JP5990804B2 - 電気化学電池用セパレータ - Google Patents
電気化学電池用セパレータ Download PDFInfo
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- JP5990804B2 JP5990804B2 JP2013520699A JP2013520699A JP5990804B2 JP 5990804 B2 JP5990804 B2 JP 5990804B2 JP 2013520699 A JP2013520699 A JP 2013520699A JP 2013520699 A JP2013520699 A JP 2013520699A JP 5990804 B2 JP5990804 B2 JP 5990804B2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 229920000620 organic polymer Polymers 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 17
- 229920000098 polyolefin Polymers 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- -1 aryl sulfonic acid Chemical compound 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000005486 organic electrolyte Substances 0.000 claims description 8
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 239000006183 anode active material Substances 0.000 claims description 3
- 239000012229 microporous material Substances 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 49
- 150000007524 organic acids Chemical class 0.000 description 23
- 229910052809 inorganic oxide Inorganic materials 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- 239000003990 capacitor Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920002313 fluoropolymer Polymers 0.000 description 8
- 239000004811 fluoropolymer Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910001593 boehmite Inorganic materials 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920007859 Kynar® HSV 900 Polymers 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 231100000647 material safety data sheet Toxicity 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940021019 disal Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 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
- 239000002904 solvent Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/491—Porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
メチルエチルケトン中のDISPAL 10SR(SASOL North America、Houston,TXから入手可能な表面改質された酸化アルミニウムの商品名)の20重量%分散体を調製した。SASOLによるDISPAL 10SRの製品安全データシート(MSDS)によれば、酸化アルミニウムはアルミニウムベーマイトであり、表面改質はp−トルエンスルホン酸(PTSA)を含む。別途、N−メチルピロリドン(NMP)中のKYNAR HSV 900の10重量%溶液を調製した。撹拌したフルオロポリマー溶液に酸化アルミニウム分散体を加え、乾燥重量比5:1で酸化アルミニウムおよびフルオロポリマーを含む分散体を調製した。この分散体の固形の割合は、約17%であった。
実施例1の酸化アルミニウムおよびフルオロポリマーの分散体を、Ube製の厚さ20ミクロンのポリオレフィンセパレータに被覆し、ポリオレフィンセパレータの収縮および溶融を防止するために90℃で乾燥させた。コーティングの厚さは、乾燥した状態で1ミクロン〜4ミクロンと異なり、ポリオレフィンセパレータの片側または両側に被覆した。ポリオレフィンセパレータの片側または両側に2ミクロンの厚さの酸化アルミニウム微多孔質コーティングがなされた、実施例1に記載したボタン電池を調製し、ポリオレフィンセパレータのみを有する比較対照のボタン電池に、同等の55℃での安定性、循環、および伝導性を付与した。
