系溶媒中で重合して調製した場合には、水溶液または水分散体の状態でそのまま混合し、溶媒として水を含むバインダー組成物を調製することができる。
また、例えば、水溶性重合体と非導電性粒子とを混合した後、任意の粒子状重合体を添加するなど、バインダー組成物の調製と、後述する機能層用組成物の調製とを同時に実施してもよい。<Method for preparing binder composition>
The binder composition of the present invention can be prepared by mixing the above-mentioned water-soluble polymer, any particulate polymer, solvent and other components by a known method. Specifically, a binder composition is prepared by mixing the above components using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a fill mix. Can be prepared.
Incidentally, when the water-soluble polymer and any particulate polymer are prepared by polymerizing in an aqueous solvent, they are mixed as they are in the state of an aqueous solution or an aqueous dispersion to prepare a binder composition containing water as a solvent. can do.
Further, for example, after mixing the water-soluble polymer and the non-conductive particles, such as adding an arbitrary particulate polymer, the preparation of the binder composition and the preparation of the functional layer composition described later are carried out at the same time. You may.
[含有量]
本発明のバインダー組成物が粒子状重合体を含む場合、バインダー組成物中における粒子状重合体の含有量は、水溶性重合体１００質量部に対して、５質量部以上であることが好ましく、１０質量部以上であることがより好ましく、２５質量部以上であることがさらに好ましく、２０００質量部以下であることが好ましく、３５０質量部以下であることがより好ましい。[Content]
When the binder composition of the present invention contains a particulate polymer, the content of the particulate polymer in the binder composition is preferably 5 parts by mass or more based on 100 parts by mass of the water-soluble polymer, The amount is more preferably 10 parts by mass or more, further preferably 25 parts by mass or more, preferably 2000 parts by mass or less, and more preferably 350 parts by mass or less.
（電気化学素子機能層用組成物）
本発明の機能層用組成物は、機能層の形成用途に用いられる組成物であり、上述したバインダー組成物を含み、任意に、機能性粒子とその他の成分を更に含有する。なお、本発明の機能層用組成物は、本発明のバインダー組成物を含有し、溶媒、機能性粒子及びその他の任意成分を更に含有する電気化学素子機能層用スラリー組成物であっても良い。そして、本発明の機能層用組成物は、上述したバインダー組成物を含んでいるので、本発明の機能層用組成物を例えば基材上で乾燥することで、耐熱性及びイオン伝導性に優れる機能層を得ることができる。そして、当該機能層を備える電池部材を使用すれば、電気化学素子に優れた特性、特には、高い耐熱性と優れたレート特性を発揮させることができる。(Composition for electrochemical device functional layer)
The functional layer composition of the present invention is a composition used for forming a functional layer, contains the binder composition described above, and optionally further contains functional particles and other components. The functional layer composition of the present invention may be an electrochemical element functional layer slurry composition containing the binder composition of the present invention and further containing a solvent, functional particles and other optional components. .. Since the functional layer composition of the present invention contains the binder composition described above, by drying the functional layer composition of the present invention on, for example, a substrate, it is excellent in heat resistance and ion conductivity. A functional layer can be obtained. When the battery member including the functional layer is used, the electrochemical device can exhibit excellent characteristics, particularly high heat resistance and excellent rate characteristics.
＜バインダー組成物＞
バインダー組成物としては、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含有する水溶性重合体を含む、上述した本発明のバインダー組成物を用いる。
なお、機能層用組成物中のバインダー組成物の配合量は、特に限定されることなく、機能性粒子としての非導電性粒子１００質量部当たり、水溶性重合体の量が０．０５質量部以上５０質量部以下となる量とすることができる。<Binder composition>
As the binder composition, the above-described binder composition of the present invention containing a water-soluble polymer containing a hydroxyl group-containing monomer unit in a ratio of 15.000 mass% or more and 90.000 mass% or less is used.
The amount of the binder composition in the functional layer composition is not particularly limited, and the amount of the water-soluble polymer is 0.05 parts by mass per 100 parts by mass of the non-conductive particles as the functional particles. The amount may be 50 parts by mass or more and 50 parts by mass or less.
＜機能性粒子＞
ここで、機能層に所期の機能を発揮させるための機能性粒子としては、例えば、非導電性粒子が挙げられる。非導電性粒子としては、特に限定されることなく、電気化学素子に用いられる既知の非導電性粒子を挙げることができる。
具体的には、非導電性粒子としては、無機微粒子と有機微粒子との双方を用いることができるが、通常は無機微粒子が用いられる。なかでも、非導電性粒子の材料としては、電気化学素子の使用環境下で安定に存在し、電気化学的に安定である材料が好ましい。このような観点から非導電性粒子の材料の好ましい例を挙げると、酸化アルミニウム（アルミナ）、水和アルミニウム酸化物（ベーマイト）、酸化ケイ素、酸化マグネシウム（マグネシア）、酸化カルシウム、酸化チタン（チタニア）、ＢａＴｉＯ３、ＺｒＯ、アルミナ−シリカ複合酸化物等の酸化物粒子；窒化アルミニウム、窒化ホウ素等の窒化物粒子；シリコン、ダイヤモンド等の共有結合性結晶粒子；硫酸バリウム、フッ化カルシウム、フッ化バリウム等の難溶性イオン結晶粒子；タルク、モンモリロナイト等の粘土微粒子；などが挙げられる。また、これらの粒子は必要に応じて元素置換、表面処理、固溶体化等が施されていてもよい。
なお、上述した非導電性粒子は、１種類を単独で使用してもよいし、２種類以上を組み合わせて用いてもよい。<Functional particles>
Here, examples of the functional particles for causing the functional layer to exhibit a desired function include non-conductive particles. The non-conductive particles are not particularly limited, and examples thereof include known non-conductive particles used in electrochemical devices.
Specifically, both inorganic fine particles and organic fine particles can be used as the non-conductive particles, but inorganic fine particles are usually used. Among them, the material of the non-conductive particles is preferably a material that stably exists in the environment in which the electrochemical device is used and that is electrochemically stable. From this point of view, preferred examples of the material of the non-conductive particles include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania). , BaTiO 3 , ZrO, oxide particles such as alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalent bond crystal particles such as silicon and diamond; barium sulfate, calcium fluoride, barium fluoride. And the like, and slightly soluble ionic crystal particles such as talc and clay fine particles such as talc and montmorillonite. Further, these particles may be subjected to element substitution, surface treatment, solid solution treatment or the like, if necessary.
The non-conductive particles described above may be used alone or in combination of two or more.
＜その他の成分＞
機能層用組成物に配合し得るその他の成分としては、特に限定することなく、本発明のバインダー組成物に配合し得るその他の成分と同様のものが挙げられる。なお、その他の成分は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。<Other ingredients>
Other components that can be added to the functional layer composition are not particularly limited, and include the same components as other components that can be added to the binder composition of the present invention. The other components may be used alone or in combination of two or more kinds at any ratio.
＜機能層用組成物の調製＞
機能層用組成物の調製方法は、特に限定はされない。例えば、バインダー組成物と、機能性粒子としての非導電性粒子と、必要に応じて用いられるその他の成分とを、溶媒の存在下で混合して機能層用組成物を調製することができる。なお、機能層用組成物の調製の際に用いる溶媒は、機能層用組成物に含まれていたものも含まれる。また、混合方法は特に制限されないが、通常用いられうる撹拌機や、分散機を用いて混合を行う。<Preparation of functional layer composition>
The method for preparing the functional layer composition is not particularly limited. For example, the composition for functional layer can be prepared by mixing the binder composition, the non-conductive particles as the functional particles, and other components used as necessary in the presence of a solvent. The solvent used in the preparation of the functional layer composition also includes those contained in the functional layer composition. Further, the mixing method is not particularly limited, but the mixing is performed using a stirrer or a disperser which can be usually used.
