WO2022124125A1 - 電気化学素子用積層体及び電気化学素子 - Google Patents
電気化学素子用積層体及び電気化学素子 Download PDFInfo
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- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical class CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical class CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical class CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical class CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 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
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical class CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-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 class 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
- 230000002093 peripheral effect Effects 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001568 sexual effect Effects 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
- 239000002409 silicon-based active material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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 class CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical class CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
-
- 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
- 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
-
- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- 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
- H01M50/443—Particulate material
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; 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
Definitions
- the present invention relates to a laminate for an electrochemical element and an electrochemical element.
- Electrochemical elements 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 element generally includes a plurality of electrodes and an element member such as a separator that isolates these electrodes and prevents an internal short circuit.
- Patent Document 1 uses a polyolefin porous film as a substrate, which comprises a resin and a filler, has a film thickness of less than 8.0 ⁇ m, and has a surface roughness (Ra) of 0.15 ⁇ m or less.
- Ra surface roughness
- a separator laminated on top is disclosed. According to Patent Document 1, the porous layer provided in the separator is excellent in ion permeability and peel strength.
- element members such as electrodes and separators may be stored and transported in a rolled state, and during such storage and transportation, the element members stick to each other via the functional layer (that is, blocking).
- the functional layer that is, blocking
- the laminate used as the element member is required to suppress blocking through the functional layer (improve blocking resistance).
- the functional layer provided in the laminate is required to exhibit excellent adhesiveness in the manufacture of the electrochemical element.
- the hot-pressing time is shortened for the purpose of improving the production efficiency of the cell, heat is generated.
- the laminate used as the element member is also required to exhibit the above-mentioned blocking resistance and to exhibit excellent adhesiveness at low temperature (excellent low temperature adhesiveness).
- the above-mentioned conventional laminated body could not exhibit blocking resistance and low-temperature adhesiveness in a well-balanced manner when used as an element member.
- an object of the present invention is to provide a laminate for an electrochemical element that can be advantageously used as an element member having excellent blocking resistance and low-temperature adhesiveness, and an electrochemical element including the laminate for the electrochemical element as an element member. And.
- the present inventor has made diligent studies to achieve the above object. Then, when the laminate is produced, the present inventor has adhesive particles containing heat-resistant fine particles (fine particles capable of exhibiting heat resistance) and a polyester polymer having a glass transition temperature within a predetermined range (exhibiting adhesiveness). By forming a functional layer on the base material using (possible particles) and a binder and giving the functional layer the predetermined properties, the obtained laminate can be obtained with blocking resistance and low temperature adhesiveness. We have found that it can be used as an excellent element member for both, and completed the present invention.
- the present invention aims to advantageously solve the above problems, and the laminate for an electrochemical element of the present invention includes a base material and a functional layer arranged on the base material.
- the functional layer is a laminate for an electrochemical element, and the functional layer contains heat-resistant fine particles, adhesive particles containing an adhesive polymer, and a binder, and the adhesive polymer has a glass transition temperature.
- the functional layer contains a polyester polymer having a temperature in the range of 10 ° C. or higher and 95 ° C. or lower, and when viewed in plan from the functional layer side, the functional layer has an adhesive region made of the adhesive particles, the heat-resistant fine particles, and the binding.
- the above-mentioned laminate can be advantageously used as an element member having excellent blocking resistance and low-temperature adhesiveness.
- the "glass transition temperature” can be measured by using the method described in Examples.
- the "volume average particle diameter" of the adhesive particles can be measured by using the method described in Examples.
- the "average height in the stacking direction" of the heat-resistant region can be measured by using the method described in Examples.
- the adhesive particles further contain a meltable additive having a melting point in the range of 40 ° C. or higher and 95 ° C. or lower. If the adhesive particles contain a meltable additive having a melting point within the above range, the low temperature adhesiveness of the element member made of the laminated body can be further improved.
- the "melting point" of the meltable additive is measured by using a differential scanning calorimeter (DSC) under the condition of raising the temperature at 100 ° C./min, and the maximum value of the obtained DSC curve is obtained. Can be obtained by taking.
- DSC differential scanning calorimeter
- the meltable additive is a group consisting of an ester wax, a paraffin wax, and a crystalline polyester resin having a glass transition temperature in the range of 10 ° C. or higher and 95 ° C. or lower. It is preferably at least one selected from.
- the "crystalline polyester resin” does not have a glass transition temperature in the range of 10 ° C. or higher and 95 ° C. or lower, and therefore has a component different from that of the "polyester polymer” having a glass transition temperature within the range. be.
- the volume average particle diameter of the adhesive particles is 1.0 ⁇ m or more and 10.0 ⁇ m or less.
- the volume average particle diameter of the adhesive particles is within the above-mentioned range, it is possible to further improve the blocking resistance and the low temperature adhesiveness while increasing the heat resistance of the element member made of the laminated body.
- the ratio of the volume average particle diameter of the adhesive particles to the average height in the stacking direction of the heat-resistant region is 1.1 or more and 10.0 or less. If the ratio of the volume average particle diameter of the adhesive particles to the average height in the stacking direction of the heat-resistant region (volume average particle diameter of the adhesive particles / average height in the stacking direction of the heat-resistant region) is within the above range, the laminated body is used. It is possible to further improve the blocking resistance and the low temperature adhesiveness while increasing the heat resistance of the element member.
- the volume ratio of the content of the heat-resistant fine particles to the content of the adhesive particles in the functional layer is 55/45 or more and 95/5 or less. Is preferable. If the volume ratio of the content of the heat-resistant fine particles (heat-resistant fine particles / adhesive particles) to the content of the adhesive particles in the functional layer is within the above-mentioned range, the heat resistance of the element member made of the laminated body is enhanced. , Low temperature adhesiveness can be further improved.
- the average circularity of the adhesive particles is 0.90 or more and 0.99 or less. If the average circularity of the adhesive particles is within the above range, the element characteristics (rate characteristics, cycle characteristics) of the electrochemical element provided with the element member can be further improved while further improving the low temperature adhesiveness of the element member made of the laminated body. Can be enhanced.
- the "average circularity" of the adhesive particles can be measured by using the method described in Examples.
- the heat-resistant fine particles are inorganic fine particles. If inorganic fine particles are used as the heat-resistant fine particles, the heat resistance of the element member made of the laminated body can be improved.
- the inorganic fine particles include at least one selected from the group consisting of alumina particles, boehmite particles, barium sulfate particles, and magnesium hydroxide particles.
- the present invention is intended to advantageously solve the above problems, and the electrochemical element of the present invention is characterized by comprising a laminate for any of the above-mentioned electrochemical elements.
- An electrochemical device provided with any of the above-mentioned laminates as a device member is excellent in device characteristics such as rate characteristics and cycle characteristics.
- a laminate for an electrochemical element that can be advantageously used as an element member having excellent blocking resistance and low temperature adhesiveness, and an electrochemical element including the laminate for the electrochemical element as an element member. Can be done.
- the laminate for an electrochemical element of the present invention can be used as an element member such as a separator or an electrode (positive electrode and negative electrode).
- the electrochemical element of the present invention includes a laminate for an electrochemical element of the present invention as an element member.
- the laminate of the present invention includes a base material and a functional layer formed on the base material.
- the functional layer on the base material includes at least an adhesive region made of adhesive particles and a heat-resistant region made of heat-resistant fine particles and a binder when the laminated body is viewed in a plan view from the functional layer side.
- the volume average particle diameter of the adhesive particles constituting the adhesive region is larger than the average height in the stacking direction of the heat-resistant region.
- the laminated body of the present invention having such a structure has many places where the adhesive particles in the adhesive region protrude from the heat-resistant region in the functional layer, but it is good with the adherend through the functional layer. Can adhere to.
- the polyester polymer derived from the adhesive particles melted by the hot press penetrates into the matrix of the heat-resistant region formed by binding the heat-resistant fine particles with the binder, and becomes an anchor (anchor effect).
- anchor effect the low-temperature adhesiveness of the element member made of the laminated body is improved.
- the heat-resistant region suppresses the polyester polymer derived from the adhesive particles melted by the hot press from spreading excessively in the direction parallel to the spreading direction of the surface of the base material, and as a result, the path of the charge carrier such as lithium ion is prevented. It is presumed that this is possible, but the element characteristics such as rate characteristics and cycle characteristics are improved.
- FIG. 1 is a plan view schematically showing an example when the laminate 100 for an electrochemical element according to the present invention is viewed in a plan view from the functional layer side.
- a heat-resistant region 12 and a plurality of adhesive regions 11 surrounded by the heat-resistant region 12 exist on the surface of the functional layer 10 included in the laminate 100 for an electrochemical element.
- FIG. 2 is a cross-sectional view schematically showing an example of a stacking direction cross section of the layered body 100 for an electrochemical element according to the present invention.
- FIG. 1 is a plan view schematically showing an example when the laminate 100 for an electrochemical element according to the present invention is viewed in a plan view from the functional layer side.
- a heat-resistant region 12 and a plurality of adhesive regions 11 surrounded by the heat-resistant region 12 exist on the surface of the functional layer 10 included in the laminate 100 for an electrochemical element.
- FIG. 2 is a cross-sectional view schematically showing an example of a stacking direction cross section of the layered body 100 for
- the laminate 100 for an electrochemical element has a functional layer 10 laminated on a base material 20, and the functional layer 10 has an adhesive region 11 and a heat-resistant region 12.
- the adhesive region 11 is composed of adhesive particles 11a.
- the heat-resistant region 12 is formed by binding the heat-resistant fine particles 12a by the binder 12b and overlapping them in the laminating direction (thickness direction). Then, in FIG. 2, the particle diameter (height in the stacking direction from the surface of the base material 20) D of the adhesive particles 11a is larger than the height T in the stacking direction of the heat-resistant region 12.
- the volume average particle diameter of the adhesive particles is larger than the average height in the stacking direction of the heat-resistant region, it is considered that there are many places where the adhesive particles protrude as shown in FIG.
- the laminate of the present invention is not limited to the examples shown in FIGS. 1 and 2.
- the functional layers may be provided on both sides of the base material.
- at least one of the functional layers may be a functional layer satisfying predetermined properties.
- the adhesive region of the functional layer may be composed of one adhesive particle as shown in FIG. 2, but may be formed by a plurality of adhesive particles aggregated.
- the adhesive region of the functional layer may be composed of only adhesive particles as shown in FIG. 2, but is composed of adhesive particles, a binder and other components described later.
- the heat-resistant region of the functional layer may be composed only of the heat-resistant fine particles and the binder as shown in FIG. 2, but the heat-resistant fine particles and the binder will be described later. It may be composed of other components.
- the volume average particle diameter of the adhesive particles is not particularly limited as long as it is larger than the average height in the stacking direction of the heat-resistant region, but is preferably 1.0 ⁇ m or more, more preferably 2.5 ⁇ m or more, and 5 It is more preferably 9.0 ⁇ m or more, more preferably 10.0 ⁇ m or less, more preferably 9.0 ⁇ m or less, and further preferably 8.0 ⁇ m or less. If the volume average particle diameter of the adhesive particles is 1.0 ⁇ m or more, it is presumed that the adhesive particles in the adhesive region protrude further than the heat-resistant region, but the low-temperature adhesiveness of the element member made of the laminated body is further improved. Can be improved.
- the heat-resistant fine particles can be more densely aggregated in the heat-resistant region adjacent to the adhesive region due to the increase in the volume average particle diameter of the adhesive particles. Can be improved.
- the blocking resistance of the element member made of the laminated body can be further improved.
- the volume average particle diameter of the adhesive particles is 10.0 ⁇ m or less, the number of adhesive particles (number of particles) per unit volume of the functional layer increases, so that the element member and the adherend provided with the functional layer It is presumed that this is because the number of bonding points at the time of bonding is increased, but the low-temperature adhesiveness of the element member can be further improved.
- the volume average particle diameter of the adhesive particles can be adjusted, for example, by changing the production conditions of the adhesive particles.
- the average height of the heat-resistant region in the stacking direction is not particularly limited as long as it is smaller than the volume average particle diameter of the adhesive particles, but is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more. It is more preferably 1.0 ⁇ m or more, preferably less than 6.0 ⁇ m, preferably less than 5.0 ⁇ m, more preferably less than 4.0 ⁇ m, and less than 2.5 ⁇ m. More preferred.
- the average height of the heat-resistant region in the stacking direction is 0.5 ⁇ m or more, sufficient heat resistance of the element member provided with the functional layer can be sufficiently ensured, and if it is less than 6.0 ⁇ m, the ion diffusivity of the functional layer is improved. It can be secured to improve the rate characteristics and cycle characteristics of the electrochemical element.
- the average height in the stacking direction of the heat-resistant region is, for example, the conditions for forming the functional layer (the content ratio of the heat-resistant fine particles and / or the binder in the composition for the functional layer used for forming the functional layer, the composition for the functional layer). Can be adjusted by changing the thickness of the coating film obtained by supplying the mixture onto the substrate.
- the ratio of the volume average particle diameter of the adhesive particles to the average height in the stacking direction of the heat-resistant region should be 1.1 or more. It is preferably 1.2 or more, more preferably 1.6 or more, more preferably 10.0 or less, more preferably 5.0 or less, and 3.5 or less. It is more preferable to have. If the value of the above ratio is 1.1 or more, it is presumed that the adhesive particles in the adhesive region protrude sufficiently from the heat-resistant region, but the low-temperature adhesiveness of the element member made of the laminated body is further improved.
- the functional layer included in the laminate of the present invention having the above-mentioned structure includes heat-resistant fine particles, adhesive particles, and a binder.
- the functional layer may contain heat-resistant fine particles, adhesive particles, and components (other components) other than the binder.
- the heat-resistant fine particles contained in the functional layer are not particularly limited, and are fine particles made of an inorganic material (that is, fine particles that are stably present and electrochemically stable in the environment in which the electrochemical element is used (that is,). Inorganic fine particles) and fine particles made of an organic material (that is, organic fine particles) can be mentioned.
- the heat-resistant fine particles the inorganic fine particles and the organic fine particles may be used alone, or the inorganic fine particles and the organic fine particles may be used in combination.
- inorganic fine particles examples include aluminum oxide (alumina, Al 2 O 3 ), aluminum oxide hydrate (bemite, AlOOH), gibsite (Al (OH) 3 ), silicon oxide, magnesium oxide (magnesia), magnesium hydroxide, and the like.
- Inorganic oxide particles such as calcium oxide, titanium oxide (titania), barium titanate (BaTIO 3 ), ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalent bonds such as silicon and diamond.
- Sexual crystal particles sparingly soluble ion crystal particles such as barium sulfate, calcium fluoride, barium fluoride; clay fine particles such as talc and montmorillonite; and the like. These particles may be subjected to element substitution, surface treatment, solid solution formation or the like, if necessary. Inorganic fine particles may be used alone or in combination of two or more.
- the organic fine particles are fine particles made of a polymer having no adhesiveness, unlike adhesive particles and a binder containing an adhesive polymer such as a polyester polymer.
- an adhesive polymer such as a polyester polymer.
- the organic fine particles crosslinked polymethyl methacrylate, crosslinked polystyrene, crosslinked polyvinylbenzene, styrene-divinylbenzene copolymer crosslinked product, polystyrene, polyimide, polyamide, polyamideimide, melamine resin, phenol resin, benzoguanamine-formaldehyde.
- Examples thereof include various crosslinked polymer particles such as condensates, heat-resistant polymer particles such as polysulphon, polyacrylonitrile, polyaramid, polyacetal and thermoplastic polyimide, and modified products and derivatives thereof.
- the organic fine particles may be used alone or in combination of two or more. As described above, the organic fine particles are composed of a polymer having no adhesiveness. Specifically, the glass transition temperature of the polymer constituting the organic fine particles is preferably 150 ° C. or higher.
- inorganic fine particles and organic fine particles composed of a polymer having a glass transition temperature of 150 ° C. or higher are preferable from the viewpoint of further improving the heat resistance of the element member made of a laminated body, and the inorganic fine particles are preferable. More preferably, particles made of alumina (alumina particles), particles made of boehmite (boehmite particles), particles made of barium sulfate (barium sulfate particles), and particles made of magnesium hydroxide (magnesium hydroxide particles) are even more preferable.
- the heat-resistant fine particles have a volume average particle diameter of preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, further preferably 0.3 ⁇ m or more, and 1.0 ⁇ m or less. Is more preferable, 0.9 ⁇ m or less is more preferable, and 0.8 ⁇ m or less is further preferable.
- the volume average particle diameter of the heat-resistant fine particles is 0.1 ⁇ m or more, it is possible to suppress the decrease in ionic conductivity of the functional layer due to the excessively dense filling of the heat-resistant fine particles in the functional layer. , It is possible to make an electrochemical element exhibit excellent element characteristics (particularly, rate characteristics).
- the volume average particle diameter of the heat-resistant fine particles is 1.0 ⁇ m or less, even if the functional layer is thinned, the element member made of the laminate provided with the functional layer can sufficiently exhibit excellent heat resistance. can. Therefore, it is possible to increase the capacity of the electrochemical element while sufficiently ensuring the heat resistance of the element member.
- the adhesive particles are particles containing an adhesive polymer containing at least a polyester polymer, and the particles may contain a component (arbitrary component) other than the adhesive polymer. That is, the adhesive particles may be particles substantially composed of only the adhesive polymer, or may be particles composed of the adhesive polymer and an arbitrary component.
- the adhesive polymer contains at least a polyester polymer as described above, and optionally contains an adhesive polymer other than the polyester polymer (other adhesive polymers).
- the polyester polymer is a polymer obtained by condensation polymerization of an alcohol component and a carboxylic acid component.
- the polyester polymer is a condensation polymer having a repeating unit (alcohol unit) derived from an alcohol component and a repeating unit (carboxylic acid unit) derived from a carboxylic acid component.
- a polyhydric alcohol can be used.
- examples of the polyhydric alcohol include divalent alcohols and trihydric or higher alcohols.
- Examples of the divalent alcohol include a chain aliphatic diol, a diol having an oxyalkylene group, and a diol having a carbocyclic ring.
- Examples of the chain aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Examples thereof include 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol.
- diol having an oxyalkylene group examples include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
- diol having a carbon ring examples include 1,4-cyclohexanedimethanol, bisphenols (eg, bisphenol A, bisphenol F, bisphenol S), hydrogenated bisphenols, and alkylene oxide adducts of bisphenols (eg, bisphenols). Ethylene oxide adducts, propylene oxide adducts, butylene oxide adducts) and the like.
- trihydric or higher alcohol examples include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.
- the alcohol component may be used alone or in combination of two or more.