メチルエチルケトン中のDISPAL 10F4(SASOL North America、Houston,TXから入手可能な表面改質されたアルミニウムベーマイトの商品名)の20重量%分散体を、40分間撹拌しながら2200rpmで混合した。満足のいく分散体は得られず、ほぼ全ての顔料が混合容器の底に沈殿した。SASOLによるDISPAL 10F4の製品安全データシート(MSDS)によれば、表面改質はギ酸を含む。別途、NMP中のKYNAR HSV 900の10重量%溶液を調製した。アルミニウムベーマイトおよびフルオロポリマーを乾燥重量比3:1で撹拌したフルオロポリマー溶液に、分散しなかったメチルエチルケトン中のDISPAL 10F4混合物を2200rpmで40分間撹拌を続けながら加えた。満足のいく分散体は得られず、ほぼ全ての顔料が混合容器の底に沈殿した。混合物は、放出基板上のセパレータ層を被覆するのに好適ではなかった。
NMP中のKYNAR HSV 900の7.5重量%溶液を調製した。2200rpmで撹拌中のこのフルオロポリマー溶液に、乾燥重量比5:1のアルミニウムベーマイトおよびフルオロポリマー中のDISPAL 10F4を2200rpmで40分間撹拌を続けながら徐々に加えた。満足のいく分散体は得られず、ほぼ全ての顔料が混合容器の底に沈殿した。混合物は、放出基板上のセパレータ層を被覆するのに好適ではなかった。
比較例1および2は、ギ酸を用いた酸化アルミニウムの表面改質は、NMPおよびメチルエチルケトンに代表されるような非プロトン性溶媒における分散性を提供せず、結果的に、可溶性のためにNMP等の非プロトン性溶媒を必要とするポリフッ化ビニリデン(PVDF)および他のフルオロポリマーでセパレータを被覆すること、ならびに例えばセパレータまたはバッテリー電極の被覆等のコーティングにおける使用には好適ではないことを示している。
Claims (16)
- 電流発生電池用セパレータであって、
前記セパレータは、(a)少なくとも50重量%の改質酸化アルミニウムと、(b)有機ポリマーと、を含む微多孔層を備え、
前記改質酸化アルミニウムは、スルホン酸を用いて改質された酸化アルミニウムを有しており、非プロトン性溶媒に分散可能であり、
前記有機ポリマーは、ポリフッ化ビニリデンポリマーを含む、
セパレータ。 - 前記スルホン酸は、アリールスルホン酸である、請求項1に記載のセパレータ。
- 前記スルホン酸は、トルエンスルホン酸である、請求項1に記載のセパレータ。
- 前記改質酸化アルミニウムは、式Al2O3・xH2Oの水和酸化アルミニウムを含み、式中、xは、1.0〜1.5の範囲である、請求項1〜3のいずれかに記載のセパレータ。
- 前記セパレータは、前記微多孔層の重量に基づく60〜90重量%の前記改質酸化アルミニウムを含む、請求項4に記載のセパレータ。
- 前記微多孔層は、平均孔径2nm〜70nmのキセロゲル層である、請求項4に記載のセパレータ。
- 前記電流発生電池は、リチウムイオン二次電池またはリチウム一次電池である、請求項1〜6のいずれかに記載のセパレータ。
- 前記微多孔層は、少なくとも1つの微多孔ポリオレフィン層の片側または両側に被覆される、請求項1〜3のいずれかに記載のセパレータ。
- アノードと、カソードと、リチウム塩を含む有機電解質と、前記アノードと前記カソードとの間に介在するセパレータと、を備える電気化学電池であって、
前記セパレータは、(a)少なくとも50重量%の改質酸化アルミニウムであって、スルホン酸を用いて改質された酸化アルミニウムを有する改質酸化アルミニウムと、(b)有機ポリマーと、を含む微多孔層を備え、
前記改質酸化アルミニウムは、非プロトン性溶媒に分散可能であり、
前記有機ポリマーは、ポリフッ化ビニリデンポリマーを含む、
電気化学電池。 - 前記スルホン酸は、アリールスルホン酸である、請求項9に記載の電池。
- 前記スルホン酸は、トルエンスルホン酸である、請求項9に記載の電池。
- 前記改質酸化アルミニウムは、式Al2O3・xH2Oの水和酸化アルミニウムを含み、式中、xは、1.0〜1.5の範囲である、請求項9〜11のいずれかに記載の電池。
- 前記微多孔層は、平均孔径2nm〜70nmのキセロゲル層である、請求項9〜11のいずれかに記載の電池。
- 前記微多孔層は、少なくとも1つの微多孔ポリオレフィン層の片側または両側に被覆される、請求項9〜11のいずれかに記載の電池。
- 前記アノードのアノード活性材料は、リチウムである、請求項9〜11のいずれかに記載の電池。
- 前記リチウム塩は、ヘキサフルオロリン酸リチウムである、請求項9〜11のいずれかに記載の電池。
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PL2596538T3 (pl) | 2019-06-28 |
CN103283060A (zh) | 2013-09-04 |
CN106784556A (zh) | 2017-05-31 |
JP2017004961A (ja) | 2017-01-05 |
US11728544B2 (en) | 2023-08-15 |
EP3444867A1 (en) | 2019-02-20 |
US20170271638A1 (en) | 2017-09-21 |
EP2596538A2 (en) | 2013-05-29 |
WO2012011944A2 (en) | 2012-01-26 |
US20240113392A1 (en) | 2024-04-04 |
KR20140018171A (ko) | 2014-02-12 |
DK2596538T3 (en) | 2019-04-01 |
EP2596538B1 (en) | 2018-12-19 |
JP2013535773A (ja) | 2013-09-12 |
US20130171500A1 (en) | 2013-07-04 |
JP6505052B2 (ja) | 2019-04-24 |
US20210175581A1 (en) | 2021-06-10 |
EP3444867B1 (en) | 2020-03-25 |
ES2713517T3 (es) | 2019-05-22 |
US10833307B2 (en) | 2020-11-10 |
CN103283060B (zh) | 2017-02-15 |
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