（電気化学素子用機能層）
本発明の機能層は、電気化学素子内において補強、接着などの機能を担う層であり、機能層としては、例えば、電気化学素子の耐熱性や強度を向上させるための多孔膜層、電極を保護するための保護膜層、及び電気化学素子に備えられる部材間の接着性を向上させるための接着層などが挙げられる。そして、本発明の機能層は、上述した本発明の機能層用組成物から形成されたものであり、例えば、上述した機能層用組成物を適切な基材の表面に塗布して塗膜を形成した後、形成した塗膜を乾燥することにより、形成することができる。即ち、本発明の機能層は、上述した機能層用組成物の乾燥物よりなり、通常、少なくとも、水溶性重合体を含有する。なお、機能層中に含まれている各成分は、上記機能層用組成物中に含まれていたものであるため、それら各成分の好適な存在比は、機能層用組成物中の各成分の好適な存在比と同じである。また、例えば、水溶性重合体が、多官能エチレン性不飽和カルボン酸エステル単量体単位、及び、任意でその他の架橋性の単量体単位を含む場合等には、当該水溶性重合体には、機能層用組成物の乾燥時、或いは、乾燥後に任意に実施される熱処理時などに架橋構造が形成されていてもよい（即ち、機能層は、上述した水溶性重合体の架橋物を含んでいてもよい）。(Functional layer for electrochemical device)
The functional layer of the present invention is a layer having functions such as reinforcement and adhesion in the electrochemical element, and the functional layer includes, for example, a porous film layer for improving heat resistance and strength of the electrochemical element, and an electrode. Examples thereof include a protective film layer for protection and an adhesive layer for improving adhesiveness between members provided in the electrochemical device. Then, the functional layer of the present invention is formed from the functional layer composition of the present invention described above, for example, by applying the functional layer composition described above to the surface of a suitable substrate to form a coating film. After forming, it can be formed by drying the formed coating film. That is, the functional layer of the present invention is a dried product of the functional layer composition described above, and usually contains at least a water-soluble polymer. Since each component contained in the functional layer was contained in the composition for functional layer, the preferable abundance ratio of each component is each component in the composition for functional layer. Is the same as the preferred abundance ratio of. Further, for example, when the water-soluble polymer contains a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit, and optionally other crosslinkable monomer unit, etc., in the water-soluble polymer May have a crosslinked structure formed when the functional layer composition is dried, or during a heat treatment optionally performed after drying (that is, the functional layer is formed by crosslinking the above water-soluble polymer). May be included).
本発明の機能層は、本発明のバインダー組成物を含む本発明の機能層用組成物から形成されているので、優れたイオン伝導性を有すると共に、本発明の機能層を備える電気化学素子に、優れた電気化学的特性（レート特性など）及び耐熱性を発揮させることができる。 Since the functional layer of the present invention is formed from the composition for a functional layer of the present invention containing the binder composition of the present invention, it has excellent ionic conductivity and an electrochemical device including the functional layer of the present invention. , And can exhibit excellent electrochemical characteristics (rate characteristics, etc.) and heat resistance.
［基材］
ここで、機能層用組成物を塗布する基材に制限は無く、例えば、離型基材の表面に機能層用組成物の塗膜を形成し、その塗膜を乾燥して機能層を形成し、機能層から離型基材を剥がすようにしてもよい。このように、離型基材から剥がされた機能層を自立膜として二次電池の電池部材の形成に用いることもできる。
しかし、機能層を剥がす工程を省略して電池部材の製造効率を高める観点からは、基材として、セパレータ基材、または電極基材を用いることが好ましい。[Base material]
Here, there is no limitation on the base material to which the composition for functional layer is applied, and for example, a coating film of the composition for functional layer is formed on the surface of a release substrate, and the coating film is dried to form the functional layer. Alternatively, the release base material may be peeled off from the functional layer. In this way, the functional layer peeled off from the release base material can be used as a self-supporting film for forming a battery member of a secondary battery.
However, from the viewpoint of increasing the manufacturing efficiency of the battery member by omitting the step of peeling the functional layer, it is preferable to use a separator base material or an electrode base material as the base material.
セパレータ基材としては、特に限定されないが、有機セパレータ基材などの既知のセパレータ基材が挙げられる。有機セパレータ基材は、有機材料からなる多孔性部材であり、有機セパレータ基材の例を挙げると、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、芳香族ポリアミド樹脂などを含む微多孔膜または不織布などが挙げられ、強度に優れることからポリエチレン製の微多孔膜や不織布が好ましい。 The separator substrate is not particularly limited, and examples thereof include known separator substrates such as organic separator substrates. The organic separator substrate is a porous member made of an organic material, and examples of the organic separator substrate include polyethylene, polyolefin resin such as polypropylene, and a microporous membrane or nonwoven fabric containing an aromatic polyamide resin. A polyethylene microporous membrane or a non-woven fabric is preferable because of its excellent strength.
電極基材（正極基材及び負極基材）としては、特に限定されないが、例えば、銅、アルミニウム等の電気導電性を有し、かつ、電気化学的に耐久性のある既知の材料よりなる集電体上に、電極活物質粒子及び結着材を含む電極合材層が形成された電極基材が挙げられる。
電極基材中の電極合材層に含まれる電極活物質粒子及び結着材としては、特に限定されず、電気化学素子にて使用可能な、既知の電極活物質粒子、既知の結着材を使用することができる。The electrode base material (positive electrode base material and negative electrode base material) is not particularly limited, but for example, a collection of known materials having electrical conductivity and electrochemical durability such as copper and aluminum. An electrode base material in which an electrode mixture layer including electrode active material particles and a binder is formed on an electric body can be mentioned.
The electrode active material particles and the binder contained in the electrode mixture layer in the electrode base material are not particularly limited, and known electrode active material particles usable in the electrochemical device and known binders can be used. Can be used.
［機能層の形成方法］
上述したセパレータ基材、電極基材などの基材上に機能層を形成する方法としては、以下の方法が挙げられる。
１）本発明の機能層用組成物を基材の表面（電極基材の場合は電極合材層側の表面、以下同じ）に塗布し、次いで乾燥する方法；
２）本発明の機能層用組成物に基材を浸漬後、これを乾燥する方法；及び
３）本発明の機能層用組成物を離型基材上に塗布し、乾燥して機能層を製造し、得られた機能層を基材の表面に転写する方法。
これらの中でも、前記１）の方法が、機能層の層厚制御をしやすいことから特に好ましい。前記１）の方法は、詳細には、機能層用組成物を基材上に塗布する工程（塗布工程）と、基材上に塗布された機能層用組成物を乾燥させて機能層を形成する工程（乾燥工程）を含む。[Method of forming functional layer]
Examples of the method for forming a functional layer on a substrate such as the separator substrate and the electrode substrate described above include the following methods.
1) A method in which the functional layer composition of the present invention is applied to the surface of a base material (in the case of an electrode base material, the surface on the electrode mixture layer side, the same applies hereinafter), and then dried.
2) A method in which a base material is immersed in the functional layer composition of the present invention and then dried; and 3) the functional layer composition of the present invention is applied onto a release base material and dried to form the functional layer. A method of producing and transferring the obtained functional layer to the surface of a substrate.
Among these, the method 1) is particularly preferable because it is easy to control the layer thickness of the functional layer. The method 1) is specifically the step of applying the composition for functional layer onto a substrate (application step), and the composition for functional layer applied onto the substrate is dried to form a functional layer. The step (drying step) is included.
−塗布工程−
そして、塗布工程において、機能層用組成物を基材上に塗布する方法としては、特に制限は無く、例えば、ドクターブレード法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗り法などの方法が挙げられる。-Coating process-
Then, in the coating step, the method for coating the functional layer composition on the substrate is not particularly limited, for example, doctor blade method, reverse roll method, direct roll method, gravure method, extrusion method, brush coating The method such as the law can be mentioned.
−乾燥工程−
また、乾燥工程において、基材上の機能層用組成物を乾燥する方法としては、特に限定されず公知の方法を用いることができる。乾燥法としては、例えば、温風、熱風、低湿風による乾燥、真空乾燥、赤外線や電子線などの照射による乾燥が挙げられる。乾燥温度は、好ましくは２００℃未満であり、さらに好ましくは１５０℃未満である。-Drying process-
In the drying step, the method for drying the functional layer composition on the substrate is not particularly limited, and a known method can be used. Examples of the drying method include drying with warm air, hot air, and low humidity air, vacuum drying, and drying with irradiation with infrared rays, electron beams, or the like. The drying temperature is preferably below 200 ° C, more preferably below 150 ° C.
（電気化学素子）
本発明の電気化学素子は、上述した本発明の機能層を備えるものである。より具体的には、本発明の電気化学素子は、リチウムイオン二次電池や電気二重層キャパシタでありうる。このような本発明の電気化学素子は、耐熱性が高く、レート特性等の電気化学的特性に優れる。(Electrochemical element)
The electrochemical device of the present invention comprises the above-mentioned functional layer of the present invention. More specifically, the electrochemical device of the present invention may be a lithium ion secondary battery or an electric double layer capacitor. Such an electrochemical device of the present invention has high heat resistance and excellent electrochemical characteristics such as rate characteristics.