- a diol having a carbon ring is preferable, bisphenols, hydrogen additives of bisphenols, and alkylene oxide adducts of bisphenols are more preferable, and alkylene oxide adducts of bisphenols are more preferable, and bisphenol A is more preferable.
- the alkylene oxide adduct is particularly preferable, and the ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A are most preferable.
- Carboxylic acid component As the carboxylic acid component, a polyvalent carboxylic acid, an anhydride thereof, and a halide thereof can be used.
- the polyvalent carboxylic acid include chain aliphatic polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and glutaconic acid.
- Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthalenedicarboxylic acid and pyromellitic acid;
- the carboxylic acid component may be used alone or in combination of two or more.
- terephthalic acid, isophthalic acid, fumaric acid, trimellitic acid, and anhydrides thereof are preferable.
- the method for condensation polymerization of the alcohol component and the carboxylic acid component described above is not particularly limited, and known polymerization aids and polymerization conditions can be adopted.
- the polyester polymer needs to have a glass transition temperature of 10 ° C. or higher and 95 ° C. or lower, preferably 15 ° C. or higher, more preferably 30 ° C. or higher, and 40 ° C. or higher. More preferably, it is more preferably 56 ° C. or higher, particularly preferably 90 ° C. or lower, and even more preferably 80 ° C. or lower.
- the glass transition temperature of the polyester polymer is less than 10 ° C., the blocking resistance of the element member made of the laminated body is lowered.
- the glass transition temperature of the polyester polymer is more than 95 ° C., the low temperature adhesiveness of the element member made of the laminated body is lowered.
- the glass transition temperature of the polyester polymer can be controlled by changing the types of the alcohol component and / or the carboxylic acid component used in the preparation of the polyester polymer and the polymerization conditions.
- the melting point of the polyester polymer may be observed by the above-mentioned method applied to a "meltable additive" such as "crystalline polyester resin” described later (that is, the polyester polymer has crystalline property). May be). However, even if the polyester polymer has a melting point, the melting point is preferably outside the range of 40 ° C. or higher and 95 ° C. or lower. In other words, it is preferable that the polyester polymer does not have a melting point in the range of 40 ° C. or higher and 95 ° C. or lower.
- the adhesive polymer other than the polyester polymer optionally contained in the adhesive particles at least a polymer containing an aromatic monovinyl monomer unit (aromatic vinyl polymer) is preferable.
- the aromatic vinyl-based polymer may contain a monomer unit (other monomer unit) other than the aromatic monovinyl monomer unit.
- the adhesive polymer contains a polymer containing an aromatic monovinyl monomer unit
- the elasticity of the adhesive particles can be improved and the strength of the functional layer can be increased.
- the example of the aromatic monovinyl monomer capable of forming the aromatic monovinyl monomer unit is not particularly limited, and is, for example, styrene, ⁇ -methylstyrene, styrenesulfonic acid, butoxystyrene, vinylnaphthalene. And so on. These may be used individually by 1 type, or may be used in combination of 2 or more type. And among these, styrene is preferable.
- the content ratio of the aromatic monovinyl monomer unit in the aromatic vinyl polymer is preferably 30% by mass or more, more preferably, when all the monomer units in the aromatic vinyl polymer are 100% by mass. It is preferably 60% by mass or more, preferably 90% by mass or less, and more preferably 85% by mass or less.
- the content ratio of the aromatic monovinyl monomer unit is 30% by mass or more, the elasticity of the adhesive particles can be sufficiently improved and the strength of the functional layer can be increased. Therefore, the low temperature adhesiveness of the element member made of the laminated body can be sufficiently improved.
- each "content ratio of monomer unit" contained in the polymer can be measured by using a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
- the other monomer unit is not particularly limited, but a crosslinkable monomer unit and a (meth) acrylic acid ester monomer unit are preferably mentioned.
- (meth) acrylic means acrylic and / or methacrylic.
- the crosslinkable monomer that can form a crosslinkable monomer unit is a monomer that can form a crosslinkable structure during or after polymerization by heating or irradiation with energy rays.
- the aromatic vinyl-based polymer contains a crosslinkable monomer unit, the elasticity of the adhesive particles can be improved, and as a result, the low-temperature adhesiveness of the element member made of the laminated body can be sufficiently improved. ..
- Examples of the monomer capable of forming a crosslinkable monomer unit include a polyfunctional monomer having two or more polymerization reactive groups.
- Examples of such a polyfunctional monomer include divinyl compounds such as allyl methacrylate and divinylbenzene; di (meth) such as diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate and 1,3-butylene glycol diacrylate.
- Acrylic acid ester compounds Tri (meth) acrylic acid ester compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; Ethylene unsaturated monomers containing epoxy groups such as allylglycidyl ether and glycidyl methacrylate; Can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type. And among these, divinylbenzene is preferable.
- the content ratio of the crosslinkable monomer unit in the aromatic vinyl-based polymer is preferably 0.01% by mass when the amount of all the monomer units in the aromatic vinyl-based polymer is 100% by mass.
- the above is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less.
- the aromatic vinyl-based polymer contained in the adhesive particles can be sufficiently suppressed from being eluted into the electrolytic solution. Further, the elasticity of the adhesive particles can be improved, and as a result, the low temperature adhesiveness of the element member made of the laminated body can be sufficiently improved.
- examples of the (meth) acrylic acid ester monomer capable of forming a (meth) acrylic acid ester monomer unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and butyl acrylate (n-butyl).
- Alkyl acrylates such as acrylates and t-butyl acrylates), pentyl acrylates, hexyl acrylates, heptyl acrylates, octyl acrylates (2-ethylhexyl acrylates, etc.), nonyl acrylates, decyl acrylates, lauryl acrylates, n-tetradecyl acrylates, stearyl acrylates, etc.
- Estres as well as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate (such as n-butyl methacrylate and t-butyl methacrylate), pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate (such as 2-ethylhexyl methacrylate).
- These (meth) acrylic acid ester monomers may be used alone or in combination of two or more.
- n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable.
- the content ratio of the (meth) acrylic acid ester monomer unit in the aromatic vinyl-based polymer is preferably 5 when all the monomer units in the aromatic vinyl-based polymer are 100% by mass. By mass or more, more preferably 10% by mass or more, preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 35% by mass or less.
- the content ratio of the (meth) acrylic acid ester monomer unit is 5% by mass or more, the glass transition temperature of the aromatic vinyl-based polymer is suppressed from being excessively lowered, and the element member made of the laminated body is formed. The blocking resistance can be sufficiently improved.
- the content ratio of the (meth) acrylic acid ester monomer unit is 65% by mass or less, the low-temperature adhesiveness of the element member made of the laminated body can be sufficiently improved.
- the other monomer unit is not particularly limited, and the monomer described later in the section of "Binder" is used. Units (excluding those corresponding to any of an aromatic monovinyl monomer unit, a crosslinkable monomer unit, and a (meth) acrylic acid ester monomer unit) can be mentioned.
- the content ratio of the above-mentioned aromatic monovinyl monomer unit, crosslinkable monomer unit, and monomer unit other than the (meth) acrylic acid ester monomer unit in the aromatic vinyl-based polymer is
- the total monomer unit in the aromatic vinyl polymer is 100% by mass, it is preferably 0% by mass or more from the viewpoint of ensuring the stability of the composition for the functional layer used for forming the functional layer. It is 0% by mass or less, more preferably 0% by mass or more and 7% by mass or less, and further preferably 0% by mass or more and 5% by mass or less.
- the glass transition temperature of other adhesive polymers such as the above-mentioned aromatic vinyl-based polymer is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and more preferably 40 ° C. or higher. More preferably, it is more preferably 90 ° C. or lower, and even more preferably 80 ° C. or lower.
- the glass transition temperature in the adhesive particles is 10 ° C. or higher, the blocking resistance of the element member made of the laminated body can be further improved, and when the temperature is 90 ° C. or lower, the low temperature adhesiveness of the element member is further improved. Can be made to.
- the glass transition temperature of the other adhesive polymer can be controlled by changing the type and / or ratio of the monomer used for preparing the polymer and the polymerization conditions.
- the adhesive polymer contained in the adhesive particles is composed of a polyester polymer and another adhesive polymer
- these two or more (plural) polymers are two or more different from each other.
- the polymer forms particles having a heterogeneous structure formed by physically or chemically bonding.
- a core-shell structure formed of spherical particles whose central portion (core portion) and outer shell portion (shell portion) are different from each other; two or more polymers.
- the "core-shell structure” includes a structure in which the shell portion completely covers the outer surface of the core portion and a structure in which the shell portion partially covers the outer surface of the core portion.
- the adhesive polymer is composed of the polyester polymer and other adhesive polymers
- the core portion is composed of other adhesive polymers (for example, the above-mentioned aromatic vinyl-based polymer), and the shell is formed. It is preferable that the portion is composed of a polyester polymer.
- a meltable additive having a melting point in the range of 40 ° C. or higher and 95 ° C. or lower is preferably mentioned.
- the adhesive particles contain the meltable additive, the low temperature adhesiveness of the element member made of the laminated body can be further improved.
- the meltable additive needs to have a melting point of 40 ° C. or higher and 95 ° C. or lower, preferably 42 ° C. or higher, more preferably 45 ° C. or higher, and 50 ° C. or higher. It is more preferably 90 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 60 ° C. or lower. If the melting point of the meltable additive is 40 ° C. or higher, the blocking resistance of the element member made of the laminated body is not excessively impaired, and if the melting point of the meltable additive is 95 ° C. or lower, the laminated body is used. It is possible to sufficiently improve the low temperature adhesiveness of the element member.
- the meltable additive may be used alone or in combination of two or more.
- plant wax examples include candelilla wax, carnauba wax, rice wax, wood wax, and jojoba oil.
- animal wax examples include beeswax.
- petroleum-based waxes examples include paraffin wax, microcrystalline wax, and petrolatum wax.
- Synthetic waxes can be classified into Fischer-Tropsch waxes, polyolefin waxes, ester waxes and the like.
- the polyolefin wax include polyethylene wax, polypropylene wax, and polybutylene wax.
- the ester wax either a monohydric alcohol fatty acid ester or a polyhydric alcohol fatty acid ester can be used.
- specific examples of the monohydric alcohol fatty acid ester include behenyl stearate and the like.
- polyhydric alcohol fatty acid ester examples include pentaerythritol tetramyrystate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, pentaerythritol tetralaurate, pentaerythritol tetrabehenate and the like;
- examples thereof include dipentaerythritol esters such as pentaerythritol hexamillistate, dipentaerythritol hexapalmitate, and dipentaerythritol hexalaurate.
- the crystalline polyester resin has a melting point in the range of 40 ° C. or higher and 95 ° C. or lower, and does not have a glass transition temperature in the range of 10 ° C. or higher and 95 ° C. or lower (in other words, has a glass transition temperature itself). No, or if it has a glass transition temperature in the range of less than 10 ° C and / or more than 95 ° C), it is not particularly limited, and a polymer obtained by condensation polymerization of an alcohol component and a carboxylic acid component is used. Can be done.
- the alcohol component and the carboxylic acid component used for preparing the crystalline polyester resin those described above can be used in the section of "polyester polymer".
- the alcohol component a chain aliphatic diol is preferable, and 1,6-hexanediol is more preferable.
- the carboxylic acid component a chain aliphatic polyvalent carboxylic acid is preferable, and sebacic acid is more preferable.
- the method for condensation polymerization of the alcohol component and the carboxylic acid component described above is not particularly limited, and known polymerization aids and polymerization conditions can be adopted.
- ester wax is more preferred.
- the content of the meltable additive in the adhesive particles is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 5 parts by mass per 100 parts by mass of the adhesive polymer.
- the above is more preferably, 6 parts by mass or more is further preferable, 10 parts by mass or more is particularly preferable, 30 parts by mass or less is preferable, and 25 parts by mass or less is more preferable. , 20 parts by mass or less, more preferably 15 parts by mass or less.
- the content of the meltable additive in the adhesive particles is 30 parts by mass or less per 100 parts by mass of the adhesive polymer, the bleed-out of the meltable additive is sufficiently suppressed and the element made of a laminated body is formed. It is possible to improve the rate characteristics and cycle characteristics of the electrochemical element provided with the element member while further enhancing the blocking resistance of the member.
- the content of the meltable additive in the functional layer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 5 parts by mass or more per 100 parts by mass of the adhesive polymer. It is more preferably 6 parts by mass or more, particularly preferably 10 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass. It is more preferably parts by mass or less, and particularly preferably 15 parts by mass or less.
- the content of the meltable additive in the functional layer is 1 part by mass or more per 100 parts by mass of the adhesive polymer, the low temperature adhesiveness of the element member made of the laminated body can be further improved.
- the content of the functional layer in the adhesive particles is 30 parts by mass or less per 100 parts by mass of the adhesive polymer, the bleed-out of the meltable additive is sufficiently suppressed, and the element member made of the laminated body is formed. It is possible to improve the rate characteristics and cycle characteristics of the electrochemical element provided with the element member while further improving the blocking resistance.
- the adhesive particles preferably have an average circularity of 0.90 or more, more preferably 0.92 or more, further preferably 0.95 or more, and 0.97 or more. Is particularly preferable, and 0.99 or less is particularly preferable.
- the average circularity of the adhesive particles is 0.90 or more, the low temperature adhesiveness of the element member made of the laminated body can be further improved.
- the element member made of the laminated body can exhibit good adhesiveness even in the electrolytic solution.
- the average circularity of the adhesive particles is 0.99 or less, the resistance of the element member made of the laminated body in the electrolytic solution is reduced, and the rate characteristics and cycle characteristics of the electrochemical element provided with the element member are improved. Can be made to.
- the average circularity of the adhesive particles can be adjusted by changing the method for preparing the adhesive particles.
- the method for preparing the adhesive particles containing the adhesive polymer is a method of preparing the adhesive particles containing the polyester polymer and optional components such as a meltable additive used as necessary (collectively, "adhesiveness". It is not particularly limited as long as it can be made into particles, for example, 1) to 4): 1) The adhesive particle material is dissolved and / or dispersed in at least an organic solvent in which a polyester polymer can be dissolved to prepare a liquid composition, the liquid composition is dispersed in an aqueous medium, and then the organic solvent is used.
- a method of atomizing an adhesive particle material by removing it (dissolution suspension method), 2) A method of dispersing an adhesive particle material in an aqueous medium using a surfactant and / or a dispersion stabilizer and aggregating the dispersed fine particles to atomize the adhesive particle material (emulsification aggregation method). 3) A method of melt-kneading an adhesive particle material, cooling it, and then crushing the obtained kneaded material to pulverize the adhesive particle material (crushing method). 4) A method of suspend-polymerizing a monomer used for preparing other adhesive polymers in the presence of a polyester polymer and an optional component used as necessary to garble the adhesive particle material into particles (suspension). Suspension polymerization method), Can be mentioned.
- the dissolution-suspension method, the emulsification aggregation method, and the suspension polymerization method are preferable from the viewpoint that the volume average particle size and the average circularity of the adhesive particles can be easily adjusted.
- Suspension polymerization method is more preferable.
- the dissolution / suspension method, the emulsification / aggregation method, the pulverization method, and the suspension polymerization method can be carried out by adopting known methods and conditions, respectively.
- the content ratio of the heat-resistant fine particles to the adhesive particles in the functional layer is not particularly limited, but the volume ratio of the content of the heat-resistant fine particles to the content of the adhesive particles (heat-resistant fine particles / adhesive particles).
- the value of is preferably 55/45 or more, more preferably 60/40 or more, preferably 95/5 or less, more preferably 80/20 or less, and 75/25 or less. Is more preferable.
- the value of the heat-resistant fine particles / adhesive particles (volume standard) is 55/45 or more, the heat resistance of the element member made of the laminated body can be improved, and when it is 95/5 or less, the element member of the element member is concerned. The low temperature adhesiveness can be further improved.
- the value of the mass ratio (heat-resistant fine particles / adhesive particles) of the content of the heat-resistant fine particles to the content of the adhesive particles is preferably 49/51 or more, and more preferably 58/42 or more. It is preferably 64/36 or more, more preferably 99/1 or less, more preferably 94/6 or less, and even more preferably 91/9 or less. If the value of the heat-resistant fine particles / adhesive particles (based on mass) is 49/51 or more, the heat resistance of the element member made of the laminated body provided with the functional layer can be improved, and if it is 99/1 or less, the heat resistance can be improved. The low temperature adhesiveness of the element member can be further improved.
- the binder binds the heat-resistant fine particles to each other in the heat-resistant region.
- the binder include known polymers used as the binder, for example, conjugated diene-based polymers, acrylic-based polymers, polyvinylidene fluoride (PVDF), and polyvinyl alcohol (PVOH).
- conjugated diene-based polymers for example, conjugated diene-based polymers, acrylic-based polymers, polyvinylidene fluoride (PVDF), and polyvinyl alcohol (PVOH).
- PVDF polyvinylidene fluoride
- PVOH polyvinyl alcohol
- one type may be used alone, or two or more types may be used in combination.
- a conjugated diene-based polymer As the binder, a conjugated diene-based polymer, an acrylic-based polymer, a polyvinylidene fluoride (PVDF), or other water-insoluble polymer that can be dispersed in a dispersion medium such as water is preferable, and the conjugated diene-based polymer is preferable.
- Polymers and acrylic polymers are more preferable, and acrylic polymers are even more preferable.
- water-insoluble means that when 0.5 g of the polymer is dissolved in 100 g of water at a temperature of 25 ° C., the insoluble content is 90% by mass or more. ..
- the conjugated diene-based polymer refers to a polymer containing a conjugated diene monomer unit derived from the conjugated diene monomer.
- Specific examples of the conjugated diene polymer include, without limitation, an aromatic monovinyl monomer unit such as a styrene-butadiene copolymer (SBR) and an aliphatic conjugated diene monomer unit. Examples thereof include polymers, butadiene rubber (BR), nitrile rubber (NBR) (polymers containing acrylonitrile units and 1,3-butadiene units), and hydrides thereof.
- the acrylic polymer refers to a polymer containing a (meth) acrylic acid ester monomer unit.
- the acrylic polymer preferably contains, for example, at least one of a crosslinkable monomer unit and an acid group-containing monomer unit in addition to the (meth) acrylic acid ester monomer unit.
- Examples of the (meth) acrylic acid ester monomer that can form a (meth) acrylic acid ester monomer unit include the same as those described above in the section of “adhesive particles”. These may be used individually by 1 type and may be used in combination of 2 or more type. And among these, n-butyl acrylate is preferable. Further, the content ratio of the (meth) acrylic acid ester monomer unit in the binder (acrylic polymer) is preferably 65 when all the monomer units in the binder are 100% by mass.
- More than mass% more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass. % Or less.
