CN103804892A - Porous polymer membrane, preparation method thereof and application of porous polymer membrane as gel polymer electrolyte - Google Patents
Porous polymer membrane, preparation method thereof and application of porous polymer membrane as gel polymer electrolyte Download PDFInfo
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- CN103804892A CN103804892A CN201310231733.1A CN201310231733A CN103804892A CN 103804892 A CN103804892 A CN 103804892A CN 201310231733 A CN201310231733 A CN 201310231733A CN 103804892 A CN103804892 A CN 103804892A
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- porous film
- polymer porous
- electrolyte
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005597 polymer membrane Polymers 0.000 title abstract 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 60
- 238000001879 gelation Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 97
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 37
- 229910001416 lithium ion Inorganic materials 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 32
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 27
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000693 micelle Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- -1 through stirring Substances 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- PNGAWASQASFPNE-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-dioxonin-2-one Chemical compound C1(OCCCCC=CO1)=O PNGAWASQASFPNE-UHFFFAOYSA-N 0.000 claims description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 101150004907 litaf gene Proteins 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003527 tetrahydropyrans Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims 2
- 239000011244 liquid electrolyte Substances 0.000 abstract description 21
- 239000003792 electrolyte Substances 0.000 abstract description 10
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- 229920002635 polyurethane Polymers 0.000 abstract description 2
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- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 16
- 238000013019 agitation Methods 0.000 description 13
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- 238000007654 immersion Methods 0.000 description 7
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- 108010010803 Gelatin Proteins 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
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- 101100460844 Mus musculus Nr2f6 gene Proteins 0.000 description 3
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- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
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- 241001330002 Bambuseae Species 0.000 description 1
- 240000005308 Juniperus chinensis Species 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 235000015110 jellies Nutrition 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a porous polymer membrane prepared from a polyvinyl acetal polymer treated by using polyurethane and a preparation method of the porous polymer membrane. Communicated holes are uniformly distributed in the porous polymer membrane, the porous polymer membrane has better electrolyte adsorption capacity and high electrolyte uptake rate up to over 300%, the gelation of the system is realized through adsorbing swelled electrolyte, and the porous polymer membrane and a gel system can stably exist for a long term. The conductivity of a gel polymer electrolyte approaches to the average value 1.0*10<-3>S/cm of the conductivity of a liquid electrolyte, the electrochemical stability window is 2.0-5.0V, the mechanical performance and the electrode compatibility are remarkably improved, the porous polymer membrane can be applied as the gel polymer electrolyte, and the safety of a battery is improved. Meanwhile, diaphragms in a liquid electrolyte system or other battery systems do not need to be used as supports.
Description
Technical field
The invention belongs to polymeric film preparation and application technical field, particularly a kind of polymer porous film and preparation method thereof, and adsorb the stabilising system of swelling electrolytic solution as the application of gel polymer electrolyte.
Background technology
Being widely used of gelatin polymer, the gel polymer electrolyte system of lithium ion battery liquid electrolyte as an alternative, possessed approach liquid electrolyte compared with high ionic conductivity, possessed again the without leakage feature of solid electrolyte.Can solve organic electrolyte and there is high volatility and combustibility, under short-circuit conditions, may occur breaking, the safety problem such as on fire and blast.For large-scale lithium ion battery is in new-energy automobile field, the application in sun power, wind power generation energy storage device provides safeguard.
The gel polymer electrolyte that the polymkeric substance that what at present research was more mainly contain polyoxyethylene (PEO), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polyvinylidene difluoride (PVDF) (PVDF) etc. contain polar group is matrix.
The easy crystallization of PEO base gel polymer electrolyte, causes room-temperature conductivity low; In PAN base gel polymer electrolyte, gelatin polymer film and lithium electrode interface passivation phenomenon are serious, and in the high situation of plasticizer loading, mechanical property declines more serious; PMMA base gel polymer electrolyte mechanical property is poor; In PVDF base gel polymer electrolyte, polymer architecture is regular, and easily crystallization, is unfavorable for ionic conduction.
Visible conventional gelatin polymer kip is all over existing problems, gel-film stability, mechanical property and still need to improve with the consistency of electrode.The problem of in addition, oozing out electrolytic solution from gel is not also properly settled.
Summary of the invention
The advantages such as polyvinyl acetal and derivative thereof have film-forming properties, thermotolerance, water tolerance is good, chemical structure is relatively stable, be applied in already in the fields such as tackiness agent, chemical coating, medical sthptic sponge and be widely used, also have a small amount of investigator to use it in lithium ion battery gel polymer electrolyte system.It mainly contains following several structural unit (wherein R=H, methyl, ethyl or propyl group):
Interior field is controlled etc. and in patent of invention [CN101176233A], have been prepared a kind of gel polymer electrolyte, is made up of polyvinyl acetal or derivatives thereof, solvent, lithium hexafluoro phosphate.Lithium hexafluoro phosphate plays certain katalysis, makes the further polymerization of polyvinyl acetal or derivatives thereof, forms polymer dielectric, suppresses spilling of electrolytic solution, and discharge performance is improved simultaneously.
Bamboo field good fortune history etc. is mentioned in patent of invention [CN101288198A], by the proportion of composing of ring compound and wire compound in adjustment organic solvent, improves solvability and the ionic conductivity of polyvinyl acetal.