ここで、以下では、一例として電気化学素子がリチウムイオン二次電池である場合について説明するが、本発明は下記の一例に限定されるものではない。本発明の電気化学素子としてのリチウムイオン二次電池は、通常、電極（正極及び負極）、電解液、及びセパレータを備える。より具体的には、本発明に従う電気化学素子としてのリチウムイオン二次電池は、電極及びセパレータ等の電池部材のうちの少なくとも一つが本発明の機能層を備えるか、或いは、これらの電池部材と包材とを接着させるための接着層として本発明の機能層を備えるものでありうる。 Here, a case where the electrochemical element is a lithium ion secondary battery will be described below as an example, but the present invention is not limited to the following example. The lithium-ion secondary battery as the electrochemical device of the present invention usually comprises an electrode (positive electrode and negative electrode), an electrolytic solution, and a separator. More specifically, the lithium ion secondary battery as the electrochemical device according to the present invention, at least one of the battery members such as electrodes and separators is provided with the functional layer of the present invention, or these battery members and The functional layer of the present invention may be provided as an adhesive layer for adhering the packaging material.
＜正極、負極及びセパレータ＞
本発明に従う電気化学素子としてのリチウムイオン二次電池の正極、負極及びセパレータとしては、上述した本発明の機能層を備える正極、負極及び／又はセパレータ、或いは、本発明の機能層を備えない正極、負極及び／又はセパレータが挙げられる。なお、本発明の機能層を備えない正極、負極及びセパレータとしては、特に限定されることなく、既知の正極、負極及びセパレータを用いることができる。<Positive electrode, negative electrode and separator>
The positive electrode, the negative electrode and the separator of the lithium ion secondary battery as the electrochemical device according to the present invention include a positive electrode having the functional layer of the present invention, a negative electrode and / or a separator, or a positive electrode not having the functional layer of the present invention. , A negative electrode and / or a separator. The positive electrode, negative electrode, and separator not having the functional layer of the present invention are not particularly limited, and known positive electrodes, negative electrodes, and separators can be used.
＜電解液＞
電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウムイオン二次電池においてはリチウム塩が用いられる。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などが挙げられる。なかでも、溶媒に溶けやすく高い解離度を示すので、ＬｉＰＦ６、ＬｉＣｌＯ４、ＣＦ３ＳＯ３Ｌｉが好ましい。なお、電解質は１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。通常は、解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなる傾向があるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。<Electrolyte>
As the electrolytic solution, an organic electrolytic solution prepared by dissolving a supporting electrolyte in an organic solvent is usually used. As the supporting electrolyte, for example, a lithium salt is used in a lithium ion secondary battery. 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 the like. Among them, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable because they are easily dissolved in a solvent and exhibit a high dissociation degree. The electrolyte may be used alone or in combination of two or more. Generally, the higher the dissociation degree of the supporting electrolyte, the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
電解液に使用する有機溶媒としては、支持電解質を溶解できるものであれば特に限定されないが、例えばリチウムイオン二次電池においては、ジメチルカーボネート（ＤＭＣ）、エチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、エチルメチルカーボネート（ＥＭＣ）、ビニレンカーボネート（ＶＣ）等のカーボネート類；γ−ブチロラクトン、ギ酸メチル等のエステル類；１，２−ジメトキシエタン、テトラヒドロフラン等のエーテル類；スルホラン、ジメチルスルホキシド等の含硫黄化合物類；などが好適に用いられる。また、これらの溶媒の混合液を用いてもよい。中でも、誘電率が高く、安定な電位領域が広いので、カーボネート類が好ましい。通常、用いる溶媒の粘度が低いほどリチウムイオン伝導度が高くなる傾向があるので、溶媒の種類によりリチウムイオン伝導度を調節することができる。
なお、電解液中の電解質の濃度は適宜調整することができる。また、電解液には、既知の添加剤を添加してもよい。The organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, in a lithium ion secondary battery, dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC). , Propylene carbonate (PC), butylene carbonate (BC), ethylmethyl carbonate (EMC), vinylene carbonate (VC) and other carbonates; γ-butyrolactone, methyl formate and other esters; 1,2-dimethoxyethane, tetrahydrofuran, etc. And the like; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; Moreover, you may use the mixed liquid of these solvents. Among them, carbonates are preferable because they have a high dielectric constant and a wide stable potential region. Generally, the lower the viscosity of the solvent used, the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted by the type of the solvent.
The concentration of the electrolyte in the electrolytic solution can be adjusted appropriately. Known additives may be added to the electrolytic solution.
＜リチウムイオン二次電池の製造方法＞
上述した本発明の電気化学素子としてのリチウムイオン二次電池は、例えば、正極と負極とをセパレータを介して重ね合わせ、これを必要に応じて、巻く、折るなどして電池容器（包材）に入れ、電池容器に電解液を注入して封口することで製造することができる。なお、上述のように、正極、負極、セパレータのうち、少なくとも一つの部材を、本発明の機能層を備える電池部材とすることができる。或いは、これらの電池部材を積層させて得た積層体と、電池容器との間に、本発明の機能層を介在させることも可能である。また、電池容器には、必要に応じてエキスパンドメタルや、ヒューズ、ＰＴＣ素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をしてもよい。電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。<Method for manufacturing lithium-ion secondary battery>
The lithium ion secondary battery as the electrochemical device of the present invention described above is a battery container (packaging material), for example, by stacking a positive electrode and a negative electrode via a separator, and winding or folding the same as required. Can be manufactured by injecting the electrolyte solution into the battery container and sealing the battery container. As described above, at least one of the positive electrode, the negative electrode, and the separator can be the battery member having the functional layer of the present invention. Alternatively, it is possible to interpose the functional layer of the present invention between the battery container and the laminated body obtained by laminating these battery members. If necessary, an expanded metal, a fuse, an overcurrent preventing element such as a PTC element, a lead plate, or the like may be placed in the battery container to prevent a pressure increase and overcharging / discharging inside the battery. The shape of the battery may be, for example, a coin type, a button type, a sheet type, a cylindrical type, a prismatic type, a flat type, or the like.
以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の説明において、量を表す「％」及び「部」は、特に断らない限り、質量基準である。
実施例及び比較例において、水溶性重合体のガラス転移温度、機能層の接着性、電気化学素子の耐熱性、及び電気化学素子のレート特性は、下記の方法で評価した。Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
In Examples and Comparative Examples, the glass transition temperature of the water-soluble polymer, the adhesiveness of the functional layer, the heat resistance of the electrochemical device, and the rate property of the electrochemical device were evaluated by the following methods.
＜水溶性重合体のガラス転移温度＞
水溶性重合体を含む水溶液を、相対湿度５０％、温度２３℃〜２６℃の環境下で３日間乾燥させて、厚み１±０．３ｍｍに成膜した。成膜したフィルムを、温度６０℃の真空乾燥機で１０時間乾燥させた。その後、乾燥させたフィルムをサンプルとし、ＪＩＳ Ｋ７１２１に準拠して、測定温度−１００℃〜１８０℃、昇温速度５℃／分の条件下、示差走査熱量分析計（ナノテクノロジー社製、製品名「ＤＳＣ６２２０ＳＩＩ」）を用いてガラス転移温度（℃）を測定した。<Glass transition temperature of water-soluble polymer>
An aqueous solution containing a water-soluble polymer was dried for 3 days in an environment of relative humidity 50% and temperature 23 ° C to 26 ° C to form a film having a thickness of 1 ± 0.3 mm. The formed film was dried in a vacuum dryer at a temperature of 60 ° C. for 10 hours. Then, the dried film is used as a sample, and in accordance with JIS K7121, a differential scanning calorimeter (manufactured by Nanotechnology Co., product name, under the conditions of measurement temperature −100 ° C. to 180 ° C., heating rate 5 ° C./min. The glass transition temperature (° C) was measured using "DSC6220SII".