- crosslinkable monomer capable of forming a crosslinkable monomer unit examples include those similar to those described above in the section of “adhesive particles”. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, allyl methacrylate and allyl glycidyl ether are preferable.
- the content ratio of the crosslinkable monomer unit in the binder (acrylic polymer) is preferably 0.1% by mass when all the monomer units in the binder are 100% by mass. The above is preferably 3.0% by mass or less, and more preferably 2.5% by mass or less.
- the rate characteristics and cycle characteristics of the electrochemical element can be improved, and if it is 3.0% by mass or less, the element made of a laminated body.
- the low temperature adhesiveness of the member can be further improved.
- Examples of the acid group-containing monomer that can form an acid group-containing monomer unit include a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, a monomer having a phosphoric acid group, and a monomer having a phosphoric acid group.
- a monomer having a hydroxyl group can be mentioned.
- Examples of the monomer having a carboxylic acid group include monocarboxylic acid and dicarboxylic acid.
- Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
- Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, ethyl (meth) acrylic acid-2-sulfonate, and 2-acrylamide-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid.
- “(meth) allyl” means allyl and / or metallyl.
- examples of the monomer having a phosphate group include -2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl. And so on.
- "(meth) acryloyl” means acryloyl and / or methacryloyl.
- examples of the monomer having a hydroxyl group include -2-hydroxyethyl acrylate, -2-hydroxypropyl acrylate, -2-hydroxyethyl methacrylate, and -2-hydroxypropyl methacrylate.
- these acid group-containing monomers one type may be used alone, or two or more types may be used in combination. Among these, a monomer having a carboxylic acid group is preferable, and methacrylic acid is more preferable.
- the content ratio of the acid group-containing monomer unit in the binder (acrylic polymer) is preferably 0.1 mass when all the monomer units in the binder are 100% by mass. % Or more, preferably 3.0% by mass or less, and more preferably 2.5% by mass or less.
- the acrylic polymer as a binder is a monomer unit other than the above-mentioned (meth) acrylic acid ester monomer unit, crosslinkable monomer unit, and acid group-containing monomer unit (others). (Monomer unit) can be included.
- 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl- Fat group conjugated diene monomers such as 1,3-butadiene, 2-chlor-1,3-butadiene; aromatic monovinyl monomers described above in the section of "adhesive particles"; nitriles such as acrylonitrile and methacrylonitrile Group-containing monomer; Olefin monomer such as ethylene and propylene; Halogen atom-containing monomer such as vinyl chloride and vinylidene chloride; Vinyl ester monomer such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; vinyl ketone monomers such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl vinyl
- acrylonitrile is preferable as the other monomer.
- these other monomers one type may be used alone, or two or more types may be used in combination at any ratio. Further, the content ratio of other monomer units in the acrylic polymer may be appropriately adjusted.
- the binder may contain an aromatic monovinyl monomer unit, but the content ratio of the aromatic monovinyl monomer unit in the binder (particularly, an acrylic polymer) is the binding.
- the total monomer unit in the material is 100% by mass, it is preferably less than 30% by mass, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. It is preferably 0% by mass (that is, does not contain the aromatic monovinyl monomer unit).
- the glass transition temperature of the binder is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 90 ° C. or higher, further preferably ⁇ 80 ° C. or higher, and preferably lower than 30 ° C. , 20 ° C or lower, more preferably 15 ° C or lower, and particularly preferably less than 10 ° C. If the glass transition temperature of the binder is -100 ° C or higher, the binding ability and strength of the binder can be enhanced, and if it is less than 30 ° C, the flexibility of the functional layer including the binder is sufficient. Can be secured.
- the content of the binder in the functional layer is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and 0.5 part by mass per 100 parts by mass of the heat-resistant fine particles. It is more preferably parts by mass or more, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and preferably 6 parts by mass or less. Especially preferable.
- the content of the binder in the functional layer is 0.1 part by mass or more per 100 parts by mass of the heat-resistant fine particles, the heat-resistant fine particles existing in the heat-resistant region are sufficiently suppressed from falling off from the functional layer.
- the low temperature adhesiveness of the element member provided with the functional layer can be further improved.
- the content of the binder in the functional layer is 20 parts by mass or less per 100 parts by mass of the heat-resistant fine particles, the rate characteristics and cycle characteristics of the electrochemical device including the element member made of a laminated body are to be improved. Can be done.
- the binder is not particularly limited, and can be prepared, for example, by polymerizing a monomer composition containing the above-mentioned monomer in an aqueous solvent such as water.
- the ratio of each monomer to all the monomers in the monomer composition is usually the same as the ratio of each monomer unit in the binder.
- the polymerization method and the polymerization reaction are not particularly limited, and known ones can be used.
- the functional layer provided in the laminate of the present invention is not particularly limited, and may be used as a component other than the above-mentioned heat-resistant fine particles, adhesive particles and binder, such as a dispersant and a thickener, which can be used for preparing the functional layer. It can contain known components (eg, sodium dodecylbenzene sulfonate and water-soluble polymers such as polyacrylic acid and salts thereof and carboxymethyl cellulose and salts thereof). As the other components, one type may be used alone, or two or more types may be used in combination. In the present invention, "water-soluble" means that when 0.5 g of the polymer is dissolved in 100 g of water at a temperature of 25 ° C., the insoluble content is less than 1.0% by mass. Say.
- the base material provided with the above-mentioned functional layer on at least one surface may be appropriately selected depending on the type of the element member using the laminate of the present invention.
- a separator base material is used as the base material.
- an electrode base material is used as the base material.
- the separator base material is not particularly limited, and examples thereof include known separator base materials such as an organic separator base material.
- the organic separator base material is a porous member made of an organic material, and examples of the organic separator base material include microporous resin such as polyethylene, polypropylene, polybutene, polyvinyl chloride and the like, and aromatic polyamide resin. Examples include a film or a non-woven fabric.
- a microporous membrane made of a polyolefin resin is preferable from the viewpoint that the ratio of the electrode active material in the electrochemical element can be increased to increase the capacity per volume.
- the thickness of the separator base material can be any thickness, preferably 5 ⁇ m or more and 30 ⁇ m or less, more preferably 5 ⁇ m or more and 20 ⁇ m or less, and further preferably 5 ⁇ m or more and 18 ⁇ m or less.
- the electrode base material (positive electrode base material and negative electrode base material) is not particularly limited, and examples thereof include an electrode base material in which an electrode mixture layer is formed on a current collector.
- a method for forming the electrode mixture layer on the current collector a known material can be used, and for example, the method described in Japanese Patent Application Laid-Open No. 2013-145763 can be used.
- the method for producing the laminate of the present invention is not particularly limited, and for example, a method of forming a functional layer on a release sheet and transferring the functional layer onto a substrate can also be used.
- the laminate is a step of supplying a composition for a functional layer containing at least heat-resistant fine particles, adhesive particles, a binder and a dispersion medium onto a substrate ( It is preferable to carry out the production through a step (supply step) and a step (drying step) of drying the composition for the functional layer supplied on the substrate.
- the composition for a functional layer contains at least heat-resistant fine particles, adhesive particles and a binder in the dispersion medium, and optionally contains other components.
- the dispersion medium is not particularly limited, but water can be preferably used.
- the method for preparing the composition for the functional layer is not particularly limited, and a known mixing method or dispersion method can be used.
- the functional layer provided in the laminate is made of a dried product of the composition for the functional layer. Therefore, each component contained in the functional layer is contained in the composition for the functional layer, and a suitable abundance ratio of each component in the composition for the functional layer is determined in the above-mentioned functional layer. It is the same as the suitable abundance ratio of each component.
- the above-mentioned functional layer composition is supplied onto the base material to form a film of the functional layer composition on the base material.
- the method for supplying the composition for the functional layer on the base material is not particularly limited, and the composition for the functional layer may be applied to the surface of the base material, or the base material may be immersed in the composition for the functional layer. May be good. Since it is easy to control the thickness of the manufactured functional layer (particularly, the average height in the stacking direction of the heat-resistant region), it is preferable to apply the composition for the functional layer to the surface of the base material.
- the method of applying the composition for the functional layer to the surface of the base material is not particularly limited, and for example, the doctor blade method, the reverse roll method, the direct roll method, the gravure coating method, the bar coating method, the extrusion method, and the brush coating method. Methods such as the law can be mentioned.
- a coating film of the functional layer composition may be formed on only one surface of the base material, or a coating film of the functional layer composition may be formed on both surfaces of the substrate.
- the coating film of the composition for the functional layer formed on the substrate in the supply step is dried to remove the dispersion medium, and the functional layer is formed.
- the method for drying the film of the composition for the functional layer is not particularly limited, and a known method can be used. For example, drying by warm air, hot air, low humidity air, vacuum drying, drying by irradiation with infrared rays or electron beams, etc. can be used. The law is mentioned.
- the drying conditions are not particularly limited, but the drying temperature is preferably 50 to 150 ° C., and the drying time is preferably 1 to 30 minutes.
- the laminate of the present invention after performing a supply step and a drying step on one surface of the base material to form a functional layer, further, on the other side of the base material. , The supply step and the drying step may be carried out to form a functional layer.
- the electrochemical element of the present invention comprises an electrode and a separator, and the laminate of the present invention described above is provided as at least one of the electrode and the separator. Since the electrochemical element of the present invention uses the above-mentioned laminate of the present invention as at least one element member of the electrode and the separator, it is excellent in element characteristics such as rate characteristics and cycle characteristics.
- the electrochemical element of the present invention is not particularly limited, and is, for example, a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor, preferably a lithium ion secondary battery.
- Electrode and the negative electrode an electrode made of the known electrode base materials (positive electrode base material and negative electrode base material) described above in the “base material” section can be used.
- an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
- a lithium salt is used in a lithium ion secondary battery.
- 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 N Li. , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi and the like.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable because they are easily soluble in a solvent and show a high degree of dissociation.
- One type of electrolyte may be used alone, or two or more types may be used in combination. Normally, the more the supporting electrolyte with a higher degree of dissociation is used, the higher the lithium ion conductivity tends to be. Therefore, the lithium ion conductivity can be adjusted by the type of the supporting electrolyte.
- the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but for example, in a lithium ion secondary battery, dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC). , Propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (ethyl methyl carbonate (EMC)), vinylene carbonate and other carbonates; ⁇ -butyrolactone, methyl formate and other esters; 1,2-dimethoxyethane, Ethers such as tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethylsulfoxide; and the like are preferably used.
- DMC dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- PC butylene carbonate
- EMC methyl ethyl carbonate
- vinylene carbonate and other carbonates ⁇ -butyrolactone,
- a mixed solution of these solvents may be used.
- carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
- the lower the viscosity of the solvent used the higher the lithium ion conductivity tends to be. Therefore, the lithium ion conductivity can be adjusted depending on the type of solvent.
- the concentration of the electrolyte in the electrolytic solution can be appropriately adjusted.
- a known additive may be added to the electrolytic solution.
- the method for manufacturing the electrochemical device of the present invention is not particularly limited.
- a positive electrode and a negative electrode are laminated via a separator, and the positive electrode and the negative electrode are placed in a battery container by winding or folding them as necessary.
- It can be manufactured by injecting an electrolytic solution into a battery container and sealing it.
- at least one element member among the positive electrode, the negative electrode, and the separator is the laminated body of the present invention.
- an expanded metal, a fuse, an overcurrent prevention element such as a PTC element, a lead plate, or the like may be placed in the battery container to prevent the pressure inside the battery from rising and overcharging / discharging.
- the shape of the battery may be, for example, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, or the like.
- the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
- “%” and “part” representing quantities are based on mass unless otherwise specified.
- the ratio of the repeating unit (monomer unit) formed by polymerizing a certain monomer in the polymer is not specified. As long as it is usually, it is the same as the ratio (preparation ratio) of the certain monomer to all the monomers used for the polymerization of the polymer.
- the glass transition temperature, volume average particle diameter, average circularity, average height in the stacking direction of the heat-resistant region, ratio of the volume average particle diameter of the adhesive particles to the average height in the stacking direction of the heat-resistant region, and adhesion The ratio of the content of heat-resistant fine particles to the content of sex particles (volume ratio, mass ratio), low-temperature adhesion of the separator having a functional layer, blocking resistance, and heat resistance, and the rate characteristics of the lithium ion secondary battery. And the cycle characteristics were evaluated by the following method.
- Tg Glass transition temperature of polyester polymer and binder
- the polyester polymer and the binder were used as measurement samples, respectively.
- EXSTAR DSC6220 manufactured by SII Nanotechnology
- the intersection with was determined as the glass transition temperature (° C).
- ⁇ Volume average particle size of binder> The volume average particle size of the binder was measured by a laser diffraction method. Specifically, an aqueous dispersion solution containing the prepared binder (adjusted to a solid content concentration of 0.1% by mass) was used as a sample.
- the cumulative volume calculated from the small diameter side is 50%.
- the particle size D50 was defined as the volume average particle size.
- the particle size (D50) at which the cumulative volume calculated from the small diameter side is 50% was defined as the volume average particle size of the heat-resistant fine particles.
- a diluted solution (“Isoton II” manufactured by Beckman Coulter) was added to the above beaker, and the mixture was dispersed in a 20 W (Watt) ultrasonic disperser for 3 minutes.
- the volume of the adhesive particles is under the conditions of aperture diameter: 20 ⁇ m, medium: Isoton II, and number of measured particles: 100,000.
- the average particle size was measured.
- ⁇ Average circularity of adhesive particles> 10 mL of ion-exchanged water is put in the container in advance, 0.02 g of a surfactant (alkylbenzene sulfonic acid) is added as a dispersant, 0.02 g of adhesive particles is further added, and 60 W using an ultrasonic disperser. (Watt) was used for 3 minutes for dispersion treatment.
- ⁇ Ratio of the content of heat-resistant fine particles to the content of adhesive particles The ratio (volume ratio, mass ratio) of the content of the heat-resistant fine particles to the content of the adhesive particles was determined from the charged amounts of the heat-resistant fine particles and the adhesive particles when the composition for the functional layer was prepared. The density of alumina particles as heat-resistant fine particles was calculated as 4 g / cm 3 .
- Pressing was performed using a roll press under the conditions of a temperature of 50 ° C., a load of 8 kN / m, and a pressing speed of 30 m / min to obtain an integrated product in which the positive electrode and the separator were integrated.
- a cellophane tape was attached to the surface of the positive electrode of the obtained integrated product with the surface of the positive electrode on the current collector side facing down.
- the cellophane tape specified in JIS Z1522 was used.
- the cellophane tape was fixed on a horizontal test table. After that, the stress when one end of the separator was pulled vertically upward at a tensile speed of 50 mm / min and peeled off was measured.
- the same operation as in the case of using the positive electrode was performed on the negative electrodes produced in Examples and Comparative Examples, and the stress was measured.
- the above-mentioned stress measurement was performed three times for each of the positive electrode and the separator integrated product and the negative electrode and the separator integrated product three times, for a total of six times, the average value of the stress was obtained, and the obtained average value was used as the peel strength (N). / M).
- the peel strength N. / M
- the low temperature adhesiveness of the separator provided with the functional layer was evaluated according to the following criteria. The larger the peel strength, the more the separator as an element member can exhibit excellent low-temperature adhesiveness depending on the functional layer.
- Two separated separators (provided on both sides with functional layers having an average height of 2.0 ⁇ m in the stacking direction of the heat-resistant region) having a width of 4 cm and a length of 4 cm were cut out as test pieces. The two obtained test pieces were superposed on each other via the functional layer side, and then pressed for 2 minutes under pressure at a temperature of 40 ° C. and a pressure of 5 MPa to obtain a pressed body.
- the blocking resistance was evaluated according to the following criteria. The smaller the blocking strength, the better the functional layer suppresses the occurrence of blocking, that is, the higher the blocking resistance of the functional layer.
- Blocking strength is less than 4N / m
- B Blocking strength is 4N / m or more and less than 6N / m
- C Blocking strength is 6N / m or more ⁇ heat resistance>
- the prepared separator (equipped with functional layers having an average height of 2.0 ⁇ m in the stacking direction of the heat-resistant region on both sides) was cut into a square having a width of 12 cm and a length of 12 cm, and one side was placed inside (one side) of the obtained square. Draws a 10 cm square and uses it as a test piece. Then, after the test piece was placed in a constant temperature bath at 150 ° C.
- the prepared lithium ion secondary battery was allowed to stand at a temperature of 25 ° C. for 5 hours after injecting the electrolytic solution.
- the cells were 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 aged at a temperature of 60 ° C. for 12 hours.
- the battery was discharged to a cell voltage of 3.00 V by a constant current method at a temperature of 25 ° C. and 0.2 C.
- CC-CV charging upper limit cell voltage 4.20V
- CC discharge was performed to 3.00V by a constant current method of 0.2C.
- This charging / discharging at 0.2C was repeated three times.
- a charge / discharge operation was performed for 100 cycles at a cell voltage of 4.20-3.00 V and a charge / discharge rate of 1.0 C.
- the discharge capacity of the first cycle was defined as X1
- the discharge capacity of the 100th cycle was defined as X2.
- the capacity retention rate ⁇ C ′ (X2 / X1) ⁇ 100 (%) was obtained and evaluated according to the following criteria.
- Example 1 ⁇ Preparation of polyester polymer> 2000 g of BPA-PO (propylene oxide adduct of bisphenol A, average number of added moles: 2.2 mol) and BPA-EO (ethylene oxide adduct of bisphenol A, average number of added moles: 2.2 mol) as alcohol components. 800 g, 600 g of fumaric acid as a carboxylic acid component, 500 g of trimellitic anhydride, and 4 g of dibutyltin oxide were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a heat transfer adduct. The reaction was carried out at 220 ° C. for 8 hours.
- BPA-PO propylene oxide adduct of bisphenol A, average number of added moles: 2.2 mol
- BPA-EO ethylene oxide adduct of bisphenol A, average number of added moles: 2.2 mol
- the reaction was further carried out at 8.3 kPa until the softening point of the reactant (measured by the following method) reached 150 ° C. to obtain a polyester polymer.
- the glass transition temperature of the obtained polyester polymer was 62 ° C.
- -Measuring method of softening point- Using a high-grade flow tester (manufactured by Shimadzu Corporation, product name "CFT-500D"), a 1 g sample is heated at a temperature rise rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger to a diameter of 1 mm.
- the reaction was carried out at 220 ° C. for 10 hours while distilling off water.
- Add 19 g of a 10% potassium hydroxide aqueous solution containing 46.5 g of toluene and 32 g of 2-propanol and 2.0 times the acid value of potassium hydroxide stir at 70 ° C. for 30 minutes, allow to stand for 30 minutes, and then the aqueous layer.