＜機能層の接着性＞
―セパレータ上に機能層を形成した場合―
実施例１〜１０、及び比較例１〜２で作製した機能層を備えるセパレータを、長さ１００ｍｍ、幅１０ｍｍの長方形に切り出して試験片とし、機能層を有する面を下にして機能層表面をセロハンテープ（ＪＩＳ Ｚ１５２２に規定されるもの）を貼り付けた。その後、セパレータ基材の一端を垂直方向に引張り速度５０ｍｍ／分で引っ張って剥がしたときの応力（Ｎ／ｍ）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）。上記と同様の測定を３回行い、その平均値を求めてこれをピール強度とし、以下の基準により評価した。ピール強度の値が大きいほど、機能層とセパレータ基材とが強固に密着し、機能層が接着性に優れることを示す。
Ａ：ピール強度が３．０Ｎ／ｍ以上
Ｂ：ピール強度が２．５Ｎ／ｍ以上３．０Ｎ／ｍ未満
Ｃ：ピール強度が１．５Ｎ／ｍ以上２．５Ｎ／ｍ未満
Ｄ：ピール強度が１．５Ｎ／ｍ未満
―電極上に機能層を形成した場合―
実施例１１及び比較例３にて作製した最表面に機能層を備える電極（正極及び負極）を、長さ１００ｍｍ、幅１０ｍｍの長方形に切り出して試験片とし、集電体、電極（正極及び負極）合材層、及び機能層を有する面を下にして機能層表面をセロハンテープ（ＪＩＳ Ｚ１５２２に規定されるもの）で貼り付けた。その後、集電体の一端を垂直方向に引張り速度５０ｍｍ／分で引っ張って剥がしたときの応力（Ｎ／ｍ）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）。上記と同様の測定を３回行い、その平均値を求めてこれをピール強度とし、以下の基準により評価した。ピール強度の値が大きいほど、電極合材層と機能層とが強固に密着し、電極合材層上に形成した機能層が接着性に優れることを示す。
Ａ：ピール強度が３．０Ｎ／ｍ以上
Ｂ：ピール強度が２．５Ｎ／ｍ以上３．０Ｎ／ｍ未満
Ｃ：ピール強度が１．５Ｎ／ｍ以上２．５Ｎ／ｍ未満
Ｄ：ピール強度が１．５Ｎ／ｍ未満<Adhesiveness of functional layer>
-When a functional layer is formed on the separator-
The separator including the functional layer produced in each of Examples 1 to 10 and Comparative Examples 1 and 2 was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece, and the surface having the functional layer was faced down to form a functional layer surface. Cellophane tape (specified in JIS Z1522) was attached. Then, the stress (N / m) when one end of the separator substrate was pulled in the vertical direction at a pulling speed of 50 mm / min and peeled off was measured (note that the cellophane tape is fixed to the test stand). The same measurement as the above was performed 3 times, the average value thereof was determined and used as the peel strength, and evaluated according to the following criteria. The larger the peel strength value, the stronger the adhesion between the functional layer and the separator substrate, indicating that the functional layer has excellent adhesiveness.
A: Peel strength is 3.0 N / m or more B: Peel strength is 2.5 N / m or more and less than 3.0 N / m C: Peel strength is 1.5 N / m or more and less than 2.5 N / m D: Peel strength is Less than 1.5 N / m-When a functional layer is formed on the electrode-
The electrodes (positive electrode and negative electrode) provided with the functional layer on the outermost surface prepared in Example 11 and Comparative Example 3 were cut into rectangles having a length of 100 mm and a width of 10 mm to prepare test pieces, and a current collector, electrodes (positive electrode and negative electrode). ) The surface having the composite material layer and the functional layer was faced down, and the surface of the functional layer was attached with cellophane tape (defined in JIS Z1522). Then, the stress (N / m) was measured when one end of the current collector was pulled in the vertical direction at a pulling speed of 50 mm / min and peeled off (note that the cellophane tape is fixed to the test stand). The same measurement as the above was performed 3 times, the average value thereof was determined and used as the peel strength, and evaluated according to the following criteria. The larger the peel strength value, the stronger the adhesion between the electrode composite material layer and the functional layer, and the better the adhesiveness of the functional layer formed on the electrode composite material layer.
A: Peel strength is 3.0 N / m or more B: Peel strength is 2.5 N / m or more and less than 3.0 N / m C: Peel strength is 1.5 N / m or more and less than 2.5 N / m D: Peel strength is Less than 1.5 N / m
＜電気化学素子の耐熱性＞
電気化学素子の耐熱性は下記の条件に従う内部短絡試験により評価した。ここで、内部短絡試験の結果が良好であるということは、高温環境下であっても、機能層が電気化学素子内における微小内部短絡の発生を良好に抑制し得る程度に耐熱性が高い、ということを意味する。
実施例、比較例で作製した電気化学素子としてのリチウムイオン二次電池（セル）を、電解液注液後、温度２５℃で、５時間静置した。次に、温度２５℃、０．２Ｃの定電流法にて、セル電圧３．６５Ｖまで充電し、その後、温度６０℃で１２時間エージング処理を行った。そして、温度２５℃、０．２Ｃの定電流法にて、セル電圧３．００Ｖまで放電した。その後、０．２Ｃの定電流にて、ＣＣ−ＣＶ充電（上限セル電圧４．３５Ｖ）を行い、０．２Ｃの定電流にてセル電圧３．００ＶまでＣＣ放電を行った。この０．２Ｃにおける充放電を３回繰り返し実施した。
次に、温度２５℃の環境下、セル電圧４．２０−３．００Ｖ間で、０．２Ｃの定電流充放電を実施し、このときの放電容量をＣ０と定義した。
上記セルを、窒素雰囲気下、１３０℃で１時間加熱した。その後、同様に０．２Ｃの定電流にてＣＣ−ＣＶ充電し、温度２５℃の環境下において、０．２Ｃの定電流にて３．００Ｖまで放電を実施し、このときの放電容量をＣ１と定義した。そして、ΔＣ＝（Ｃ１／Ｃ０）×１００（％）で示される容量維持率を求め、以下の基準により評価した。この容量維持率ΔＣの値が大きいほど、高温環境下にセルがおかれた状態におけるセルの微小内部短絡発生が抑制されたことを示す。
Ａ：容量維持率ΔＣが８５％以上
Ｂ：容量維持率ΔＣが７０％以上８５％未満
Ｃ：容量維持率ΔＣが６５％以上７０％未満
Ｄ：容量維持率ΔＣが６５％未満<Heat resistance of electrochemical device>
The heat resistance of the electrochemical device was evaluated by an internal short circuit test according to the following conditions. Here, a good result of the internal short-circuit test means that the functional layer has high heat resistance to such an extent that the functional layer can well suppress the occurrence of a minute internal short-circuit even in a high temperature environment. It means that.
Lithium ion secondary batteries (cells) as electrochemical devices prepared in Examples and Comparative Examples were allowed to stand at a temperature of 25 ° C. for 5 hours after injecting an electrolytic solution. Next, the battery was charged to a cell voltage of 3.65 V by a constant current method at a temperature of 25 ° C. and 0.2 C, and then an aging treatment was performed at a temperature of 60 ° C. for 12 hours. Then, the cells were discharged to a cell voltage of 3.00 V by a constant current method at a temperature of 25 ° C. and 0.2 C. Then, CC-CV charge (upper limit cell voltage 4.35V) was performed at a constant current of 0.2C, and CC discharge was performed at a constant current of 0.2C to a cell voltage of 3.00V. The charging / discharging at 0.2 C was repeated 3 times.
Next, under a temperature of 25 ° C., a constant current charge / discharge of 0.2 C was performed at a cell voltage of 4.20-3.00 V, and the discharge capacity at this time was defined as C0.
The cell was heated at 130 ° C. for 1 hour under a nitrogen atmosphere. After that, CC-CV charging is similarly performed with a constant current of 0.2 C, and discharging is performed to 3.00 V with a constant current of 0.2 C under an environment of a temperature of 25 ° C. Was defined. Then, the capacity retention ratio represented by ΔC = (C1 / C0) × 100 (%) was obtained and evaluated according to the following criteria. It is indicated that the larger the value of the capacity retention ratio ΔC, the more the occurrence of the minute internal short circuit of the cell in the state where the cell was placed in the high temperature environment was suppressed.
A: Capacity maintenance ratio ΔC is 85% or more B: Capacity maintenance ratio ΔC is 70% or more and less than 85% C: Capacity maintenance ratio ΔC is 65% or more and less than 70% D: Capacity maintenance ratio ΔC is less than 65%
＜電気化学素子のレート特性＞
実施例、比較例で作製した電気化学素子としてのリチウムイオン二次電池を、電解液注液後、温度２５℃で、５時間静置した。次に、温度２５℃、０．２Ｃの定電流法にて、セル電圧３．６５Ｖまで充電し、その後、温度６０℃で１２時間エージング処理を行った。そして、温度２５℃、０．２Ｃの定電流法にて、セル電圧３．００Ｖまで放電した。その後、０．２Ｃの定電流にて、ＣＣ−ＣＶ充電（上限セル電圧４．３５Ｖ）を行い、０．２Ｃの定電流にてセル電圧３．００ＶまでＣＣ放電を行った。この０．２Ｃにおける充放電を３回繰り返し実施した。
次に、温度２５℃の環境下、セル電圧４．２０−３．００Ｖ間で、０．２Ｃの定電流充放電を実施し、このときの放電容量をＣ０と定義した。その後、同様に０．２Ｃの定電流にてＣＣ−ＣＶ充電し、温度−１０℃の環境下において、０．５Ｃの定電流にて２．５Ｖまで放電を実施し、このときの放電容量をＣ１と定義した。そして、レート特性として、ΔＣ＝（Ｃ１／Ｃ０）×１００（％）で示される容量維持率を求め、以下の基準により評価した。この容量維持率ΔＣの値が大きいほど、低温環境下、高電流での放電容量が高く、そして内部抵抗が低いことを示す。
Ａ：容量維持率ΔＣが６５％以上
Ｂ：容量維持率ΔＣが６０％以上６５％未満
Ｃ：容量維持率ΔＣが５５％以上６０％未満
Ｄ：容量維持率ΔＣが５５％未満<Rate characteristics of electrochemical device>
Lithium ion secondary batteries as electrochemical devices manufactured in Examples and Comparative Examples were allowed to stand at a temperature of 25 ° C. for 5 hours after injecting an electrolytic solution. Next, the battery was charged to a cell voltage of 3.65 V by a constant current method at a temperature of 25 ° C. and 0.2 C, and then an aging treatment was performed at a temperature of 60 ° C. for 12 hours. Then, the cells were discharged to a cell voltage of 3.00 V by a constant current method at a temperature of 25 ° C. and 0.2 C. Then, CC-CV charge (upper limit cell voltage 4.35V) was performed at a constant current of 0.2C, and CC discharge was performed at a constant current of 0.2C to a cell voltage of 3.00V. The charging / discharging at 0.2 C was repeated 3 times.
Next, under a temperature of 25 ° C., a constant current charge / discharge of 0.2 C was performed at a cell voltage of 4.20-3.00 V, and the discharge capacity at this time was defined as C0. After that, CC-CV charging is similarly performed at a constant current of 0.2 C, and discharging is performed to 2.5 V at a constant current of 0.5 C under an environment of a temperature of -10 ° C. It was defined as C1. Then, as the rate characteristic, the capacity retention rate represented by ΔC = (C1 / C0) × 100 (%) was obtained and evaluated according to the following criteria. The larger the value of the capacity retention ratio ΔC, the higher the discharge capacity at high current in a low temperature environment and the lower the internal resistance.
A: Capacity maintenance ratio ΔC is 65% or more B: Capacity maintenance ratio ΔC is 60% or more and less than 65% C: Capacity maintenance ratio ΔC is 55% or more and less than 60% D: Capacity maintenance ratio ΔC is less than 55%
（実施例１）
＜水溶性重合体の調製＞
セプタム付き１Ｌフラスコに、イオン交換水７２０ｇを投入して、温度４０℃に加熱し、流量１００ｍＬ／分の窒素ガスでフラスコ内を置換した。次に、イオン交換水１０ｇと、ヒドロキシル基含有単量体としての２−ヒドロキシエチルアクリレートを３９．８８０部と、多官能エチレン性不飽和カルボン酸エステル単量体（多官能化合物）としてのポリエチレングリコールジアクリレート（２官能化合物、オキシアルキレン構造の繰り返し数ｎ＝４）を０．１２０部と、エチレン性不飽和カルボン酸単量体としてのアクリル酸を２５．０００部と、（メタ）アクリルアミド単量体としてのアクリルアミドを３５．０００部と、を混合して、シリンジでフラスコ内に注入した。その後、重合開始剤としての過硫酸カリウムの２．５％水溶液８部をシリンジでフラスコ内に追加した。更に、その１５分後に、重合促進剤としてのテトラメチルエチレンジアミンの２．０％水溶液２２部をシリンジで追加した。４時間後、重合開始剤としての過硫酸カリウムの２．５％水溶液４部をフラスコ内に追加し、更に重合促進剤としてのテトラメチルエチレンジアミンの２．０％水溶液１１部を追加して、温度を６０℃に昇温し、重合反応を進めた。３時間後、フラスコを空気中に開放して重合反応を停止させ、生成物を温度８０℃で脱臭し、残留単量体を除去した。その後、水酸化リチウムの１０％水溶液を用いて生成物のｐＨを８に調整することにより、ヒドロキシル基含有単量体単位、多官能エチレン性不飽和カルボン酸エステル単量体単位、エチレン性不飽和カルボン酸単量体単位、及び（メタ）アクリルアミド単量体単位を所定の割合で含有する重合体を含む水溶液を得た。
なお、得られた重合体が含有する各単量体単位の組成は、重合体の重合に用いた全単量体に占める各単量体の比率（仕込み比率）と同じであった。また、得られた重合体０．５ｇを温度５０℃において１００ｇの水に溶解させたところ、不溶解分が０．２質量％であり水溶性であった。(Example 1)
<Preparation of water-soluble polymer>
720 g of ion-exchanged water was put into a 1 L flask with a septum, heated to a temperature of 40 ° C., and the inside of the flask was replaced with nitrogen gas having a flow rate of 100 mL / min. Next, 10 g of ion-exchanged water, 39.880 parts of 2-hydroxyethyl acrylate as a hydroxyl group-containing monomer, and polyethylene glycol as a polyfunctional ethylenically unsaturated carboxylic acid ester monomer (polyfunctional compound). 0.120 parts of diacrylate (bifunctional compound, repeating number of oxyalkylene structure n = 4), 25.000 parts of acrylic acid as an ethylenically unsaturated carboxylic acid monomer, and (meth) acrylamide monomer 35.000 parts of acrylamide as a body were mixed and injected into the flask with a syringe. Then, 8 parts of a 2.5% aqueous solution of potassium persulfate as a polymerization initiator was added to the flask with a syringe. Further, 15 minutes later, 22 parts of a 2.0% aqueous solution of tetramethylethylenediamine as a polymerization accelerator was added by a syringe. After 4 hours, 4 parts of a 2.5% aqueous solution of potassium persulfate as a polymerization initiator was added to the flask, and 11 parts of a 2.0% aqueous solution of tetramethylethylenediamine as a polymerization accelerator was further added, and the temperature was increased. Was heated to 60 ° C. to proceed the polymerization reaction. After 3 hours, the flask was opened to the air to stop the polymerization reaction, and the product was deodorized at a temperature of 80 ° C. to remove residual monomers. Then, by adjusting the pH of the product to 8 using a 10% aqueous solution of lithium hydroxide, hydroxyl group-containing monomer units, polyfunctional ethylenically unsaturated carboxylic acid ester monomer units, ethylenically unsaturated An aqueous solution containing a polymer containing a carboxylic acid monomer unit and a (meth) acrylamide monomer unit in a predetermined ratio was obtained.
The composition of each monomer unit contained in the obtained polymer was the same as the ratio (preparation ratio) of each monomer to all the monomers used for polymerizing the polymer. When 0.5 g of the obtained polymer was dissolved in 100 g of water at a temperature of 50 ° C., the insoluble content was 0.2% by mass and the polymer was water-soluble.
＜粒子状重合体の調製＞
攪拌機付き５ＭＰａ耐圧容器に、（メタ）アクリル酸エステル単量体としてのメチルメタクリレート６０部及びブチルアクリレート３５部、並びにこれらの（メタ）アクリル酸エステル単量体と共重合可能な他の単量体としてのメタクリル酸４部、及びエチレングリコールジメタクリレート１部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム１部、イオン交換水１５０部、及び、重合開始剤としての過硫酸カリウム０．５部を入れ、十分に攪拌した後、６０℃に加温することにより重合を開始した。重合転化率が９６％になった時点で冷却して重合反応を停止することにより、機能層中において接着能を呈し得る粒子状重合体としてのアクリル系重合体を含む水分散液を得た。
得られた粒子状重合体の、温度５０℃の水１００ｇ対して０．５ｇの比率として溶解させたところ、不溶解分は９４質量％であった。<Preparation of particulate polymer>
In a 5 MPa pressure vessel equipped with a stirrer, 60 parts of methyl methacrylate as a (meth) acrylic acid ester monomer and 35 parts of butyl acrylate, and other monomers copolymerizable with these (meth) acrylic acid ester monomers. 4 parts of methacrylic acid and 1 part of ethylene glycol dimethacrylate, 1 part of sodium dodecylbenzene sulfonate as an emulsifier, 150 parts of ion-exchanged water, and 0.5 parts of potassium persulfate as a polymerization initiator are sufficiently added. After stirring at room temperature, the polymerization was started by heating to 60 ° C. By cooling at the time when the conversion of polymerization reached 96% to stop the polymerization reaction, an aqueous dispersion containing an acrylic polymer as a particulate polymer capable of exhibiting adhesiveness in the functional layer was obtained.