- the portion was removed to obtain a crude product.
- 40 parts of ion-exchanged water was used for 100 parts of the crude product, and the mixture was washed with water at 70 ° C. four times to adjust the pH to 7.
- the solvent was distilled off from the obtained purified product under heating and reduced pressure conditions, and through filtration, solidification, and pulverization, 140 g of pentaerythritol tetralaurate (melting point: 44 ° C.) as an ester wax was obtained.
- the adhesive particle material (polyester polymer, ester wax) was atomized by the following procedure using the dissolution suspension method. 100 parts of polyester resin, 10 parts of ester wax, and 230 parts of toluene as an organic solvent were dispersed by a ball mill to obtain a liquid composition.
- the composition after removing the toluene was cooled, then 12N hydrochloric acid was added until the pH reached 2, and the mixture was washed, washed with water, dried, and classified to obtain adhesive particles containing a polyester polymer and an ester wax. ..
- the volume average particle diameter of the adhesive particles was 6.0 ⁇ m, and the average circularity was 0.97.
- a monomer composition is obtained by mixing 2 parts of methacrylic acid as a weight, 2 parts of acrylonitrile as a nitrile group-containing monomer, and 1 part of allyl methacrylate and 1 part of allyl glycidyl ether as a crosslinkable monomer.
- a monomer composition is obtained by mixing 2 parts of methacrylic acid as a weight, 2 parts of acrylonitrile as a nitrile group-containing monomer, and 1 part of allyl methacrylate and 1 part of allyl glycidyl ether as a crosslinkable monomer.
- the obtained monomer composition was continuously added to a reactor equipped with the above-mentioned stirrer for 4 hours to carry out polymerization. During the addition, the reaction was carried out at 60 ° C. After completion of the addition, the mixture was further stirred at 70 ° C. for 3 hours and then the reaction was terminated to obtain an aqueous dispersion containing a particulate binder as an acrylic polymer.
- the obtained binder had a volume average particle diameter of 0.25 ⁇ m and a glass transition temperature of ⁇ 40 ° C.
- composition for functional layer ⁇ Preparation of composition for functional layer> Add 0.5 part of polyacrylic acid as a water-soluble polymer to 100 parts of alumina (volume average particle size: 0.5 ⁇ m) as heat-resistant fine particles, and ion-exchanged water so that the solid content concentration becomes 55%. Was added and mixed using a ball mill to obtain an alumina-containing slurry. Further, 100 parts of the adhesive particles, 0.2 part of sodium dodecylbenzene sulfonate (manufactured by Kao Chemical Co., Ltd., "Neoperex G-15") as a dispersant, and ion-exchanged water are mixed to obtain a solid content concentration. Obtained a mixed solution containing 40% adhesive particles.
- the alumina-containing slurry and the adhesive particle-containing mixed solution are mixed so that the ratio of alumina to the adhesive particles (alumina / adhesive particles) is 70/30 on a volume basis (90/10 on a mass basis). did.
- ion exchange was carried out with 6 parts of an aqueous dispersion containing the above binder per 100 parts of alumina, and 1.5 parts of carboxymethyl cellulose as a water-soluble polymer (thickener). Water was added to obtain a composition for a functional layer (solid content concentration: 40%).
- solid content concentration 40%
- the composition for the functional layer obtained above was applied to one side of the prepared separator base material by the bar coater method.
- the coating film was dried at 50 ° C.
- the same operation as described above was performed on the other surface of the separator base material to obtain a separator having a functional layer having a functional layer on both sides of the separator base material.
- Both of the two functional layers of the obtained separator have an adhesive region made of adhesive particles and a heat-resistant region made of alumina as heat-resistant fine particles and a binder, and have an average height in the stacking direction of the heat-resistant region. was 2.0 ⁇ m.
- the low temperature adhesiveness, blocking resistance and heat resistance of the separator having functional layers on both sides were evaluated. The results are shown in Table 1.
- the slurry composition for a positive electrode was applied to an aluminum foil having a thickness of 20 ⁇ m as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was performed by transporting the aluminum foil at a speed of 0.5 m / min in an oven at 60 ° C. for 2 minutes. Then, it was heat-treated at 120 degreeC for 2 minutes, and the positive electrode raw material before pressing was obtained. The raw electrode of the positive electrode before pressing was rolled by a roll press to obtain a positive electrode provided with a positive electrode mixture layer (thickness: 60 ⁇ m).
- a 5% aqueous sodium hydroxide solution was added to the mixture containing the binder for the negative electrode mixture layer to adjust the pH to 8, and then unreacted monomers were removed by hot vacuum distillation. Then, the mixture was cooled to 30 ° C. or lower to obtain an aqueous dispersion containing a desired binder for a negative electrode mixture layer.
- 80 parts of artificial graphite (volume average particle size: 15.6 ⁇ m) as a negative electrode active material and 16 parts of silicon-based active material SiOx (volume average particle size: 4.9 ⁇ m) are blended, and a sodium carboxymethyl cellulose salt as a viscosity modifier.
- a 2% aqueous solution of (manufactured by Nippon Paper Co., Ltd., "MAC350HC") was mixed with 2.5 parts equivalent to solid content and ion-exchanged water to adjust the solid content concentration to 68%, and then further mixed at 25 ° C. for 60 minutes. .. Further, the solid content concentration was adjusted to 62% with ion-exchanged water, and then the mixture was further mixed at 25 ° C. for 15 minutes to obtain a mixed solution. To this mixed solution, 1.5 parts of an aqueous dispersion containing the binder for the negative electrode mixture layer and ion-exchanged water are added in an amount equivalent to the solid content, and the final solid content concentration is adjusted to 52%.
- the mixture was further mixed for 10 minutes to obtain a mixed solution.
- This mixed solution was defoamed under reduced pressure to obtain a slurry composition for a negative electrode having good fluidity.
- the slurry composition for a negative electrode was applied to a copper foil having a thickness of 20 ⁇ m as a current collector with a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was performed by transporting the copper foil at a rate of 0.5 m / min in an oven at 60 ° C. for 2 minutes. Then, it was heat-treated at 120 degreeC for 2 minutes, and the negative electrode raw fabric before pressing was obtained.
- the negative electrode raw material before pressing was rolled by a roll press to obtain a negative electrode provided with a negative electrode mixture layer (thickness: 80 ⁇ m).
- a negative electrode mixture layer thickness: 80 ⁇ m.
- the positive electrode produced as described above is cut into a rectangle of 49 cm ⁇ 5 cm, placed so that the surface on the positive electrode mixture layer side is on the upper side, and the separator cut out to 120 cm ⁇ 5.5 cm is placed on the positive electrode mixture layer. (Providing functional layers on both sides) was arranged so that the positive electrode was located on one side in the longitudinal direction of the separator.
- Example 2 In preparing the adhesive particles, the amount of the ester wax as a meltable additive was 5 parts (Example 2), 20 parts (Example 3), 30 parts (Example 4), and 35 parts (Example), respectively. Except for the change to 5), the polyester polymer, the ester wax, the adhesive particles, the binder, the composition for the functional layer, the separator, the negative electrode, the positive electrode, and the lithium ion secondary battery were used in the same manner as in Example 1. Obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 6 In the preparation of the ester wax as a meltable additive, behenic acid was used instead of lauric acid to obtain pentaerythritol tetrabehenate (melting point: 81 ° C.) as the ester wax.
- a polyester polymer, adhesive particles, a binder, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion secondary battery were obtained in the same manner as in Example 1 except that the ester wax was used. .. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 7 The polyester polymer, the adhesive particles, and the binder are the same as in Example 1 except that the ester wax, which is a meltable additive, was not prepared and the meltable additive was not used in the preparation of the adhesive particles. , A composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 8 In the preparation of the adhesive particles, the polyester polymer was obtained in the same manner as in Example 1 except that the concentration of the hydroxyabatite aqueous solution was changed to 10% and the volume average particle diameter of the adhesive particles in the laminate was changed to 3 ⁇ m. , Esther wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 9 In the preparation of the adhesive particles, the polyester polymer was obtained in the same manner as in Example 1 except that the concentration of the hydroxyabatite aqueous solution was changed to 3% and the volume average particle diameter of the adhesive particles in the laminate was changed to 9 ⁇ m. , Esther wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.
- Example 10 For polyester polymer, adhesive particles, binder, functional layer in the same manner as in Example 1 except that a crystalline polyester resin prepared as described below was used as the meltable additive in place of the ester wax. A composition, a separator, a negative electrode, a positive electrode, and a lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.
- ⁇ Preparation of crystalline polyester resin (meltable additive)> In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, sebacic acid as a carboxylic acid component and 1,6-hexanediol as an alcohol component were added to a hydroxyl group and a carboxyl group. It was charged so that the molar ratio of OH / COOH was 0.85, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, and then heated to 200 ° C.
- Example 11 Except for using 5 parts of paraffin wax (manufactured by Nippon Seiwa Co., Ltd., product name "HNP-11", melting point: 68 ° C.) instead of 10 parts of ester wax as a meltable additive in the preparation of adhesive particles.
- a polyester polymer, adhesive particles, a binder, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.
- Example 12 When preparing the composition for the functional layer, the mixing ratio of the alumina particles and the adhesive particles (alumina particles / adhesive particles) was 80/20 on a volume basis (94/6 on a mass basis, Example 12), respectively. Polyester polymer and ester in the same manner as in Example 1 except that the alumina-containing slurry and the adhesive particle-containing mixed solution were mixed so as to be 55/45 (82/18 by volume, Example 13). Wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.
- Example 14 Ester wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion in the same manner as in Example 1 except that the polyester polymer prepared as follows was used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2. ⁇ Preparation of polyester polymer> 143 parts of BPA-PO (propylene oxide adduct of bisphenol A, average number of moles added: 2.2 mol) as an alcohol component, 133 parts of terephthalic acid and 33 parts of isophthalic acid as a carboxylic acid component, and 0.2 of dibutyltin oxide. The parts were placed in a reaction vessel.
- BPA-PO propylene oxide adduct of bisphenol A, average number of moles added: 2.2 mol
- the temperature was gradually raised while blowing nitrogen gas into the reaction vessel to proceed with the condensation reaction at 180 ° C. for 5 hours, and then the reaction was completed at 230 ° C. to obtain a polyester polymer.
- the glass transition temperature of the obtained polyester polymer was 56 ° C.
- Example 15 A polyester polymer, an ester wax, a binder, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion are used in the same manner as in Example 1 except that the adhesive particles prepared as described below are used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2. ⁇ Preparation of adhesive particles> The adhesive particle material (polyester polymer, ester wax) was atomized by the following procedure using the emulsification aggregation method.
- meltable additive dispersion 100 parts of ester wax (meltable additive) obtained in the same manner as in Example 1 and Example 1 and an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Neogen (registered trademark) RK").
- an anionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "Neogen (registered trademark) RK”
- One part and 350 parts of ion-exchanged water were mixed and heated to 100 ° C., dispersed using a homogenizer (Ultratarax T50 manufactured by IKA), and then dispersed with a manton Gorin high-pressure homogenizer (manufactured by Gorin).
- a meltable additive dispersion liquid (solid content concentration: 20%) in which an ester wax having a volume average particle diameter of 200 nm was dispersed was obtained.
- ⁇ Preparation of polymer particle dispersion >> 40 parts of ethyl acetate and 25 parts of 2-butanol were added to a container equipped with a temperature control means and a nitrogen replacement means to prepare a mixed solvent, and then 100 parts of the polyester polymer obtained in the same manner as in Example 1 was gradually added. Was put into the water and dissolved. Further, a 10 mass% aqueous ammonia solution (amount equivalent to 3 times the molar ratio to the acid value of the polyester polymer) was added and stirred for 30 minutes to prepare a mixed solution.
- the inside of the container was replaced with dry nitrogen, the temperature was maintained at 40 ° C., and 400 parts of ion-exchanged water was added dropwise at a rate of 2 parts / minute while stirring the mixture to emulsify.
- the emulsion was returned to room temperature (20 ° C. or higher and 25 ° C. or lower), and bubbling was performed with dry nitrogen for 48 hours while stirring to reduce ethyl acetate and 2-butanol to 1,000 ppm or less, and further ion.
- the solid content concentration was adjusted to 20% by adding exchanged water to obtain a polymer particle dispersion liquid in which polymer particles having a volume average particle size of 200 nm were dispersed.
- Emulsification Aggregation >> A round flask (made of stainless steel) and a container A (a polyester bottle) are connected by a tube pump A, and the contained liquid contained in the container A is sent to the flask by the drive of the tube pump A, and the container A and the container B are connected to each other.
- a tube pump B was connected by a tube pump B, and a device was prepared to send the contained liquid contained in the container B to the container A by driving the tube pump B.
- the following operations were performed using this device. 500 parts of the polymer particle dispersion obtained as described above and an anionic surfactant (product name "TaycaPower (registered trademark)" were placed in a round flask of the above apparatus, and 0.1 N nitric acid was added.
- the liquid feeding speed of the tube pump A was set to 0.70 parts / minute
- the liquid feeding speed of the tube pump B was set to 0.14 parts / minute
- the temperature inside the round flask during the formation of agglomerated particles was 37.
- the tube pumps A and B were driven from the time when the temperature reached 0 ° C., and the feeding of each dispersion was started.
- the mixed dispersion liquid in which the polymer particles and the meltable additive were dispersed was sent from the container A to the round flask in which the aggregated particles were being formed.
- each dispersion liquid to the round flask was completed, and the temperature in the round flask was maintained for 30 minutes from the time when the temperature reached 48 ° C.
- 50 parts of the polymer particle dispersion obtained as described above was gently added to the round flask and held for 1 hour.
- a 0.1 N aqueous sodium hydroxide solution was added to adjust the pH to 8.5, and then the mixture was heated to 85 ° C. while continuing stirring and kept for 5 hours. Then, by cooling to 20 ° C.
- the adhesive particles containing the polyester polymer and the ester wax (the amount of the ester wax is reduced). , 10 parts per 100 parts of polyester polymer).
- the volume average particle diameter of the adhesive particles was 6.0 ⁇ m, and the average circularity was 0.96.
- Example 16 A polyester polymer, an ester wax, a binder, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion are used in the same manner as in Example 1 except that the adhesive particles prepared as described below are used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2. ⁇ Preparation of adhesive particles> The adhesive particle material (polyester polymer, ester wax) was atomized by the following procedure using the pulverization method.
- 100 parts of the polyester polymer and 10 parts of the ester wax were melt-kneaded using a twin-screw extruder rotating in the same direction (total length of the kneaded portion: 1560 mm, screw diameter: 42 mm, barrel inner diameter: 43 mm), and then cooled and coarsely pulverized. ..
- the raw material supply speed to the extruder during melt kneading was 10 kg / hour, and the average residence time was about 18 seconds.
- the obtained crude pulverized product was pulverized by a jet mill and classified to obtain adhesive particles containing a polyester polymer and an ester wax.
- the volume average particle diameter of the adhesive particles was 6.0 ⁇ m, and the average circularity was 0.94.
- Example 17 A polyester polymer, an ester wax, a binder, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion are used in the same manner as in Example 1 except that the adhesive particles prepared as described below are used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of adhesive particles> ⁇ Preparation of Monomer Composition >> 4.7 parts of polyester polymer obtained in the same manner as in Example 1, 61.2 parts of styrene as an aromatic monovinyl monomer, and n-butyl acrylate 34.1 as a (meth) acrylic acid ester monomer.
- the obtained mixed solution is stirred with high shear for 1 minute at a rotation speed of 15,000 rpm using an in-line type emulsifying disperser (manufactured by Pacific Kiko Co., Ltd., product name "Cavitron"), and a monomer is added to the colloidal dispersion. Droplets of the composition were formed.
- the colloidal dispersion in which droplets of the monomer composition were formed was placed in a reactor, heated to 90 ° C. and polymerized for 5 hours to obtain an aqueous dispersion containing adhesive particles.
- the adhesive particles contained an adhesive polymer having a core-shell structure including a core portion made of an aromatic monovinyl polymer and a shell portion made of a polyester polymer, and an ester wax.
- Example 18 In the preparation of the composition for the functional layer, the polyester polymer, the ester wax, the adhesive particles, and the binder were formed in the same manner as in Example 1 except that the organic fine particles prepared as described below were used instead of the alumina particles. A coating material, a composition for a functional layer, a separator, a negative electrode, a positive electrode, and a lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.
- a monomer composition for seed particles 10.0 parts of acrylonitrile, 0.8 parts of sodium dodecyl sulfate, and 40 parts of ion-exchanged water were mixed to prepare a monomer composition for seed particles.
- This monomer composition for seed particles was continuously added to the above-mentioned reactor A over 4 hours to carry out a polymerization reaction.
- the temperature in the reactor during the continuous addition of the monomer composition for seed particles was maintained at 65 ° C. Further, after the continuous addition was completed, the polymerization reaction was further continued at 80 ° C. for 3 hours. As a result, an aqueous dispersion of seed particles was obtained.
- the volume average particle diameter of the seed particles was measured in the same manner as that of the binder, it was 120 nm.
- the glass transition temperature of the obtained organic fine particles was measured by the same method as that for the adhesive particles and the binder, but no peak was observed in the measurement temperature range (-100 ° C to 200 ° C). As a result, it was confirmed that the glass transition temperature of the organic fine particles was over 200 ° C.
- Example 1 A binder, a composition for a functional layer, a separator, a negative electrode, and a positive electrode are used in the same manner as in Example 1 except that the polyester polymer and the ester wax are not prepared and the adhesive particles prepared as described below are used. , And a lithium ion secondary battery was obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of adhesive particles> 81.9 parts of styrene as an aromatic monovinyl monomer, 18 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid ester monomer, and 0.1 part of ethylene glycol dimethacrylate as a crosslinkable monomer are mixed. , A monomeric composition was prepared. A colloidal dispersion was prepared in the same manner as in Example 17 except that the above-mentioned monomer composition was used, and suspension polymerization and drying were carried out to obtain adhesive particles.
- Example 2 A binder, a composition for a functional layer, a separator, a negative electrode, and a positive electrode are used in the same manner as in Example 1 except that the polyester polymer and the ester wax are not prepared and the adhesive particles prepared as described below are used. , And a lithium ion secondary battery was obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of adhesive particles> 60.9 parts of styrene as an aromatic monovinyl monomer, 39 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid ester monomer, and 0.1 part of ethylene glycol dimethacrylate as a crosslinkable monomer are mixed. , A monomeric composition was prepared. A colloidal dispersion was prepared in the same manner as in Example 17 except that the above-mentioned monomer composition was used, and suspension polymerization and drying were carried out to obtain adhesive particles.