When the resulting particulate polymer was dissolved in a proportion of 0.5 g with respect to 100 g of water at a temperature of 50 ° C., the insoluble content was 94% by mass.
＜機能層を有するセパレータの調製＞
非導電性粒子としてのアルミナ粒子（日本軽金属社製、「ＬＳ２５６」）の水分散液を固形分相当で１００部、上述のようにして得られた水溶性重合体の水溶液を固形分相当で１．５部、粒子状重合体を固形分相当で５．０部、ポリエチレングリコール型界面活性剤（サンノプコ社製、「サンノプコ（登録商標）ＳＮウェット３６６」）を０．２部、及び水を混合して、機能層用組成物を調製した。なお、水の量は、固形分濃度が４０％となるように調整した。セパレータ基材として、ポリエチレン製の有機セパレータ基材（セルガード社製、「２５００」、厚さ：２５μｍ）を用意した。用意した有機セパレータ基材の片面に、上述のようにして得られた機能層用組成物を塗布し、５０℃で３分乾燥させた。これにより、機能層（厚さ：２μｍ）を片面に備えるセパレータ（機能層付きセパレータ）を得た。<Preparation of separator having functional layer>
100 parts of an aqueous dispersion of alumina particles (“LS256” manufactured by Nippon Light Metal Co., Ltd.) as non-conductive particles in terms of solid content, and 1 part of aqueous solution of the water-soluble polymer obtained as described above in terms of solid content. .5 parts, 5.0 parts by weight of the particulate polymer in terms of solid content, 0.2 parts of a polyethylene glycol type surfactant ("San Nopco (registered trademark) SN Wet 366" manufactured by San Nopco Ltd.), and water are mixed. Then, the composition for functional layer was prepared. The amount of water was adjusted so that the solid content concentration was 40%. As a separator substrate, an organic separator substrate made of polyethylene (“2500” manufactured by Celgard, thickness: 25 μm) was prepared. The composition for functional layer obtained as described above was applied to one surface of the prepared organic separator substrate and dried at 50 ° C. for 3 minutes. Thereby, a separator (separator with a functional layer) having a functional layer (thickness: 2 μm) on one surface was obtained.
＜負極合材層用バインダーの調製＞
撹拌機付き５ＭＰａ耐圧容器に、芳香族ビニル単量体としてのスチレン６５部、脂肪族共役ジエン単量体としての１，３−ブタジエン３５部、カルボン酸基含有単量体としてのイタコン酸２部、ヒドロキシル基含有単量体としてのアクリル酸−２−ヒドロキシエチル１部、分子量調整剤としてのｔ−ドデシルメルカプタン０．３部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム５部、溶媒としてのイオン交換水１５０部、及び、重合開始剤としての過硫酸カリウム１部を投入し、十分に撹拌した後、温度５５℃に加温して重合を開始した。単量体消費量が９５．０％になった時点で冷却し、反応を停止した。こうして得られた重合体を含んだ水分散体に、５％水酸化ナトリウム水溶液を添加して、ｐＨを８に調整した。その後、加熱減圧蒸留によって未反応単量体の除去を行った。さらにその後、温度３０℃以下まで冷却することにより、負極合材層用バインダーを含む水分散液（負極合材層用バインダー組成物）を得た。<Preparation of binder for negative electrode mixture layer>
In a 5 MPa pressure vessel equipped with a stirrer, 65 parts of styrene as an aromatic vinyl monomer, 35 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, and 2 parts of itaconic acid as a carboxylic acid group-containing monomer. , 2-hydroxyethyl acrylate as a hydroxyl group-containing monomer, 1 part, t-dodecyl mercaptan as a molecular weight adjusting agent, 0.3 part, sodium dodecylbenzenesulfonate as an emulsifier, 5 parts, ion-exchanged water as a solvent 150 parts and 1 part of potassium persulfate as a polymerization initiator were added and sufficiently stirred, and then heated to a temperature of 55 ° C. to start polymerization. When the monomer consumption reached 95.0%, the reaction was stopped by cooling. The aqueous dispersion containing the polymer thus obtained was adjusted to pH 8 by adding a 5% aqueous sodium hydroxide solution. Then, the unreacted monomer was removed by heating under reduced pressure. After that, by further cooling to a temperature of 30 ° C. or lower, an aqueous dispersion containing the binder for the negative electrode mixture layer (binder composition for the negative electrode mixture layer) was obtained.
＜負極合材層用スラリー組成物の調製＞
プラネタリーミキサーに、負極活物質としての人造黒鉛（理論容量：３６０ｍＡｈ／ｇ）４８．７５部、天然黒鉛（理論容量：３６０ｍＡｈ／ｇ）４８．７５部と、増粘剤としてカルボキシメチルセルロースを固形分相当で１部とを投入した。さらに、イオン交換水にて固形分濃度が６０％となるように希釈し、その後、回転速度４５ｒｐｍで６０分混練した。その後、上述で得られた負極合材層用バインダー組成物を固形分相当で１．５部投入し、回転速度４０ｒｐｍで４０分混練した。そして、粘度が３０００±５００ｍＰａ・ｓ（Ｂ型粘度計、２５℃、６０ｒｐｍで測定）となるようにイオン交換水を加えることにより、負極合材層用スラリー組成物を調製した。
＜負極の製造＞
上記負極合材層用スラリー組成物を、コンマコーターで、集電体である厚さ１５μｍの銅箔の表面に、塗付量が１１±０．５ｍｇ／ｃｍ2となるように塗布した。その後、負極合材層用スラリー組成物が塗布された銅箔を、４００ｍｍ／分の速度で、温度８０℃のオーブン内を２分間、さらに温度１１０℃のオーブン内を２分間かけて搬送することにより、銅箔上のスラリー組成物を乾燥させ、集電体上に負極合材層が形成された負極原反を得た。
その後、作製した負極原反の負極合材層側を温度２５±３℃の環境下、線圧１１ｔ（トン）の条件でロールプレスし、負極合材層密度が１．６０ｇ／ｃｍ3の負極を得た。<Preparation of slurry composition for negative electrode mixture layer>
In a planetary mixer, 48.75 parts of artificial graphite (theoretical capacity: 360 mAh / g) as the negative electrode active material, 48.75 parts of natural graphite (theoretical capacity: 360 mAh / g), and carboxymethyl cellulose as a thickener in solid content. In fact, 1 part was added. Furthermore, it was diluted with ion-exchanged water so that the solid content concentration became 60%, and then kneaded at a rotation speed of 45 rpm for 60 minutes. Then, 1.5 parts of the binder composition for a negative electrode mixture layer obtained above was added in an amount corresponding to the solid content, and kneaded at a rotation speed of 40 rpm for 40 minutes. Then, ion-exchanged water was added so that the viscosity was 3000 ± 500 mPa · s (B-type viscometer, measured at 25 ° C., 60 rpm) to prepare a slurry composition for a negative electrode mixture layer.
<Manufacture of negative electrode>
The slurry composition for a negative electrode mixture layer was applied to the surface of a copper foil having a thickness of 15 μm, which is a current collector, with a comma coater so that the applied amount was 11 ± 0.5 mg / cm 2 . Then, the copper foil coated with the slurry composition for the negative electrode mixture layer is conveyed at a speed of 400 mm / min in an oven at a temperature of 80 ° C. for 2 minutes and further in an oven at a temperature of 110 ° C. for 2 minutes. Thus, the slurry composition on the copper foil was dried to obtain a negative electrode raw material having a negative electrode mixture layer formed on the current collector.