- Example 3 A binder, a composition for a functional layer, a separator, a negative electrode, and a positive electrode are used in the same manner as in Example 1 except that the polyester polymer and the ester wax are not prepared and the adhesive particles prepared as described below are used. , And a lithium ion secondary battery was obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of adhesive particles> 81.9 parts of styrene as an aromatic monovinyl monomer, 18 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid ester monomer, and 0.1 part of ethylene glycol dimethacrylate as a crosslinkable monomer were mixed.
- a colloidal dispersion was prepared in the same manner as in Example 17 except that the above-mentioned monomer composition was used, and suspension polymerization and drying were carried out to obtain adhesive particles.
- Example 4 Polyester polymer, ester wax, adhesive particles, binder, composition for functional layer, separator, in the same manner as in Example 1 except that alumina particles were not used in the preparation of the composition for the functional layer. A negative electrode, a positive electrode, and a lithium ion secondary battery were obtained. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.
- polyester polymer Ester wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion in the same manner as in Example 1 except that the polyester polymer prepared as follows was used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of polyester polymer> 1661 parts of terephthalic acid as a carboxylic acid component, 1316 parts of bisphenoxyethanol fluorene (BPEF) as an alcohol component, 1094 parts of neopentyl glycol, and 2.7 parts of trimethylolpropane (terephthalic acid: BPEF: neopentyl glycol: trimethylol).
- BPEF bisphenoxyethanol fluorene
- the mixture consisting of propane 100: 30: 105: 0.2 (molar ratio)) was controlled in an autoclave at 0.3 MPa and 260 ° C. for 3 hours while stirring, and then released for 3 hours.
- the reaction was carried out at a pressure of 260 ° C.
- the temperature was raised to 270 ° C.
- 6.8 parts of tetrabutyl titanate (20 ⁇ 10 -4 mol per mol of terephthalic acid) was added as a catalyst, and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. , The reaction continued. Condensation was carried out until the viscosity became appropriate, and a pellet-shaped polyester polymer was obtained using a strand cutter.
- the glass transition temperature of the obtained polyester polymer was 100 ° C.
- Example 6 Ester wax, adhesive particles, binder, composition for functional layer, separator, negative electrode, positive electrode, and lithium ion in the same manner as in Example 1 except that the polyester polymer prepared as follows was used. Obtained a secondary battery. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3. ⁇ Preparation of polyester polymer> 900 parts of ethylene glycol as an alcohol component, 2000 parts of dimethyl terephthalate as a carboxylic acid component, and 4 parts of dibutyltin oxide, 4 mouths of 5 liters equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a heat transfer It was placed in a flask and heated from 165 ° C.
- PES polymer refers to a polyester polymer
- Aromatic indicates an aromatic vinyl-based polymer
- Additive refers to a meltable additive
- PET resin indicates a crystalline polyester resin
- Acrylic indicates an acrylic polymer
- Organic refers to organic fine particles
- Particle diameter of adhesive particles / height of heat-resistant region indicates the volume average particle diameter of adhesive particles / average height of the heat-resistant region in the stacking direction.
- PE indicates a microporous membrane made of polyethylene.
- Examples 1 to 18 From Tables 1 to 3, it can be seen that the laminates of Examples 1 to 18 can be satisfactorily used as a separator having excellent low temperature adhesiveness, blocking resistance and heat resistance. Further, in Examples 1 to 18, it can be seen that lithium ion secondary batteries having excellent rate characteristics and cycle characteristics are obtained.
- a laminate for an electrochemical element that can be advantageously used as an element member having excellent blocking resistance and low temperature adhesiveness, and an electrochemical element including the laminate for the electrochemical element as an element member. Can be done.
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Abstract
Description
その一方で、積層体が備える機能層は、電気化学素子の製造に際しては優れた接着性を発揮することが求められる。特に、電極及びセパレータ等の素子部材を複数枚積み重ね、任意に捲回させた後で熱プレスしてセルを作製する場合、セルの生産効率向上などを目的として熱プレスの時間を短くすると、熱が十分に伝わり難いセル中央部に位置する積層体において機能層が十分な接着性を発現し難いという問題があった。すなわち素子部材として用いられる積層体には、上述した耐ブロッキング性を確保する一方で、低温下において優れた接着性を発揮する(低温接着性に優れる)ことも求められる。
なお、本発明において、「ガラス転移温度」は、実施例に記載の方法を用いて測定することができる。
また、本発明において、接着性粒子の「体積平均粒子径」は、実施例に記載の方法を用いて測定することができる。
そして、本発明において、耐熱領域の「積層方向平均高さ」は、実施例に記載の方法を用いて測定することができる。
なお、本発明において、溶融性添加剤の「融点」は、示差走査熱量分析機(DSC)を用いて、100℃/分で昇温する条件で測定を行い、得られたDSC曲線の極大値を取ることにより求めることができる。
なお本発明において、「結晶性ポリエステル樹脂」は、ガラス転移温度を10℃以上95℃以下の範囲に有さないため、当該範囲内にガラス転移温度を有する「ポリエステル重合体」とは異なる成分である。
なお、本発明において、接着性粒子の「平均円形度」は、実施例に記載の方法を用いて測定することができる。
ここで、本発明の電気化学素子用積層体は、セパレータや電極(正極及び負極)といった素子部材として用いることができる。そして、本発明の電気化学素子は、素子部材として本発明の電気化学素子用積層体を備える。
本発明の積層体は、基材と、基材上に形成された機能層を備える。ここで基材上の機能層は、積層体を機能層側から平面視した際に、接着性粒子からなる接着領域と、耐熱性微粒子と結着材からなる耐熱領域とを少なくとも備える。そして、接着領域を構成する接着性粒子の体積平均粒子径が、耐熱領域の積層方向平均高さよりも大きいことを特徴とする。
加えて、熱プレスで溶融した接着性粒子由来のポリエステル重合体が、結着材により耐熱性微粒子が結着されて形成される耐熱領域のマトリックス内に侵入することで、アンカーとなる(アンカー効果が得られる)ためと推察されるが、積層体からなる素子部材の低温接着性が向上する。一方、耐熱領域は、熱プレスで溶融した接着性粒子由来のポリエステル重合体が基材表面の広がり方向と並行な方向へ過度に広がるのを抑制し、その結果リチウムイオン等の電荷担体の通り道を確保しうるためと推察されるが、レート特性及びサイクル特性などの素子特性が向上する。
図1は、本発明に係る電気化学素子用積層体100を機能層側から平面視した際の一例を模式的に示す平面図である。図1において、電気化学素子用積層体100が備える機能層10の表面には、耐熱領域12と、当該耐熱領域12に囲まれた複数の接着領域11とが存在する。
図2は、本発明に係る電気化学素子用積層体100の積層方向断面の一例を模式的に示す断面図である。図2において、電気化学素子用積層体100は、基材20の上に機能層10が積層されてなり、機能層10は接着領域11と耐熱領域12を有している。また図2において、接着領域11は接着性粒子11aで構成されている。一方の耐熱領域12は、耐熱性微粒子12aが結着材12bにより結着されてなり、それらが積層方向(厚み方向)に重なり合うことで構成されている。そして、図2においては、接着性粒子11aの粒子径(基材20表面からの積層方向の高さ)Dが、耐熱領域12の積層方向の高さTよりも大きい。本発明の積層体では、接着性粒子の体積平均粒子径が耐熱領域の積層方向平均高さよりも大きいため、図2のように接着性粒子が突出した箇所が多く存在すると考えられる。
そして、接着性粒子の体積平均粒子径は、耐熱領域の積層方向平均高さよりも大きければ特に限定されないが、1.0μm以上であることが好ましく、2.5μm以上であることがより好ましく、5.0μm以上であることが更に好ましく、10.0μm以下であることが好ましく、9.0μm以下であることがより好ましく、8.0μm以下であることが更に好ましい。
接着性粒子の体積平均粒子径が1.0μm以上であれば、接着領域の接着性粒子が耐熱領域よりも更に突出するためと推察されるが、積層体からなる素子部材の低温接着性を更に向上させることができる。また、接着性粒子の体積平均粒子径が大きくなることにより、接着領域に隣接する耐熱領域において耐熱性微粒子が一層密に集合し得るためと推察されるが、積層体からなる素子部材の耐熱性を向上させることができる。くわえて、積層体からなる素子部材の耐ブロッキング性を更に向上させることができる。
一方、接着性粒子の体積平均粒子径が10.0μm以下であれば、機能層の単位体積当たりの接着性粒子の数(粒子数)が増加することにより機能層を備える素子部材と被着体を接着する際の接着点が増加するためと推察されるが、素子部材の低温接着性を更に向上させることができる。また、接着性粒子の抜け落ちを抑制して、基材上に、接着性粒子からなる接着領域が万遍なく存在する機能層を形成することができる。
なお、接着性粒子の体積平均粒子径は、例えば当該接着性粒子の製造条件を変更することにより調整することができる。
また、耐熱領域の積層方向平均高さは、接着性粒子の体積平均粒子径よりも小さければ特に限定されないが、0.5μm以上であることが好ましく、0.8μm以上であることがより好ましく、1.0μm以上であることが更に好ましく、6.0μm未満であることが好ましく、5.0μm未満であることが好ましく、4.0μm未満であることがより好ましく、2.5μm未満であることが更に好ましい。耐熱領域の積層方向平均高さが0.5μm以上であれば、機能層を備える素子部材の耐熱性を十分に確保することができ、6.0μm未満であれば、機能層のイオン拡散性を確保して電気化学素子のレート特性及びサイクル特性を向上させることができる。
なお、耐熱領域の積層方向平均高さは、例えば機能層の形成条件(機能層の形成に用いる機能層用組成物中の耐熱性微粒子及び/又は結着材の含有割合、機能層用組成物を基材上に供給して得られる被膜の厚み)を変更することにより調整することができる。
そして、耐熱領域の積層方向平均高さに対する接着性粒子の体積平均粒子径の比(接着性粒子の体積平均粒子径/耐熱領域の積層方向平均高さ)は、1.1以上であることが好ましく、1.2以上であることがより好ましく、1.6以上であることが更に好ましく、10.0以下であることが好ましく、5.0以下であることがより好ましく、3.5以下であることが更に好ましい。上記比の値が1.1以上であれば、接着領域の接着性粒子が耐熱領域よりも十分に突出するためと推察されるが、積層体からなる素子部材の低温接着性を更に向上させることができる。一方、上記比の値が10.0以下であれば、機能層の単位体積当たりの接着性粒子の数(粒子数)が増加することにより機能層を備える素子部材と被着体を接着する際の接着点が増加するためと推察されるが、積層体からなる素子部材の低温接着性を更に向上させることができる。
上述した構造を有する本発明の積層体が備える機能層は、耐熱性微粒子と、接着性粒子と、結着材とを含む。なお機能層は、耐熱性微粒子、接着性粒子、及び結着材以外の成分(その他の成分)を含んでいてもよい。
ここで、機能層中に含まれる耐熱性微粒子としては、特に限定されることなく、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、無機材料からなる微粒子(即ち、無機微粒子)及び有機材料からなる微粒子(即ち、有機微粒子)が挙げられる。
なお、耐熱性微粒子としては、無機微粒子及び有機微粒子をそれぞれ単独で使用してもよいし、無機微粒子と有機微粒子を組み合わせて使用してもよい。
無機微粒子としては、酸化アルミニウム(アルミナ、Al2O3)、酸化アルミニウムの水和物(ベーマイト、AlOOH)、ギブサイト(Al(OH)3)、酸化ケイ素、酸化マグネシウム(マグネシア)、水酸化マグネシウム、酸化カルシウム、酸化チタン(チタニア)、チタン酸バリウム(BaTiO3)、ZrO、アルミナ-シリカ複合酸化物等の無機酸化物粒子;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。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、無機微粒子は、1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
有機微粒子は、ポリエステル重合体などの接着性重合体を含有する接着性粒子及び結着材とは異なり、接着性を有さない重合体からなる微粒子である。
ここで、有機微粒子としては、架橋ポリメタクリル酸メチル、架橋ポリスチレン、架橋ポリジビニルベンゼン、スチレン-ジビニルベンゼン共重合体架橋物、ポリスチレン、ポリイミド、ポリアミド、ポリアミドイミド、メラミン樹脂、フェノール樹脂、ベンゾグアナミン-ホルムアルデヒド縮合物などの各種架橋高分子粒子や、ポリスルフォン、ポリアクリロニトリル、ポリアラミド、ポリアセタール、熱可塑性ポリイミドなどの耐熱性高分子粒子、並びにこれらの変性体及び誘導体が挙げられる。なお、有機微粒子は、1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
なお、上述した通り、有機微粒子は接着性を有さない重合体で構成される。具体的に、有機微粒子を構成する重合体のガラス転移温度は、150℃以上であることが好ましい。
耐熱性微粒子は、体積平均粒子径が、0.1μm以上であることが好ましく、0.2μm以上であることがより好ましく、0.3μm以上であることが更に好ましく、1.0μm以下であることが好ましく、0.9μm以下であることがより好ましく、0.8μm以下であることが更に好ましい。耐熱性微粒子の体積平均粒子径が0.1μm以上であれば、機能層中で耐熱性微粒子が過度に密に充填されることに起因して機能層のイオン伝導性が低下するのを抑制し、電気化学素子に優れた素子特性(特に、レート特性)を発揮させることができる。一方、耐熱性微粒子の体積平均粒子径が1.0μm以下であれば、機能層を薄くした場合でも、当該機能層を備える積層体からなる素子部材に優れた耐熱性を十分に発揮させることができる。したがって、素子部材の耐熱性を十分に確保しつつ、電気化学素子の容量を高めることができる。
接着性粒子は、少なくともポリエステル重合体を含む接着性重合体を含有する粒子であり、当該粒子は、接着性重合体以外の成分(任意成分)を含んでいてもよい。すなわち接着性粒子は、実質的に接着性重合体のみからなる粒子であってもよいし、接着性重合体と、任意成分とで構成される粒子であってもよい。
接着性重合体は、上述した通りポリエステル重合体を少なくとも含み、任意にポリエステル重合体以外の接着性重合体(その他の接着性重合体)を含む。
ポリエステル重合体は、アルコール成分とカルボン酸成分とを縮合重合させて得られる重合体である。換言すると、ポリエステル重合体は、アルコール成分に由来する繰り返し単位(アルコール単位)と、カルボン酸成分に由来する繰り返し単位(カルボン酸単位)とを有する縮合重合体である。
アルコール成分としては、多価アルコールを用いることができる。ここで多価アルコールとしては、2価のアルコール、3価以上のアルコールが挙げられる。