After that, the negative electrode composite material layer side of the prepared negative electrode raw material was roll-pressed under the condition of a temperature of 25 ± 3 ° C. and a linear pressure of 11 t (ton), and the negative electrode composite material layer density was 1.60 g / cm 3 . Got
＜正極の製造＞
プラネタリーミキサーに、正極活物質としてのＣｏ−Ｎｉ−Ｍｎのリチウム複合酸化物系の活物質（ＮＭＣ１１１、ＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2、）を９６部、導電材としてのアセチレンブラック２部（電気化学工業製、商品名「ＨＳ−１００」）、結着材としてのポリフッ化ビニリデン（クレハ化学製、商品名「ＫＦ−１１００」）２部を添加し、さらに、分散媒としてのＮ−メチル−２−ピロリドン（ＮＭＰ）を全固形分濃度が６７％となるように加えて混合し、正極合材層用スラリー組成物を調製した。
続いて、得られた正極合材層用スラリー組成物を、コンマコーターで、集電体である厚さ２０μｍのアルミニウム箔の上に、塗布量が２０±０．５ｍｇ／ｃｍ2となるように塗布した。
さらに、２００ｍｍ／分の速度で、温度９０℃のオーブン内を２分間、さらに温度１２０℃のオーブン内を２分間かけて搬送することにより、アルミニウム箔上のスラリー組成物を乾燥させ、集電体上に正極合材層が形成された正極原反を得た。
その後、作製した正極原反の正極合材層側を温度２５±３℃の環境下、線圧１４ｔ（トン）の条件でロールプレスし、正極合材層密度が３．４０ｇ／ｃｍ3の正極を得た。<Manufacture of positive electrode>
In a planetary mixer, 96 parts of Co-Ni-Mn lithium composite oxide-based active material (NMC111, LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) as a positive electrode active material and a conductive material were used. 2 parts of acetylene black (manufactured by Denki Kagaku Kogyo, trade name "HS-100"), and 2 parts of polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd., trade name "KF-1100") as a binder are added and further dispersed. N-methyl-2-pyrrolidone (NMP) as a medium was added and mixed so that the total solid content concentration was 67% to prepare a slurry composition for a positive electrode mixture layer.
Then, the obtained positive electrode mixture layer slurry composition was applied by a comma coater on an aluminum foil having a thickness of 20 μm serving as a current collector so that the coating amount was 20 ± 0.5 mg / cm 2. Applied.
Further, the slurry composition on the aluminum foil was dried at a speed of 200 mm / min for 2 minutes in an oven at a temperature of 90 ° C. and further for 2 minutes in an oven at a temperature of 120 ° C. to collect a current collector. A positive electrode raw material having a positive electrode mixture layer formed thereon was obtained.
Then, the positive electrode composite material layer side of the prepared positive electrode raw material was roll-pressed under the condition of a temperature of 25 ± 3 ° C. and a linear pressure of 14 t (ton), and the positive electrode composite material layer density was 3.40 g / cm 3 . Got
＜評価用セルの作製＞
上記の負極、正極及びコート済みセパレータを用いて、集電体／負極合材層／セパレータ／機能層／正極合材層／集電体となるように積層してから、捲回セル（放電容量５２０ｍＡｈ相当）を作製し、アルミ包材内に配置した。その後、このアルミ包材内に、電解液として濃度１．０ＭのＬｉＰＦ6溶液（溶媒：エチレンカーボネート（ＥＣ）／ジエチルカーボネート（ＤＥＣ）＝３／７（体積比）の混合溶媒、添加剤：ビニレンカーボネート２体積％（溶媒比）含有）を充填した。さらに、アルミ包材の開口を密封するために、温度１５０℃のヒートシールをしてアルミ包材を閉口し、リチウムイオン二次電池を製造した。このリチウムイオン二次電池を用いて、レート特性を評価した。結果を表１に示す。<Production of evaluation cell>
Using the above-mentioned negative electrode, positive electrode, and coated separator, the current collector / negative electrode mixture layer / separator / functional layer / positive electrode mixture layer / current collector are laminated to form a wound cell (discharge capacity). (Equivalent to 520 mAh) was prepared and placed in an aluminum packaging material. Then, in this aluminum packaging material, a LiPF 6 solution having a concentration of 1.0 M as an electrolytic solution (solvent: mixed solvent of ethylene carbonate (EC) / diethyl carbonate (DEC) = 3/7 (volume ratio), additive: vinylene) 2% by volume of carbonate (containing solvent) was charged. Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing was performed at a temperature of 150 ° C. and the aluminum packaging material was closed to manufacture a lithium ion secondary battery. Using this lithium-ion secondary battery, rate characteristics were evaluated. The results are shown in Table 1.
（実施例２〜７）
水溶性重合体の調製時に配合する各種単量体の配合量を変更して、得られる水溶性重合体の組成を表１に示す通りに変更した以外は実施例１と同様にして、各種測定及び評価を行った。結果を表１に示す。(Examples 2 to 7)
Various measurements were carried out in the same manner as in Example 1 except that the amounts of various monomers to be mixed at the time of preparing the water-soluble polymer were changed and the composition of the resulting water-soluble polymer was changed as shown in Table 1. And evaluated. The results are shown in Table 1.
（実施例８）
水溶性重合体の調製時に、ヒドロキシル基含有単量体として、２−ヒドロキシエチルアクリレートに代えてＮ−ヒドロキシエチルアクリルアミドを６９．７９０部配合し、（メタ）アクリルアミド単量体としてのアクリルアミドに代えて、ジメチルアクリルアミドを１５．０００部配合し、多官能化合物の配合量を０．２１０部に変更し、エチレン性不飽和カルボン酸単量体の配合量を１５．０００部に変更した以外は、実施例１と同様にして、各種測定及び評価を行った。結果を表１に示す。(Example 8)
When preparing the water-soluble polymer, 69.790 parts of N-hydroxyethyl acrylamide was blended as the hydroxyl group-containing monomer in place of 2-hydroxyethyl acrylate, and acrylamide was used as the (meth) acrylamide monomer. , Except that dimethyl acrylamide was mixed in an amount of 15.000, the amount of the polyfunctional compound was changed to 0.210, and the amount of the ethylenically unsaturated carboxylic acid monomer was changed to 15.000. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例９）
（メタ）アクリルアミド単量体としてのアクリルアミドの配合量を２９．０００部に変更し、多官能化合物として、実施例１と同じポリエチレングリコールジアクリレート（２官能化合物）を０．１２０部と、４官能化合物のエトキシ化ペンタエリスリトールテトラアクリレート（新中村化学工業株式会社製、「ＡＴＭ−３５Ｅ」、複数のオキシアルキレン構造の繰り返し数ｎの平均値＝８．７５）を６．０００部とを配合した以外は実施例１と同様にして、各種測定及び評価を行った。結果を表１に示す。(Example 9)
The compounding amount of acrylamide as a (meth) acrylamide monomer was changed to 29.000 parts, and as the polyfunctional compound, 0.120 parts of the same polyethylene glycol diacrylate (bifunctional compound) as in Example 1 and tetrafunctional were added. 6.000 parts except for compounding ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “ATM-35E”, average value of repeating number n of plural oxyalkylene structures = 8.75) of the compound. In the same manner as in Example 1, various measurements and evaluations were performed. The results are shown in Table 1.
（実施例１０）
（メタ）アクリルアミド単量体としてのアクリルアミドの配合量を３２．０００部に変更し、多官能化合物として、実施例１と同じポリエチレングリコールジアクリレート（２官能化合物）を０．１２０部と、４官能化合物のエトキシ化ペンタエリスリトールテトラアクリレート（新中村化学工業株式会社製、「ＡＴＭ−３５Ｅ」、複数のオキシアルキレン構造の繰り返し数ｎの平均値＝８．７５）を３．０００部とを配合した以外は実施例１と同様にして、各種測定及び評価を行った。結果を表１に示す。(Example 10)
The compounding amount of acrylamide as a (meth) acrylamide monomer was changed to 32.000 parts, and as the polyfunctional compound, 0.120 parts of the same polyethylene glycol diacrylate (bifunctional compound) as in Example 1 and tetrafunctional were added. 3.00 parts except that the compound ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “ATM-35E”, average value of repeating number n of plural oxyalkylene structures = 8.75) was blended with 3.000 parts. In the same manner as in Example 1, various measurements and evaluations were performed. The results are shown in Table 1.
（実施例１１）
実施例１と同様にして調製した機能層用組成物を、実施例１と同様にして製造した電極（正極及び負極）に対して塗布し、８０℃で３分間乾燥させ、厚み２μｍの機能層を備える電極を得て、上記方法に従って機能層の接着性を評価した。また、セパレータとして、実施例１と同じポリエチレン製の有機セパレータ基材（セルガード社製、「２５００」、厚さ：２５μｍ）を、表面に機能層を形成することなく用いた。そして、機能層を形成した負極、機能層を形成した正極、及びセパレータを用い、集電体／負極合材層／機能層／セパレータ／機能層／正極合材層／集電体となるように捲回セル（放電容量５２０ｍＡｈ相当）を作製した。これらの点以外は、実施例１と同様にして、リチウムイオン二次電池を作製し、実施例１と同様の測定及び評価を行った。結果を表１に示す。(Example 11)
The functional layer composition prepared in the same manner as in Example 1 was applied to the electrodes (positive electrode and negative electrode) manufactured in the same manner as in Example 1, dried at 80 ° C. for 3 minutes, and the functional layer having a thickness of 2 μm was applied. An electrode provided with was obtained, and the adhesion of the functional layer was evaluated according to the above method. As the separator, the same polyethylene organic separator substrate as in Example 1 (“2500” manufactured by Celgard, thickness: 25 μm) was used without forming a functional layer on the surface. Then, using the negative electrode having the functional layer formed thereon, the positive electrode having the functional layer formed thereon, and the separator, a current collector / a negative electrode mixture layer / functional layer / separator / functional layer / positive electrode mixture layer / current collector is obtained. A wound cell (corresponding to a discharge capacity of 520 mAh) was produced. A lithium ion secondary battery was produced in the same manner as in Example 1 except for these points, and the same measurements and evaluations as in Example 1 were performed. The results are shown in Table 1.
（比較例１〜２）
水溶性重合体の調製時に配合する各種単量体の配合量を変更して、得られる水溶性重合体の組成を表１に示す通りに変更した以外は実施例１と同様にして、各種測定及び評価を行った。結果を表１に示す。(Comparative Examples 1-2)
Various measurements were carried out in the same manner as in Example 1 except that the amounts of various monomers to be mixed at the time of preparing the water-soluble polymer were changed and the composition of the resulting water-soluble polymer was changed as shown in Table 1. And evaluated. The results are shown in Table 1.
（比較例３）
水溶性重合体の調製時に配合する各種単量体の配合量を変更して、得られる水溶性重合体の組成を表１に示す通りに変更した。このようにして調製した水溶性重合体を配合した以外は、実施例１と同様にして機能層用組成物を調製した。かかる機能層用組成物を、実施例１と同様にして製造した電極（正極及び負極）に対して塗布し、８０℃で３分間乾燥させ、厚み２μｍの機能層を備える電極を得て、上記方法に従って機能層の接着性を評価した。また、セパレータとして、実施例１と同じポリエチレン製の有機セパレータ基材（セルガード社製、「２５００」、厚さ：２５μｍ）を、表面に機能層を形成することなく用いた。そして、機能層を形成した負極、機能層を形成した正極、及びセパレータを用い、集電体／負極合材層／機能層／セパレータ／機能層／正極合材層／集電体となるように捲回セル（放電容量５２０ｍＡｈ相当）を作製した。これらの点以外は、実施例１と同様にして、リチウムイオン二次電池を作製し、実施例１と同様の測定及び評価を行った。結果を表１に示す。(Comparative example 3)
The composition of the resulting water-soluble polymer was changed as shown in Table 1 by changing the amounts of various monomers to be added at the time of preparing the water-soluble polymer. A functional layer composition was prepared in the same manner as in Example 1 except that the water-soluble polymer prepared as described above was blended. The functional layer composition was applied to the electrodes (positive electrode and negative electrode) produced in the same manner as in Example 1, dried at 80 ° C. for 3 minutes to obtain an electrode having a functional layer with a thickness of 2 μm, and The adhesion of the functional layer was evaluated according to the method. As the separator, the same polyethylene organic separator substrate as in Example 1 (“2500” manufactured by Celgard, thickness: 25 μm) was used without forming a functional layer on the surface. Then, using the negative electrode having the functional layer formed thereon, the positive electrode having the functional layer formed thereon, and the separator, a current collector / a negative electrode mixture layer / functional layer / separator / functional layer / positive electrode mixture layer / current collector is obtained. A wound cell (corresponding to a discharge capacity of 520 mAh) was produced. A lithium ion secondary battery was produced in the same manner as in Example 1 except for these points, and the same measurements and evaluations as in Example 1 were performed. The results are shown in Table 1.
なお、以下に示す表１中、
「ＰＥＧＤＡ」は、ポリエチレングリコールジアクリレート単位を示し、
「ＥＰＥＴＡ」は、エトキシ化ペンタエリスリトールテトラアクリレート（新中村化学工業株式会社製、「ＡＴＭ−３５Ｅ」）単位を示し、
「ＡＡ」は、アクリル酸単位を示し、
「２−ＨＥＡ」は、２−ヒドロキシエチルアクリレート単位を示し、
「ＡＡｍ」は、アクリルアミド単位を示し、
「ＡＣＲ」は、アクリル系重合体を示し、
「ＳＰ」は、セパレータを示し、
「ＨＥＡＡｍ」は、Ｎ−ヒドロキシエチルアクリルアミド単位を示し、
「ＤＭＡＡｍ」は、ジメチルアクリルアミド単位を示す。In Table 1 below,
"PEGDA" indicates a polyethylene glycol diacrylate unit,
"EPETA" represents an ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "ATM-35E") unit,
“AA” represents an acrylic acid unit,
"2-HEA" represents a 2-hydroxyethyl acrylate unit,
“AAm” indicates an acrylamide unit,
“ACR” indicates an acrylic polymer,
"SP" indicates a separator,
“HEAAm” represents N-hydroxyethyl acrylamide unit,
“DMAAm” indicates a dimethylacrylamide unit.
表１より、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む水溶性重合体を含むバインダー組成物を用いた実施例１〜１１では、電気化学素子としてのリチウムイオン二次電池に優れたレート特性及び耐熱性を発揮させ得る機能層が得られたことが分かる。
また、表１より、ヒドロキシル基含有単量体単位の含有割合が上記範囲外である比較例１〜３のバインダー組成物を用いても、電気化学素子のレート特性及び耐熱性を共に向上させ得る機能層を形成することはできなかったことが分かる。From Table 1, in Examples 1 to 11 using the binder composition containing the water-soluble polymer containing the hydroxyl group-containing monomer unit in the proportion of 15,000% by mass or more and 90.000% by mass or less, the electrochemical element was used. It can be seen that a functional layer capable of exhibiting excellent rate characteristics and heat resistance in the lithium ion secondary battery as described above was obtained.
In addition, from Table 1, it is possible to improve both the rate characteristics and the heat resistance of the electrochemical device by using the binder compositions of Comparative Examples 1 to 3 in which the content ratio of the hydroxyl group-containing monomer unit is outside the above range. It can be seen that the functional layer could not be formed.
本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用バインダー組成物を提供することができる。
また、本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る機能層を形成可能な電気化学素子機能層用組成物を提供することができる。
そして、本発明によれば、電気化学素子の耐熱性及びレート特性を向上させ得る電気化学素子用機能層を提供することができる。
さらに、本発明によれば、耐熱性及びレート特性の高い電気化学素子を提供することができる。ADVANTAGE OF THE INVENTION According to this invention, the binder composition for electrochemical element functional layers which can form the functional layer which can improve the heat resistance and rate characteristic of an electrochemical element can be provided.
Further, according to the present invention, it is possible to provide a composition for an electrochemical device functional layer capable of forming a functional layer capable of improving the heat resistance and rate characteristics of the electrochemical device.
Then, according to the present invention, it is possible to provide a functional layer for an electrochemical device capable of improving the heat resistance and rate characteristics of the electrochemical device.
Furthermore, according to the present invention, it is possible to provide an electrochemical element having high heat resistance and high rate characteristics.
Claims (8)
前記水溶性重合体が、ヒドロキシル基含有単量体単位を１５．０００質量％以上９０．０００質量％以下の割合で含む、電気化学素子機能層用バインダー組成物。A binder composition for an electrochemical device functional layer comprising a water-soluble polymer,
The binder composition for an electrochemical device functional layer, wherein the water-soluble polymer contains a hydroxyl group-containing monomer unit in a ratio of 15.000 mass% or more and 90.000 mass% or less.
An electrochemical device comprising the electrochemical device functional layer according to claim 7.
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