鎖状脂肪族ジオールとしては、エチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,4-ブタンジオール、3-メチル-1,5-ペンタンジオール、1,6-ヘキサンジオール、1,8-オクタンジオール、1,10-デカンジオール、及び1,12-ドデカンジオールなどが挙げられる。
オキシアルキレン基を有するジオールとしては、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、及びポリテトラメチレングリコールなどが挙げられる。
炭素環を有するジオールとしては、1,4-シクロヘキサンジメタノール、並びにビスフェノール類(例えば、ビスフェノールA、ビスフェノールF、ビスフェノールS)、ビスフェノール類の水素添加物、及びビスフェノール類のアルキレンオキシド付加物(例えば、エチレンオキシド付加物、プロピレンオキシド付加物、ブチレンオキシド付加物)などが挙げられる。
カルボン酸成分としては、多価カルボン酸及びその無水物、並びにそれらのハロゲン化物を用いることができる。
多価カルボン酸としては、シュウ酸、マロン酸、コハク酸、アジピン酸、セバシン酸、ドデカン二酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グルタコン酸などの鎖状脂肪族多価カルボン酸;フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ナフタレンジカルボン酸、ピロメリット酸などの芳香族多価カルボン酸;が挙げられる。
上述したアルコール成分とカルボン酸成分を縮合重合する方法は特に限定されず、既知の重合助剤、重合条件を採用することができる。
ここで、ポリエステル重合体は、ガラス転移温度が10℃以上95℃以下であることが必要であり、15℃以上であることが好ましく、30℃以上であることがより好ましく、40℃以上であることが更に好ましく、56℃以上であることが特に好ましく、90℃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い。ポリエステル重合体のガラス転移温度が10℃未満であると、積層体からなる素子部材の耐ブロッキング性が低下する。一方、ポリエステル重合体のガラス転移温度が95℃超であると、積層体からなる素子部材の低温接着性が低下する。
なお、ポリエステル重合体のガラス転移温度は、ポリエステル重合体の調製に用いるアルコール成分及び/又はカルボン酸成分の種類や、重合条件を変更することにより制御し得る。
接着性粒子が任意に含む上記ポリエステル重合体以外の接着性重合体としては、少なくとも、芳香族モノビニル単量体単位を含む重合体(芳香族ビニル系重合体)が好ましい。そして、芳香族ビニル系重合体は、芳香族モノビニル単量体単位以外の単量体単位(その他の単量体単位)を含んでいてもよい。
接着性重合体が芳香族モノビニル単量体単位を含む重合体を含有することで、接着性粒子の弾性が向上し、機能層の強度を高めることができる。
ここで、芳香族モノビニル単量体単位を形成し得る芳香族モノビニル単量体の例としては、特に限定されることなく、例えば、スチレン、α-メチルスチレン、スチレンスルホン酸、ブトキシスチレン、ビニルナフタレン等が挙げられる。これらは、1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。そしてこれらの中でも、スチレンが好ましい。
なお、本発明において、重合体中に含まれる各「単量体単位の含有割合」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。
その他の単量体単位としては、特に限定されないが、架橋性単量体単位、(メタ)アクリル酸エステル単量体単位が好ましく挙げられる。
なお、本発明において、「(メタ)アクリル」とは、アクリル及び/またはメタクリルを意味する。
これらの(メタ)アクリル酸エステル単量体は、1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。そしてこれらの中でも、n-ブチルアクリレート、2-エチルヘキシルアクリレート及びメチルメタクリレートが好ましく、n-ブチルアクリレート、2-エチルヘキシルアクリレートがより好ましい。
また、芳香族ビニル系重合体中における、上述した芳香族モノビニル単量体単位、架橋性単量体単位、及び(メタ)アクリル酸エステル単量体単位以外の単量体単位の含有割合は、芳香族ビニル系重合体中の全単量体単位を100質量%とした場合に、機能層を形成するために用いる機能層用組成物の安定性確保の観点から、好ましくは0質量%以上10質量%以下、より好ましくは0質量%以上7質量%以下、更に好ましくは0質量%以上5質量%以下である。
ここで、上述した芳香族ビニル系重合体などのその他の接着性重合体は、ガラス転移温度が、10℃以上であることが好ましく、30℃以上であることがより好ましく、40℃以上であることが更に好ましく、90℃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い。接着性粒子中のガラス転移温度が10℃以上であれば、積層体からなる素子部材の耐ブロッキング性を更に向上させることができ、90℃以下であれば、素子部材の低温接着性を更に向上させることができる。
なお、その他の接着性重合体のガラス転移温度は、当該重合体の調製に用いる単量体の種類及び/又は割合や、重合条件を変更することにより制御し得る。
そして接着性重合体が、ポリエステル重合体とその他の接着性重合体とで構成される場合、コア部がその他の接着性重合体(例えば、上述した芳香族ビニル系重合体)で構成され、シェル部がポリエステル重合体で構成されることが好ましい。
上述した接着性重合体以外の任意成分としては、融点を40℃以上95℃以下の範囲に有する溶融性添加剤が好ましく挙げられる。接着性粒子が溶融性添加剤を含むことで、積層体からなる素子部材の低温接着性を更に向上させることができる。
植物系ワックスとしては、例えば、キャンデリラワックス、カルナウバワックス、ライスワックス、木ロウ、ホホバオイルが挙げられる。
動物系ワックスとしては、例えば、ミツロウが挙げられる。
石油系ワックスとしては、例えば、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムワックスが挙げられる。
ポリオレフィンワックスとしては、例えば、ポリエチレンワックス、ポリプロピレンワックス、ポリブチレンワックスが挙げられる。
エステルワックスとしては、1価アルコール脂肪酸エステル及び多価アルコール脂肪酸エステルのいずれも用いることができる。ここで、1価アルコール脂肪酸エステルの具体例としては、ステアリン酸べへニルなどが挙げられる。また、多価アルコール脂肪酸エステルの具体例としては、ペンタエリスリトールテトラミリステート、ペンタエリスリトールテトラパルミテート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトララウレート、ペンタエリスリトールテトラベヘネート等のペンタエリスリトールエステル;ジペンタエリスリトールヘキサミリステート、ジペンタエリスリトールヘキサパルミテート、ジペンタエリスリトールヘキサラウレート等のジペンタエリスリトールエステル;が挙げられる。
結晶性ポリエステル樹脂としては、40℃以上95℃以下の範囲に融点を有し、且つ10℃以上95℃以下の範囲内にガラス転移温度を有さなければ(換言すると、ガラス転移温度自体を有さない、若しくは10℃未満及び/又は95℃超の範囲にガラス転移温度を有するものであれば)特に限定されず、アルコール成分とカルボン酸成分とを縮合重合させて得られる重合体を用いることができる。
ここで、結晶性ポリエステル樹脂の調製に用いるアルコール成分とカルボン酸成分は、何れも「ポリエステル重合体」の項で上述したものを用いることができる。そしてアルコール成分としては、鎖状脂肪族ジオールが好ましく、1,6-ヘキサンジオールがより好ましい。またカルボン酸成分としては、鎖状脂肪族多価カルボン酸が好ましく、セバシン酸がより好ましい。
なお、上述したアルコール成分とカルボン酸成分を縮合重合する方法は特に限定されず、既知の重合助剤、重合条件を採用することができる。
ここで、接着性粒子中の溶融性添加剤の含有量は、接着性重合体100質量部当たり、1質量部以上であることが好ましく、2質量部以上であることがより好ましく、5質量部以上であることが更に好ましく、6質量部以上であることが一層好ましく、10質量部以上であることが特に好ましく、30質量部以下であることが好ましく、25質量部以下であることがより好ましく、20質量部以下であることが更に好ましく、15質量部以下であることが特に好ましい。接着性粒子中の溶融性添加剤の含有量が、接着性重合体100質量部当たり1質量部以上であれば、積層体からなる素子部材の低温接着性を更に向上させることができる。一方、接着性粒子中の溶融性添加剤の含有量が、接着性重合体100質量部当たり30質量部以下であれば、溶融性添加剤のブリードアウトを十分に抑制し、積層体からなる素子部材の耐ブロッキング性を更に高めつつ、当該素子部材を備える電気化学素子のレート特性及びサイクル特性を向上させることができる。
ここで接着性粒子は、平均円形度が0.90以上であることが好ましく、0.92以上であることがより好ましく、0.95以上であることが更に好ましく、0.97以上であることが特に好ましく、0.99以下であることが特に好ましい。接着性粒子の平均円形度が0.90以上であれば、積層体からなる素子部材の低温接着性を更に向上させることができる。加えて電解液中においても積層体からなる素子部材が接着性を良好に発揮しうる。一方、接着性粒子の平均円形度が0.99以下であれば、積層体からなる素子部材の電解液中における抵抗を低減し、当該素子部材を備える電気化学素子のレート特性及びサイクル特性を向上させることができる。
なお、接着性粒子の平均円形度は、接着性粒子の調製方法を変更することにより調整することができる。
接着性重合体を含有する接着性粒子を調製する方法は、ポリエステル重合体を含有する接着性重合体と、必要に応じて用いられる溶融性添加剤などの任意成分(これらを纏めて「接着性粒子材料」と称する。)を粒子化することができれば特に限定されず、例えば以下の1)~4):
1)接着性粒子材料を、少なくともポリエステル重合体が溶解可能な有機溶媒中に溶解及び/又は分散させて液状組成物を調製し、当該液状組成物を水系媒体中に分散させ、その後有機溶媒を除去することで接着性粒子材料を粒子化する方法(溶解懸濁法)、
2)界面活性剤及び/又は分散安定剤を用いて接着性粒子材料を水系媒体中に分散させ、分散した微粒子を凝集させることで接着性粒子材料を粒子化する方法(乳化凝集法)、
3)接着性粒子材料を溶融混錬し、冷却した後、得られた混錬物を粉砕して接着性粒子材料を粒子化する方法(粉砕法)、
4)ポリエステル重合体及び必要に応じて用いられる任意成分の存在下で、その他の接着性重合体の調製に用いる単量体を懸濁重合して、接着性粒子材料を粒子化けする方法(懸濁重合法)、
が挙げられる。
なお、溶解懸濁法、乳化凝集法、粉砕法、懸濁重合法は、それぞれ既知の方法及び条件を採用して行うことができる。
ここで、機能層中における耐熱性微粒子と接着性粒子の含有量比は、特に限定されないが、接着性粒子の含有量に対する耐熱性微粒子の含有量の体積比(耐熱性微粒子/接着性粒子)の値が、55/45以上であることが好ましく、60/40以上であることがより好ましく、95/5以下であることが好ましく、80/20以下であることがより好ましく、75/25以下であることが更に好ましい。耐熱性微粒子/接着性粒子(体積基準)の値が55/45以上であれば、積層体からなる素子部材の耐熱性を向上させることができ、95/5以下であれば、当該素子部材の低温接着性を更に向上させることができる。
結着材は、上述した通り耐熱領域において耐熱性微粒子同士を結着させる。結着材としては、結着材として用いられる既知の重合体、例えば、共役ジエン系重合体、アクリル系重合体、ポリフッ化ビニリデン(PVDF)、ポリビニルアルコール(PVOH)が挙げられる。結着材は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。そして結着材としては、共役ジエン系重合体、アクリル系重合体、ポリフッ化ビニリデン(PVDF)などの、非水溶性で、水などの分散媒中に分散可能な重合体が好ましく、共役ジエン系重合体、アクリル系重合体がより好ましく、アクリル系重合体が更に好ましい。
なお、本発明において、重合体が「非水溶性」であるとは、温度25℃において重合体0.5gを100gの水に溶解した際に、不溶分が90質量%以上となることをいう。
共役ジエン系重合体とは、共役ジエン単量体に由来する共役ジエン単量体単位を含む重合体を指す。そして、共役ジエン系重合体の具体例としては、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)などの芳香族モノ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)、ニトリルゴム(NBR)(アクリロニトリル単位及び1,3-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。
アクリル系重合体とは、(メタ)アクリル酸エステル単量体単位を含む重合体を指す。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に加え、例えば、架橋性単量体単位と酸基含有単量体単位の少なくとも一方を含むことが好ましい。
また、結着材(アクリル系重合体)中の(メタ)アクリル酸エステル単量体単位の含有割合は、結着材中の全単量体単位を100質量%とした場合に、好ましくは65質量%超、より好ましくは70質量%以上、更に好ましくは80質量%以上、特に好ましくは90質量%以上であり、好ましくは99質量%以下、より好ましくは98質量%以下、更に好ましくは95質量%以下である。
また、結着材(アクリル系重合体)中の架橋性単量体単位の含有割合は、結着材中の全単量体単位を100質量%とした場合に、好ましくは0.1質量%以上であり、好ましくは3.0質量%以下、より好ましくは2.5質量%以下である。架橋性単量体単位の割合が0.1質量%以上であれば、電気化学素子のレート特性及びサイクル特性を向上させることができ、3.0質量%以下であれば、積層体からなる素子部材の低温接着性を更に向上させることができる。
そして、カルボン酸基を有する単量体としては、例えば、モノカルボン酸、ジカルボン酸などが挙げられる。モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸などが挙げられる。ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸などが挙げられる。
また、スルホン酸基を有する単量体としては、例えば、ビニルスルホン酸、メチルビニルスルホン酸、(メタ)アリルスルホン酸、(メタ)アクリル酸-2-スルホン酸エチル、2-アクリルアミド-2-メチルプロパンスルホン酸、3-アリロキシ-2-ヒドロキシプロパンスルホン酸などが挙げられる。
なお、本発明において、「(メタ)アリル」とは、アリル及び/またはメタリルを意味する。
更に、リン酸基を有する単量体としては、例えば、リン酸-2-(メタ)アクリロイルオキシエチル、リン酸メチル-2-(メタ)アクリロイルオキシエチル、リン酸エチル-(メタ)アクリロイルオキシエチルなどが挙げられる。
なお、本発明において、「(メタ)アクリロイル」とは、アクリロイル及び/またはメタクリロイルを意味する。
また、水酸基を有する単量体としては、例えば、アクリル酸-2-ヒドロキシエチル、アクリル酸-2-ヒドロキシプロピル、メタクリル酸-2-ヒドロキシエチル、メタクリル酸-2-ヒドロキシプロピルなどが挙げられる。
なお、これらの酸基含有単量体は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。そしてこれらの中でも、カルボン酸基を有する単量体が好ましく、メタクリル酸がより好ましい。
なお、これらその他の単量体は、1種を単独で用いてもよく、2種以上を任意の比率で組み合わせて用いてもよい。また、アクリル系重合体におけるその他の単量体単位の含有割合は、適宜調整すればよい。
ここで、結着材は、芳香族モノビニル単量体単位を含むこともできるが、結着材(特には、アクリル系重合体)中の芳香族モノビニル単量体単位の含有割合は、結着材中の全単量体単位を100質量%とした場合に、好ましくは30質量%未満、より好ましくは20質量%以下、更に好ましくは10質量%以下、特に好ましくは、5質量%以下、最も好ましくは0質量%(即ち、芳香族モノビニル単量体単位を含まない)である。
結着材は、ガラス転移温度が、-100℃以上であることが好ましく、-90℃以上であることがより好ましく、-80℃以上であることが更に好ましく、30℃未満であることが好ましく、20℃以下であることがより好ましく、15℃以下であることが更に好ましく、10℃未満であることが特に好ましい。結着材のガラス転移温度が-100℃以上であれば、結着材の結着能及び強度を高めることができ、30℃未満であれば、結着材を含む機能層の柔軟性を十分に確保することができる。
また、機能層中の結着材の含有量は、耐熱性微粒子100質量部当たり、0.1質量部以上であることが好ましく、0.2質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましく、20質量部以下であることが好ましく、15質量部以下であることがより好ましく、10質量部以下であることが更に好ましく、6質量部以下であることが特に好ましい。機能層中の結着材の含有量が、耐熱性微粒子100質量部当たり0.1質量部以上であれば、耐熱領域に存在する耐熱性微粒子が機能層から脱落するのを十分に抑制しつつ、機能層を備える素子部材の低温接着性を更に向上させることができる。一方、機能層中の結着材の含有量が、耐熱性微粒子100質量部当たり20質量部以下であれば、積層体からなる素子部材を備える電気化学素子のレート特性及びサイクル特性を向上させることができる。
なお、結着材は、特に限定されることなく、例えば、上述した単量体を含む単量体組成物を、水などの水系溶媒中で重合することにより調製することができる。ここで、単量体組成物中の全単量体中に占める各単量体の割合は、通常、結着材中の各単量体単位の割合と同様とする。
そして、重合方法及び重合反応としては、特に限定されず、既知のものを用いることができる。
本発明の積層体が備える機能層は、特に限定されず、上述した耐熱性微粒子、接着性粒子及び結着材以外の成分として、機能層の調製に用いうる、分散剤や増粘剤などの既知の成分(例えば、ドデシルベンゼンスルホン酸ナトリウム、並びに、ポリアクリル酸及びその塩やカルボキシメチルセルロース及びその塩などの水溶性重合体)を含むことができる。その他の成分は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
なお、本発明において、重合体が「水溶性」であるとは、温度25℃において重合体0.5gを100gの水に溶解した際に、不溶分が1.0質量%未満となることをいう。
上述した機能層を少なくとも一方の表面に備える基材は、本発明の積層体を用いる素子部材の種類に応じて適宜選択すればよい。例えば、本発明の積層体をセパレータとして用いる場合、基材としてはセパレータ基材を使用する。また例えば、本発明の積層体を電極として用いる場合、基材としては電極基材を使用する。
セパレータ基材としては、特に限定されず、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、ポリブテン、ポリ塩化ビニル等のポリオレフィン系樹脂、芳香族ポリアミド樹脂などを含む微多孔膜又は不織布などが挙げられる。
これらの中でも、電気化学素子内の電極活物質の比率を高くして体積当たりの容量を高くすることができるという観点から、ポリオレフィン系樹脂からなる微多孔膜が好ましい。
なお、セパレータ基材の厚さは、任意の厚さとすることができ、好ましくは5μm以上30μm以下であり、より好ましくは5μm以上20μm以下であり、更に好ましくは5μm以上18μm以下である。
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、集電体上に電極合材層が形成された電極基材が挙げられる。
ここで、集電体、電極合材層中の電極活物質(正極活物質、負極活物質)及び電極合材層用結着材(正極合材層用結着材、負極合材層用結着材)、並びに、集電体上への電極合材層の形成方法には、既知のものを用いることができ、例えば特開2013-145763号公報に記載のものを用いることができる。
本発明の積層体を製造する方法は、特に限定されず、例えば離型シート上に機能層を形成し、当該機能層を基材上に転写するといった方法を用いることもできる。しかしながら、転写の作業を不要とし製造効率を高める観点から、積層体は、耐熱性微粒子、接着性粒子、結着材及び分散媒を少なくとも含む機能層用組成物を基材上に供給する工程(供給工程)と、基材上に供給された機能層用組成物を乾燥する工程(乾燥工程)を経て製造することが好ましい。
上述した通り、機能層用組成物は、分散媒中に、少なくとも耐熱性微粒子、接着性粒子及び結着材を含み、任意にその他の成分を含有する。なお分散媒としては、特に限定されないが、水を好ましく用いることができる。
なお、機能層用組成物を調製する方法は、特に限定されず、既知の混合方法又は分散方法を用いることができる。
また、上記のように供給工程及び乾燥工程を経て本発明の積層体が製造される場合、当該積層体が備える機能層は、機能層用組成物の乾燥物からなる。そのため、機能層中に含まれている各成分は、機能層用組成物に含まれていたものであり、機能層用組成物中の各成分の好適な存在比は、上述した機能層中の各成分の好適な存在比と同じである。
供給工程では、上述した機能層用組成物を基材上に供給して、当該基材上に機能層用組成物の被膜を形成する。基材上に機能層用組成物を供給する方法は、特に限定されず、機能層用組成物を基材の表面に塗布してもよいし、機能層用組成物に基材を浸漬させてもよい。そして、製造される機能層の厚み(特には、耐熱領域の積層方向平均高さ)を制御し易いことから、機能層用組成物を基材の表面に塗布することが好ましい。
機能層用組成物を基材の表面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、グラビアコート法、バーコート法、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。
なお、供給工程においては、基材の一方の面のみに機能層用組成物の被膜を形成してもよいし、基材の両面に機能層用組成物の被膜を形成してもよい。
乾燥工程では、供給工程で基材上に形成された機能層用組成物の被膜を乾燥して分散媒を除去し、機能層を形成する。
機能層用組成物の被膜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、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法が挙げられる。乾燥条件は特に限定されないが、乾燥温度は好ましくは50~150℃で、乾燥時間は好ましくは1~30分である。
本発明の電気化学素子は、電極と、セパレータを備え、電極とセパレータの少なくとも一方として、上述した本発明の積層体を備えることを特徴とする。本発明の電気化学素子は、電極とセパレータの少なくとも何れかの素子部材として上述した本発明の積層体を用いているため、レート特性及びサイクル特性といった素子特性に優れる。
正極及び負極としては、「基材」の項で上述した既知の電極基材(正極基材及び負極基材)からなる電極を用いることができる。
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等が挙げられる。なかでも、溶媒に溶けやすく高い解離度を示すことから、LiPF6、LiClO4、CF3SO3Liが好ましい。なお、電解質は1種を単独で用いてもよく、2種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。
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。
本発明の電気化学素子を製造する方法は、特に限定されない。例えば、上述した本発明の電気化学素子の一例としてのリチウムイオン二次電池は、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、正極、負極、セパレータのうち、少なくとも一つの素子部材を本発明の積層体とする。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。
また、複数種類の単量体を共重合して製造される重合体において、ある単量体を重合して形成される繰り返し単位(単量体単位)の前記重合体における割合は、別に断らない限り、通常は、その重合体の重合に用いる全単量体に占める当該ある単量体の比率(仕込み比)と一致する。
ポリエステル重合体及び結着材をそれぞれ測定試料とした。測定試料10mgをアルミパンに計量し、示差熱分析測定装置(エスアイアイ・ナノテクノロジー社製、「EXSTAR DSC6220」)にて、リファレンスとして空のアルミパンを用い、測定温度範囲-100℃~200℃の間で、昇温速度10℃/分で、JIS Z 8703に規定された条件下で測定を実施し、示差走査熱量分析(DSC)曲線を得た。この昇温過程で、微分信号(DDSC)が0.05mW/分/mg以上となるDSC曲線の吸熱ピークが出る直前のベースラインと、吸熱ピーク後に最初に現れる変曲点でのDSC曲線の接線との交点を、ガラス転移温度(℃)として求めた。
<結着材の体積平均粒子径>
結着材の体積平均粒子径は、レーザー回折法にて測定した。具体的には、調製した結着材を含む水分散溶液(固形分濃度0.1質量%に調整)を試料とした。そして、レーザー回折式粒子径分布測定装置(ベックマン・コールター社製、「LS-230」)を用いて測定された粒子径分布(体積基準)において、小径側から計算した累積体積が50%となる粒子径D50を、体積平均粒子径とした。
<耐熱性微粒子の体積平均粒子径>
レーザー回折法にて測定した粒子径分布(体積基準)において、小径側から計算した累積体積が50%となる粒子径(D50)を、耐熱性微粒子の体積平均粒子径とした。
<接着性粒子の体積平均粒子径>
接着性粒子0.1g相当量を秤量し、ビーカーに取り、分散剤としてアルキルベンゼンスルホン酸水溶液(富士フイルム社製、「ドライウエル」)0.1mLを加えた。上記ビーカーに、更に、希釈液(ベックマン・コールター社製、「アイソトンII」)を10~30mL加え、20W(Watt)の超音波分散機で3分間分散させた。その後、粒径測定機(ベックマン・コールター社製、「マルチサイザー」)を用いて、アパーチャー径:20μm、媒体:アイソトンII、測定粒子個数:100,000個の条件下で、接着性粒子の体積平均粒子径を測定した。
<接着性粒子の平均円形度>
容器中に、予めイオン交換水10mLを入れ、その中に分散剤として界面活性剤(アルキルベンゼンスルホン酸)0.02gを加え、更に接着性粒子0.02gを加え、超音波分散機を用いて60W(Watt)で3分間、分散処理を行った。測定時の接着性粒子の濃度が3,000~10,000個/μLとなるように調整し、0.4μm以上の円相当径の接着性粒子1,000個についてフロー式粒子像分析装置(シメックス社製、「FPIA-3000」)を用いて測定した。なお、円形度は下記式(I)に示され、平均円形度は、測定した1,000個の接着性粒子の円形度について算術平均をとったものである。
円形度=接着性粒子の投影面積に等しい円の周囲長/接着性粒子の投影像の周囲長 ・・・(I)
<耐熱領域の積層方向平均高さ>
機能層を備えるセパレータの断面を、上記電界放出型走査電子顕微鏡(FE-SEM)を用いて観察し、得られたSEM画像から耐熱領域の任意の5点についての積層方向の高さを測定し、これらの測定値の平均値として耐熱領域の積層方向平均高さを算出した。
<耐熱領域の積層方向平均高さに対する接着性粒子の体積平均粒子径の比>
上述のようにして得た値から、体積平均粒子径/積層方向平均高さを算出した。
<接着性粒子の含有量に対する耐熱性微粒子の含有量の比>
機能層用組成物を調製した際の耐熱性微粒子及び接着性粒子の仕込み量から、接着性粒子の含有量に対する耐熱性微粒子の含有量の比(体積比、質量比)を求めた。なお、耐熱性微粒子としてのアルミナ粒子の密度は4g/cm3として計算した。
<低温接着性>
作製した正極、負極、及びセパレータ(耐熱領域の積層方向平均高さが2.0μmである機能層を両面に備える)を、それぞれ10mm幅、長さ50mm幅に切り出し、正極及びセパレータを積層させ、温度50℃、荷重8kN/m、プレス速度30m/分の条件で、ロールプレスを用いてプレスし、正極とセパレータとを一体化させた一体化物を得た。
得られた一体化物を、正極の集電体側の面を下にして、正極の表面にセロハンテープを貼り付けた。この際、セロハンテープとしてはJIS Z1522に規定されるものを用いた。また、セロハンテープは水平な試験台に固定しておいた。その後、セパレータの一端を鉛直上方に引張り速度50mm/分で引っ張って剥がしたときの応力を測定した。
また、実施例及び比較例で作製した負極に対しても、正極を用いた場合と同様の操作を行い、応力を測定した。
上述の応力の測定を、正極及びセパレータの一体化物、並びに、負極及びセパレータの一体化物でそれぞれ3回、計6回行い、応力の平均値を求めて、得られた平均値をピール強度(N/m)とした。
そして、算出されたピール強度を用いて、以下の基準により機能層を備えるセパレータの低温接着性を評価した。ピール強度が大きいほど、素子部材としてセパレータが、機能層によって優れた低温接着性を発揮し得ることを示す。
A:ピール強度3N/m以上
B:ピール強度2N/m以上3N/m未満
C:ピール強度1N/m以上2N/m未満
D:ピール強度1N/m未満
<耐ブロッキング性>
作製したセパレータ(耐熱領域の積層方向平均高さが2.0μmである機能層を両面に備える)を幅4cm×長さ4cmのサイズに2枚切り出して試験片とした。得られた2枚の試験片を、機能層側を介して重ね合わせた後に、温度40℃、圧力5MPaの加圧下で、2分間プレスしてプレス体を得た。得られたプレス体の一方端を固定し、プレス体の他方端を引張速度50mm/分で鉛直上方に引っ張って剥がしたときの応力を測定し、得られた応力をブロッキング強度とした。そして、耐ブロッキング性を、以下の基準で評価した。ブロッキング強度が小さいほど、機能層はブロッキングの発生を良好に抑制する、即ち、機能層の耐ブロッキング性が高いことを示す。
A:ブロッキング強度が4N/m未満
B:ブロッキング強度が4N/m以上6N/m未満
C:ブロッキング強度が6N/m以上
<耐熱性>
作製したセパレータ(耐熱領域の積層方向平均高さが2.0μmである機能層を両面に備える)を、幅12cm×長さ12cmの正方形に切り出し、得られた正方形の内部(片面)に1辺が10cmの正方形を描いて試験片とした。そして、試験片を150℃の恒温槽に入れて1時間放置した後、内部に描いた正方形の面積変化(={(放置前の正方形の面積-放置後の正方形の面積)/放置前の正方形の面積}×100%)を熱収縮率として求め、以下の基準で評価した。熱収縮率が小さいほど、機能層を備えるセパレータが耐熱性に優れていることを示す。
A:熱収縮率が3%未満
B:熱収縮率が3%以上5%未満
C:熱収縮率が5%以上10%未満
D:熱収縮率が10%以上
<レート特性>
作製したリチウムイオン二次電池を25℃の環境下で24時間静置させた後に、25℃の環境下で、4.35V、0.1Cの充電、3.0V、0.1Cの放電にて充放電の操作を行い、初期容量C0を測定した。その後、25℃の環境下で、4.35V、0.1C充電、3.0V、2Cの放電にて充放電の操作を行い、容量C1を測定した。レート特性は、ΔC=(C0-C1)/C0×100(%)にて評価し、この値が大きいほどリチウムイオン二次電池がレート特性に優れることを示す。
A:ΔCが90%以上
B:ΔCが85%以上90%未満
C:ΔCが80%以上85%未満
D:ΔCが80%未満
<サイクル特性>
作製した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の定電流法にて、CC-CV充電(上限セル電圧4.20V)を行い、0.2Cの定電流法にて3.00VまでCC放電した。この0.2Cにおける充放電を3回繰り返し実施した。
その後、温度25℃の環境下、セル電圧4.20-3.00V、1.0Cの充放電レートにて充放電の操作を100サイクル行った。その際、第1回目のサイクルの放電容量をX1,第100回目のサイクルの放電容量をX2と定義した。
そして、放電容量X1及び放電容量X2を用いて、容量維持率ΔC´=(X2/X1)×100(%)を求め、以下の基準により評価した。容量維持率ΔC´の値が大きいほど、リチウムイオン二次電池がサイクル特性に優れていることを示す。
A:ΔC´が93%以上
B:ΔC´が90%以上93%未満
C:ΔC´が90%未満
<ポリエステル重合体の調製>
アルコール成分としてのBPA-PO(ビスフェノールAのプロピレンオキサイド付加物、平均付加モル数:2.2モル)2000g及びBPA-EO(ビスフェノールAのエチレンオキサイド付加物、平均付加モル数:2.2モル)800g、カルボン酸成分としてのフマル酸600g及び無水トリメリット酸500g、並びにジブチルスズオキサイド4gを、窒素導入管、脱水管、撹拌器及び熱伝対を装備した5リットル容の四つ口フラスコに入れ、220℃で8時間かけて反応させた。その後さらに、8.3kPaにて反応物の軟化点(下記の方法により測定。)が150℃になるまで反応させ、ポリエステル重合体を得た。得られたポリエステル重合体のガラス転移温度は62℃であった。
―軟化点の測定方法―
高化式フローテスター(島津製作所製、製品名「CFT-500D」)を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルを押し出すようにし、これによりフローテスターのプランジャー降下量(流れ値)―温度曲線を描き、そのS字曲線の高さをhとするときh/2に対応する温度(重合体の半分が流出した温度)を軟化点とした。
<エステルワックス(溶融性添加剤)の調製>
窒素導入管、撹拌羽、及び冷却管を取り付けた0.5L容の4つ口フラスコに、ペンタエリスリトール18g(0.13mol)、及びラウリン酸104g(0.52mol)を加え、窒素気流下、生成水を留去しながら、220℃で10時間反応を行なった。トルエン46.5g及び2-プロパノール32g、酸価の2.0倍当量の水酸化カリウムを含む10%水酸化カリウム水溶液19gを加え、70℃で30分間撹拌し、30分間静置後、水層部を除去して、粗生成物を得た。
粗生成物100部に対して40部のイオン交換水を用い、70℃で水洗を4回行い、pHを7とした。得られた精製物から加熱及び減圧条件下で溶媒を留去し、ろ過、固化、及び粉砕を経て、エステルワックスとしてのペンタエリスリトールテトララウレート(融点:44℃)を140g得た。
<接着性粒子の調製>
溶解懸濁法を用いる下記の手順で接着性粒子材料(ポリエステル重合体、エステルワックス)を粒子化した。
ポリエステル樹脂100部、エステルワックス10部、及び有機溶媒としてのトルエン230部をボールミルで分散し、液状組成物を得た。
別途、ヒドロキシアバタイトの水溶液(濃度:5%)480部、ドデシルベンゼンスルホン酸ナトリウムの水溶液(濃度:1%)6部、及び水120部を混合し、水系媒体を準備した。
上記液状組成物を、上記水系媒体中にホモジナイザーを用いて分散させた。なお、ローターの周速は6~8m/秒の範囲で調整した。得られた分散液を、温度:50~70℃、圧力:30~150mmHgの条件下に置くことでトルエンを除去した。トルエン除去後の組成物を冷却し、次いで12N塩酸をpHが2になるまで加えて洗浄し、さらに水洗、乾燥、及び分級することで、ポリエステル重合体及びエステルワックスを含む接着性粒子を得た。接着性粒子の体積平均粒子径は6.0μmであり、平均円形度は0.97であった。
<結着材の調製>
撹拌機を備えた反応器に、イオン交換水70部、乳化剤としてのラウリル硫酸ナトリウム(花王ケミカル社製、「エマール(登録商標)2F」)0.15部、及び重合開始剤としての過硫酸アンモニウム0.5部を供給し、気相部を窒素ガスで置換し、60℃に昇温した。
一方、別の容器で、イオン交換水50部、分散安定剤としてのドデシルベンゼンスルホン酸ナトリウム0.5部、(メタ)アクリル酸エステル単量体としてのn-ブチルアクリレート94部、酸基含有単量体としてのメタクリル酸2部、及びニトリル基含有単量体としてのアクリロニトリル2部、並びに架橋性単量体としてのアリルメタクリレート1部及びアリルグリシジルエーテル1部を混合して、単量体組成物を調製した。
得られた単量体組成物を4時間かけて上述した撹拌機を備えた反応器に連続的に添加して重合を行った。添加中は、60℃で反応を行った。添加終了後、更に70℃で3時間撹拌してから反応を終了し、アクリル系重合体としての粒子状の結着材を含む水分散液を得た。得られた結着材は、体積平均粒子径が0.25μmであり、ガラス転移温度が-40℃であった。
<機能層用組成物の調製>
耐熱性微粒子としてのアルミナ(体積平均粒子径:0.5μm)100部に、水溶性重合体としてのポリアクリル酸0.5部を添加し、固形分濃度が55%となるようにイオン交換水を加え、ボールミルを用いて混合してアルミナ含有スラリーを得た。
また、上記接着性粒子100部と、分散剤としてのドデシルベンゼンスルホン酸ナトリウム(花王ケミカル社製、「ネオぺレックスG-15」)0.2部と、イオン交換水を混合し、固形分濃度が40%の接着性粒子含有混合液を得た。
上記アルミナ含有スラリーと上記接着性粒子含有混合液とを、アルミナと接着性粒子の比(アルミナ/接着性粒子)が、体積基準で70/30(質量基準で90/10)となるように混合した。得られた混合液に、アルミナ100部当たり上記結着材を含む水分散液を固形分相当で6部と、水溶性重合体(増粘剤)としてのカルボキシメチルセルロース1.5部と、イオン交換水とを添加して、機能層用組成物(固形分濃度:40%)を得た。
<機能層を備えるセパレータの作製>
ポリエチレン製の微多孔膜(厚み:12μm)をセパレータ基材として用意した。用意したセパレータ基材の片面に、上述で得られた機能層用組成物をバーコーター法により塗布した。また、塗膜の乾燥は50℃で実施した。そして、上記と同様の操作をセパレータ基材の他方の面に対しても行い、セパレータ基材の両面に機能層を備える機能層を備えるセパレータを得た。得られたセパレータの二つの機能層は何れも、接着性粒子からなる接着領域と、耐熱性微粒子としてのアルミナと結着材からなる耐熱領域とを備えており、耐熱領域の積層方向平均高さは2.0μmであった。
そして、この両面に機能層を備えるセパレータについて、低温接着性、耐ブロッキング性及び耐熱性を評価した。結果を表1に示す。
<正極の作製>
正極活物質としてのLiCoO2(体積平均粒子径:12μm)を100部、導電材としてのアセチレンブラック(電気化学工業社製、「HS-100」)を2部、正極合材層用結着材としてのポリフッ化ビニリデン(クレハ社製、「#7208」)を固形分相当で2部、及び溶媒としてのN-メチルピロリドンを混合し、全固形分濃度を70%とした。これらをプラネタリーミキサーにより混合し、正極用スラリー組成物を調製した。
上記正極用スラリー組成物を、コンマコーターで、集電体としての厚さ20μmのアルミ箔の上に、乾燥後の膜厚が150μm程度になるように塗布し、乾燥させた。この乾燥は、アルミ箔を0.5m/分の速度で60℃のオーブン内を2分間かけて搬送することにより行った。その後、120℃にて2分間加熱処理して、プレス前の正極原反を得た。このプレス前の正極原反をロールプレスで圧延して、正極合材層(厚さ:60μm)を備える正極を得た。
<負極の作製>
撹拌機付き5MPa耐圧容器に、1,3-ブタジエン33部、イタコン酸3.5部、スチレン63.5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0.4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、十分に撹拌した後、50℃に加温して重合を開始した。重合転化率が96%になった時点で冷却して反応を停止し、負極合材層用結着材(SBR)を含む混合物を得た。この負極合材層用結着材を含む混合物に、5%水酸化ナトリウム水溶液を添加して、pH8に調整後、加熱減圧蒸留によって未反応単量体の除去を行った。その後、30℃以下まで冷却し、所望の負極合材層用結着材を含む水分散液を得た。
負極活物質としての人造黒鉛(体積平均粒子径:15.6μm)80部及びシリコン系活物質SiOx(体積平均粒径:4.9μm)16部を配合し、粘度調整剤としてのカルボキシメチルセルロースナトリウム塩(日本製紙社製、「MAC350HC」)の2%水溶液を固形分相当で2.5部、及びイオン交換水を混合して固形分濃度68%に調整した後、25℃で60分間さらに混合した。更にイオン交換水で固形分濃度を62%に調整した後、25℃で15分間さらに混合し、混合液を得た。この混合液に、上記負極合材層用結着材を含む水分散液を固形分相当量で1.5部、及びイオン交換水を入れ、最終固形分濃度が52%となるように調整し、さらに10分間混合し、混合液を得た。この混合液を減圧下で脱泡処理して流動性の良い負極用スラリー組成物を得た。
上記負極用スラリー組成物を、コンマコーターで、集電体としての厚さ20μmの銅箔の上に、乾燥後の膜厚が150μm程度になるように塗布し、乾燥させた。この乾燥は、銅箔を0.5m/分の速度で60℃のオーブン内を2分間かけて搬送することにより行った。その後、120℃にて2分間加熱処理して、プレス前の負極原反を得た。このプレス前の負極原反をロールプレスで圧延して、負極合材層(厚さ:80μm)を備える負極を得た。
<リチウムイオン二次電池の作製>
上述のようにして作製した正極を49cm×5cmの長方形に切り出して、正極合材層側の表面が上側になるように置き、その正極合材層上に、120cm×5.5cmに切り出したセパレータ(両面に機能層を備える)を、正極がセパレータの長手方向の一方側に位置するように配置した。更に、上述のようにして作製した負極を50cm×5.2cmの長方形に切り出し、セパレータ上に、負極合材層側の表面がセパレータに対向し、且つ、負極がセパレータの長手方向の他方側に位置するように配置した。そして、得られた積層体を捲回体によって捲回し、捲回体を得た。
この捲回体を50℃、1MPaでプレスし、扁平体とした後、電池の外装としてのアルミ包材外装で包み、電解液[溶媒:エチレンカーボネート/ジエチルカーボネート/ビニレンカーボネート(体積比)=68.5/30/1.5、電解質:濃度1molのLiPF6)]を空気が残らないように注入した。そして、アルミ包材外装の開口を温度150℃でヒートシールして閉口して、容量800mAhの捲回型リチウムイオン二次電池を作製した。
得られたリチウムイオン二次電池について、レート特性及びサイクル特性を評価した。結果を表1に示す。
接着性粒子の調製に際し、溶融性添加剤であるエステルワックスの量を、それぞれ、5部(実施例2)、20部(実施例3)、30部(実施例4)、35部(実施例5)に変更した以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
溶融性添加剤であるエステルワックスの調製に際し、ラウリン酸に代えてベヘニン酸を用いてエステルワックスとしてペンタエリスリトールテトラベヘネート(融点:81℃)を得た。当該エステルワックスを使用した以外は、実施例1と同様にして、ポリエステル重合体、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
溶融性添加剤であるエステルワックスを調製せず、接着性粒子の調製に際し溶融性添加剤を使用しなかった以外は、実施例1と同様にして、ポリエステル重合体、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
接着性粒子の調製に際し、ヒドロキシアバタイト水溶液の濃度を10%に変更して積層体における接着性粒子の体積平均粒子径を3μmに変更した以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
接着性粒子の調製に際し、ヒドロキシアバタイト水溶液の濃度を3%に変更して積層体における接着性粒子の体積平均粒子径を9μmに変更した以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
溶融性添加剤として、エステルワックスに代えて下記のように調製した結晶性ポリエステル樹脂を使用した以外は、実施例1と同様にして、ポリエステル重合体、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
<結晶性ポリエステル樹脂(溶融性添加剤)の調製>
窒素導入管、脱水管、撹拌器及び熱伝対を装備した5Lの四つ口フラスコに、カルボン酸成分としてのセバシン酸、アルコール成分としての1,6-ヘキサンジオールを、水酸基とカルボキシル基とのモル比であるOH/COOHが0.85となるように仕込み、チタンテトライソプロポキシド(樹脂成分に対して500ppm)と共に、180℃で10時間反応させた後、200℃に昇温して3時間反応させ、更に8.3kPaの圧力にて2時間反応させて結晶性ポリエステル樹脂(融点:65℃)を得た。なお、この結晶性ポリエステル樹脂は、ガラス転移温度を10℃以上95℃以下の範囲に有さないことを確認した。
接着性粒子の調製に際し、溶融性添加剤として、エステルワックス10部に代えてパラフィンワックス(日本精蝋社製、製品名「HNP-11」、融点:68℃)を5部使用した以外は、実施例1と同様にして、ポリエステル重合体、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
機能層用組成物の調製に際し、アルミナ粒子と接着性粒子の混合比(アルミナ粒子/接着性粒子)が、それぞれ、体積基準で80/20(質量基準で94/6、実施例12)、体積基準で55/45(質量基準で82/18、実施例13)となるようにアルミナ含有スラリーと接着性粒子含有混合液を混合した以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
以下のようにして調製したポリエステル重合体を用いた以外は、実施例1と同様にして、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
<ポリエステル重合体の調製>
アルコール成分としてのBPA-PO(ビスフェノールAのプロピレンオキサイド付加物、平均付加モル数:2.2モル)143部、カルボン酸成分としてのテレフタル酸133部及びイソフタル酸33部、並びにジブチルスズオキサイド0.2部を反応容器に仕込んた。反応容器に窒素ガスを吹き込みながら徐々に温度を上げて180℃で5時間縮合反応をすすめたのち、230℃で反応を完結させ、ポリエステル重合体を得た。得られたポリエステル重合体のガラス転移温度は56℃であった。
以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
<接着性粒子の調製>
乳化凝集法を用いる下記の手順で接着性粒子材料(ポリエステル重合体、エステルワックス)を粒子化した。
<<溶融性添加剤分散液の調製>>
実施例1と実施例1と同様にして得られたエステルワックス(溶融性添加剤)100部と、アニオン性界面活性剤(第一工業製薬社製、製品名「ネオゲン(登録商標)RK」)1部と、イオン交換水350部とを混合して100℃に加熱し、ホモジナイザー(IKA社製ウルトラタラックスT50)を用いて分散した後、マントンゴーリン高圧ホモジナイザー(ゴーリン社製)で分散処理し、体積平均粒径200nmのエステルワックスが分散された溶融性添加剤分散液(固形分濃度:20%)を得た。
<<重合体粒子分散液の調製>>
温度調節手段及び窒素置換手段を備えた容器に、酢酸エチル40部及び2-ブタノール25部を投入し、混合溶剤とした後、実施例1と同様にして得られたポリエステル重合体100部を徐々に投入し溶解させた。さらに10質量%アンモニア水溶液(ポリエステル重合体の酸価に対してモル比で3倍量相当量)を入れて30分間撹拌し、混合液とした。
次いで、容器内を乾燥窒素で置換し、温度を40℃に保持して、混合液を撹拌しながらイオン交換水400部を2部/分の速度で滴下し、乳化を行った。滴下終了後、乳化液を室温(20℃以上25℃以下)に戻し、撹拌しつつ乾燥窒素により48時間バブリングを行うことにより、酢酸エチル及び2-ブタノールを1,000ppm以下まで低減させ、更にイオン交換水を加えて固形分濃度を20%に調整して、体積平均粒径200nmの重合体粒子が分散した重合体粒子分散液を得た。
<<乳化凝集>>
丸型フラスコ(ステンレス製)と容器A(ポリエステル製ボトル)とをチューブポンプAで接続し、チューブポンプAの駆動により容器Aに収容した収容液をフラスコへ送液し、容器Aと容器BとをチューブポンプBで接続し、チューブポンプBの駆動により容器Bに収容した収容液を容器Aへ送液する装置を準備した。この装置を用いて、以下の操作を実施した。
上述のようにして得られた重合体粒子分散液500部及びアニオン性界面活性剤(製品名「TaycaPower(登録商標)」を上記装置の丸型フラスコに入れ、0.1Nの硝酸を添加してpHを3.5に調整した後、ポリ塩化アルミニウム濃度が10質量%の硝酸水溶液30部を添加した。続いて、ホモジナイザー(IKA社製ウルトラタラックスT50)を用いて30℃において分散した後、加熱用オイルバス中で1℃/30分のペースで温度を上げながら、凝集粒子の粒径を成長させた。
一方、上記装置の容器Aに上述のようにして得られた重合体粒子分散液150部を入れ、同じく容器Bに上述のようにして得られた溶融性添加剤分散液を25部入れた。次に、チューブポンプAの送液速度を0.70部/分、チューブポンプBの送液速度を0.14部/分に設定し、凝集粒子形成中の丸型フラスコ内の温度が37.0℃に到達した時点からチューブポンプA及びBを駆動させ、各分散液の送液を開始した。これにより、溶融性添加剤の濃度を次第に高めながら、重合体粒子及び溶融性添加剤が分散された混合分散液を容器Aから凝集粒子形成中の丸型フラスコへ送液した。
そして、丸型フラスコへの各分散液の送液が完了し、丸型フラスコ内の温度が48℃になった時点から30分保持した。
その後、上述のようにして得られた重合体粒子分散液50部を丸型フラスコに緩やかに追加して1時間保持した。次いで、0.1Nの水酸化ナトリウム水溶液を添加してpHを8.5に調整した後、撹拌を継続しながら85℃まで加熱し、5時間保持した。そして、20℃/分の速度で20℃まで冷却し、濾過し、イオン交換水で充分に洗浄し、その後乾燥することにより、ポリエステル重合体及びエステルワックスを含む接着性粒子(エステルワックスの量は、ポリエステル重合体100部当たり10部)を得た。接着性粒子の体積平均粒子径は6.0μmであり、平均円形度は0.96であった。
以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表2に示す。
<接着性粒子の調製>
粉砕法を用いる下記の手順で接着性粒子材料(ポリエステル重合体、エステルワックス)を粒子化した。
ポリエステル重合体100部、エステルワックス10部を、同方向回転二軸押出機(混練部分の全長:1560mm、スクリュー径:42mm、バレル内径:43mm)を用いて溶融混練した後、冷却、粗粉砕した。溶融混練の際の押出機への原料供給速度は10kg/時、平均滞留時間は約18秒であった。
その後、得られた粗粉砕物をジェットミルにより粉砕し分級することで、ポリエステル重合体及びエステルワックスを含む接着性粒子を得た。接着性粒子の体積平均粒子径は6.0μmであり、平均円形度は0.94であった。
以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<接着性粒子の調製>
<<単量体組成物の調製>>
実施例1と同様にして得られたポリエステル重合体4.7部、芳香族モノビニル単量体としてのスチレン61.2部、(メタ)アクリル酸エステル単量体としてのn-ブチルアクリレート34.1部、架橋性単量体としてのジビニルベンゼン0.01部を混合した。得られた混合液に、さらに実施例1と同様にして得られたエステルワックス12部を加えて再度混合し、単量体組成物を調製した。
<<分散安定剤(金属水酸化物)を含むコロイド分散液の調製>>
イオン交換水200部に塩化マグネシウム8.0部を溶解してなる水溶液(塩化マグネシウム水溶液)に、イオン交換水50部に水酸化ナトリウム5.6部を溶解してなる水溶液(水酸化ナトリウム水溶液)を撹拌下で徐々に添加して、分散安定剤(金属水酸化物)としての水酸化マグネシウムを含むコロイド分散液を調製した。
<<懸濁重合>>
上記コロイド分散液に、上記単量体組成物を投入し、更に撹拌した後、重合開始剤としてのt-ブチルパーオキシ-2-エチルヘキサノエート(日油社製、製品名「パーブチルO」)2.0部を添加して混合液を得た。得られた混合液を、インライン型乳化分散機(太平洋機工社製、製品名「キャビトロン」)を用いて15,000rpmの回転数で1分間高剪断撹拌して、コロイド分散液中に単量体組成物の液滴を形成した。
単量体組成物の液滴が形成された上記コロイド分散液を反応器に入れ、90℃に昇温して5時間重合反応を行ない、接着性粒子を含む水分散液を得た。
<<乾燥>>
更に、上記接着性粒子を含む水分散液を撹拌しながら、室温(25℃)下で硫酸を滴下し、pHが6.5以下となるまで酸洗浄を行った。次いで、濾過分離を行い、得られた固形分にイオン交換水500部を加えて再スラリー化させて、水洗浄処理(洗浄、濾過及び脱水)を数回繰り返し行った。それから、濾過分離を行い、得られた固形分を乾燥器の容器内に入れ、40℃で48時間乾燥を行い、接着性粒子を得た。
なお接着性粒子は、芳香族モノビニル重合体からなるコア部及びポリエステル重合体からなるシェル部を備えるコアシェル構造を有する接着性重合体と、エステルワックスとを含んでいた。
機能層用組成物の調製に際し、アルミナ粒子に代えて、以下のようにして調製した有機微粒子を用いた以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<有機微粒子(耐熱性微粒子)の調製>
撹拌機を備えた反応器Aに、ドデシル硫酸ナトリウムを0.20部、過硫酸アンモニウムを0.30部、及びイオン交換水を180部入れて混合し混合物とし、65℃に昇温した。一方、別の容器中で、(メタ)アクリル酸エステル単量体としてのn―ブチルアクリレート80.0部、酸基含有単量体としてのメタクリル酸10.0部、ニトリル基含有単量体としてのアクリロニトリル10.0部、ドデシル硫酸ナトリウム0.8部、及びイオン交換水40部を混合して、シード粒子用単量体組成物を調製した。
このシード粒子用単量体組成物を、4時間かけて、上述の反応器Aに連続的に添加して重合反応を行った。シード粒子用単量体組成物の連続添加中における反応器内の温度は、65℃に維持した。また、連続添加終了後、さらに80℃で3時間重合反応を継続させた。これにより、シード粒子の水分散液を得た。なお、シード粒子の体積平均粒子径を結着材と同様にして測定したところ、120nmであった。
次に、撹拌機を備えた反応器に、上述のシード粒子の水分散液を、固形分相当で20部(この内、n-ブチルアクリレート単位は16部、メタクリル酸単位は2部、アクリロニトリル単位は2部)、架橋性単量体としてのエチレングリコールジメタクリレート(共栄社化学株式会社、製品名「ライトエステルEG」)を80部、ドデシルベンゼンスルホン酸ナトリウムを0.8部、重合開始剤としてのt-ブチルパーオキシ-2-エチルヘキサノエート(日油社製、製品名「パーブチルO」)を3.2部、及びイオン交換水を160部入れ、35℃で12時間撹拌することで、シード粒子に架橋性単量体及び重合開始剤を完全に吸収させた。その後、反応器内の温度を90℃に維持し、5時間重合反応(シード重合)を行った。
次いで、スチームを導入して未反応の単量体及び開始剤分解生成物を除去し、有機微粒子(体積平均粒子径:0.5μm)の水分散液を得た。そして、得られた有機微粒子のガラス転移温度を、接着性粒子及び結着材と同様の方法で測定したが、測定温度範囲(-100℃~200℃)においてピークが観測されなかった。これにより、有機微粒子のガラス転移温度が200℃超であることを確認した。
ポリエステル重合体及びエステルワックスを調製せず、以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<接着性粒子の調製>
芳香族モノビニル単量体としてのスチレン81.9部、(メタ)アクリル酸エステル単量体としての2-エチルヘキシルアクリレート18部、架橋性単量体としてのエチレングリコールジメタクリレート0.1部を混合し、単量体組成物を調製した。
上記単量体組成物を用いた以外は、実施例17と同様にして、コロイド分散液を調製し、そして懸濁重合及び乾燥を行い、接着性粒子を得た。
ポリエステル重合体及びエステルワックスを調製せず、以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<接着性粒子の調製>
芳香族モノビニル単量体としてのスチレン60.9部、(メタ)アクリル酸エステル単量体としての2-エチルヘキシルアクリレート39部、架橋性単量体としてのエチレングリコールジメタクリレート0.1部を混合し、単量体組成物を調製した。
上記単量体組成物を用いた以外は、実施例17と同様にして、コロイド分散液を調製し、そして懸濁重合及び乾燥を行い、接着性粒子を得た。
ポリエステル重合体及びエステルワックスを調製せず、以下のようにして調製した接着性粒子を用いた以外は、実施例1と同様にして、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<接着性粒子の調製>
芳香族モノビニル単量体としてのスチレン81.9部、(メタ)アクリル酸エステル単量体としての2-エチルヘキシルアクリレート18部、架橋性単量体としてのエチレングリコールジメタクリレート0.1部を混合した。得られた混合液に、ポリエチレンワックス(融点:95℃、数平均分子量:7,300)5部を加えて再度混合し、単量体組成物を調製した。
上記単量体組成物を用いた以外は、実施例17と同様にして、コロイド分散液を調製し、そして懸濁重合及び乾燥を行い、接着性粒子を得た。
機能層用組成物の調製に際し、アルミナ粒子を使用しなかった以外は、実施例1と同様にして、ポリエステル重合体、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
以下のようにして調製したポリエステル重合体を用いた以外は、実施例1と同様にして、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<ポリエステル重合体の調製>
カルボン酸成分としてのテレフタル酸1661部、並びにアルコール成分としてのビスフェノキシエタノールフルオレン(BPEF)1316部、ネオペンチルグリコール1094部、及びトリメチロールプロパン2.7部(テレフタル酸:BPEF:ネオペンチルグリコール:トリメチロールプロパン=100:30:105:0.2(モル比))からなる混合物を、撹拌しながら、オートクレーブ中、3時間、0.3MPa、260℃で制御し、次いで放圧したのち3時間、常圧、260℃で反応をおこなった。次いで、270℃に昇温し、触媒としてテトラブチルチタネート6.8部(テレフタル酸1モルあたり20×10-4モル)を投入し、系の圧力を徐々に減じて1.5時間後に13Paとし、反応を継続した。適当な粘度になるまで縮合をおこない、ストランドカッターを用いて、ペレット状のポリエステル重合体を得た。得られたポリエステル重合体のガラス転移温度は100℃であった。
以下のようにして調製したポリエステル重合体を用いた以外は、実施例1と同様にして、エステルワックス、接着性粒子、結着材、機能層用組成物、セパレータ、負極、正極、及びリチウムイオン二次電池を得た。そして、実施例1と同様にして各種評価を行った。結果を表3に示す。
<ポリエステル重合体の調製>
アルコール成分としてのエチレングリコール900部、カルボン酸成分としてのテレフタル酸ジメチル2000部、並びにジブチルスズオキサイド4部を、窒素導入管、脱水管、撹拌器及び熱伝対を装備した5リットル容の四つ口フラスコに入れ、165℃から200℃まで70分間かけて昇温し反応させた。次いでトリメチルホスファートを1部添加し、35分間反応させた。次いでカルボン酸成分としてのドデカン二酸を1000部添加し、240℃まで30分かけて昇温し反応させた。さらに265℃まで昇温し、0.1mmHgにて4時間反応させ、ポリエステル重合体を得た。得られたポリエステル重合体のガラス転移温度は0℃であった。
「PES重合体」は、ポリエステル重合体を示し、
「芳香族」は、芳香族ビニル系重合体を示し、
「添加剤」は、溶融性添加剤を示し、
「PES樹脂」は、結晶性ポリエステル樹脂を示し、
「アクリル」は、アクリル系重合体を示し、
「有機」は、有機微粒子を示し、
「接着性粒子の粒子径/耐熱領域の高さ」は、接着性粒子の体積平均粒子径/耐熱領域の積層方向平均高さを示し、
「PE」は、ポリエチレン製の微多孔膜を示す。
10 機能層
11 接着領域
11a 接着性粒子
12 耐熱領域
12a 耐熱性微粒子
12b 結着材
20 基材
T 耐熱領域の積層方向の高さ
D 接着性粒子の粒子径
Claims (10)
- 基材と、前記基材上に配置された機能層とを備える電気化学素子用積層体であって、
前記機能層は、耐熱性微粒子と、接着性重合体を含む接着性粒子と、結着材とを含有し、
前記接着性重合体は、ガラス転移温度を10℃以上95℃以下の範囲に有するポリエステル重合体を含有し、
前記機能層側から平面視した際に、前記機能層は前記接着性粒子からなる接着領域と、前記耐熱性微粒子及び前記結着材からなる耐熱領域とを備え、
前記接着性粒子の体積平均粒子径が、前記耐熱領域の積層方向平均高さよりも大きい、電気化学素子用積層体。 - 前記接着性粒子は、融点を40℃以上95℃以下の範囲に有する溶融性添加剤を更に含有する、請求項1に記載の電気化学素子用積層体。
- 前記溶融性添加剤は、エステルワックス、パラフィンワックス、及びガラス転移温度を10℃以上95℃以下の範囲に有さない結晶性ポリエステル樹脂からなる群から選択される少なくとも1つである、請求項2に記載の電気化学素子用積層体。
- 前記接着性粒子の体積平均粒子径が1.0μm以上10.0μm以下である、請求項1~3の何れかに記載の電気化学素子用積層体。
- 前記耐熱領域の積層方向平均高さに対する前記接着性粒子の体積平均粒子径の比が1.1以上10.0以下である、請求項1~4の何れかに記載の電気化学素子用積層体。
- 前記機能層中における前記接着性粒子の含有量に対する前記耐熱性微粒子の含有量の体積比が、55/45以上95/5以下である、請求項1~5の何れかに記載の電気化学素子用積層体。
- 前記接着性粒子の平均円形度が0.90以上0.99以下である、請求項1~6の何れかに記載の電気化学素子用積層体。
- 前記耐熱性微粒子が無機微粒子である、請求項1~7の何れかに記載の電気化学素子用積層体。
- 前記無機微粒子は、アルミナ粒子、ベーマイト粒子、硫酸バリウム粒子、及び水酸化マグネシウム粒子からなる群から選択される少なくとも1つを含む、請求項8に記載の電気化学素子用積層体。
- 請求項1~9の何れかに記載の電気化学素子用積層体を備える、電気化学素子。
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