The former clear man of Chinese juniper waits and mentions in patent of invention [CN101103070A], reduce the ratio of vinyl alcohol units in polyvinyl acetal by the method for sour modification, implement the Intramolecular exchange reaction that sour modification not only causes acetal ring, and isolated vinyl alcohol units becomes the structure of multiple connections, improve thus the gelatinization performance of organic solvent.
Visible polyvinyl acetal based polyalcohol has the good prospect being applied on lithium ion battery gel polymer, but polyvinyl acetal and derivative thereof solvability in the organic solvents such as carbonic ether is high, can not stable existence, therefore when above-mentioned gel polymer electrolyte is prepared jelly glue polymer battery by polymerized in-situ technique, all must place diaphragm element, cause interface to be increased.
Li Fang magnitude has been prepared a kind of cross-linked pioloform Polyurethane of soluble reticularly in patent of invention [CN1800234A], wherein use dibutyl tin laurate or two lauric acid as catalyzer, utilize 4,4 ’ ?diphenylmethanediisocyanate (MDI) Polyvinyl acetal is learned and is cross-linked into reticulated structure, this kind of polyurethane-reinforcement pressed powder solubilized, for purposes such as coating, paint, binding agents.
In the article of delivering and patent, there is not yet at present and adopt this patent inventive method to prepare polyvinyl acetal Quito pore membrane, and make its gelation become the report of polymer dielectric.
The object of utilization of the present invention is, a kind of polyvinyl acetal and derivative porous-film thereof and preparation method thereof are provided, and this porous-film becomes three-dimensional netted rock steady structure by chemically crosslinked.Above-mentioned polymer porous film has been brought into play excellent film-forming properties that polyvinyl acetal and derivative thereof have, thermotolerance, the good advantage such as water tolerance, metastable chemical structure, simultaneously above-mentioned polymer porous film and preparation method thereof has solved that the solvability in the organic solvents such as carbonic ether of polyvinyl acetal and derivative thereof is high, problem that can not stable existence, and chemical stability significantly improves.Above-mentioned polymer porous film has good absorption electrolytic solution ability, pick up can reach more than 300%, realized (comprising take carbonic ether as main electrolyte system) gelation of system by adsorbing swelling electrolytic solution, and porous-film and gelling system can steady in a long-termly exist.
In addition, the object of the invention is to, above-mentioned polymer porous film is applied in gel polymer electrolyte, be particularly applied in gel polymer lithium ion battery.Because the gel polymer electrolyte of above-mentioned polymer porous film and formation can steady in a long-termly exist, the problem that there will not be the dissolving of polymer porous film in system and electrolytic solution to ooze out, above-mentioned polymer porous film will or cause when polymerized in-situ and electrolytic solution becomes one in electrolytic solution swell gel, do not need to adopt barrier film in liquid electrolytic plastome or other battery systems as support, therefore avoid interface to increase, can effectively improve the ionic conductivity of gel polymer electrolyte.And, because this polymer porous film has been realized (comprising take carbonic ether as main electrolyte system) gelation of system by the swelling electrolytic solution of absorption, in the time being applied in gel polymer electrolyte, possessed the without leakage feature of solid electrolyte; Meanwhile, because the transmission speed of ion in gel polymer electrolyte is greater than the transmission speed in solid state electrolyte, when this polymer porous film is applied in gel polymer electrolyte, can obtain the specific conductivity higher with respect to solid state electrolyte.And for liquid electrolyte, when being applied in gel polymer electrolyte, this polymer porous film can not produce the leakage problem that liquid electrolyte exists, simultaneously can obtain the specific conductivity substantially equating with liquid electrolyte, and this polymer porous film is applied to gel polymer electrolyte can facilitates battery assembling.In addition, traditionally, polyvinyl acetal and derivative thereof, as binding agent, have good adhesive property.Polymer porous film according to the present invention has been brought into play the bonds well performance of polyvinyl acetal and derivative thereof, therefore, than other polymer porous film, the gel polymer electrolyte that above-mentioned polymer porous film forms has the bonding force good with electrode and consistency, reduce interfacial electrochemistry polarization, electrochemical stability is high, and specific conductivity approaches the mean value 10 of liquid electrolyte specific conductivity
?3s/cm.And there is high mechanical property, adopt that above-mentioned gel polymer electrolyte assembled battery operation is convenient, technique is simple.
Polymer porous film in the present invention is through chemically crosslinked processing, and the chemically crosslinked structure of its polyurethane-reinforcement is as follows:
(wherein: R=H, methyl, ethyl or propyl group)
The step of preparation process of polymer porous film is as follows:
(a) polyvinyl formal or its homologue and organic solvent are dissolved in to organic solvent according to mass ratio 1:5-1:20, are configured to solution;
(b) in the solution of above-mentioned configuration, add the diisocyanates material that can make polyvinyl formal or its homologue generation chemically crosslinked, mass ratio according to polyvinyl formal or its homologue and diisocyanates material is 10:1-2:1, stirs 30min;
(c) to the non-solvent that adds a certain proportion of polyvinyl acetal and polyurethane-reinforcement product thereof in the solution of above-mentioned configuration, mass ratio according to the non-solvent of polyvinyl formal or its homologue and polyvinyl acetal and chemically crosslinked product thereof is 10:1-1:1, separate out white micelle, through stirring, micelle is dissolved;
(d), after solution formulated above-mentioned steps is evenly applied, the non-solvent that is immersed in polyvinyl acetal and polyurethane-reinforcement product thereof is bathed or the mixing in bath of its solvent and non-solvent, separates out white film;
(e) by the dry white film polymer porous film that obtains.
The preferred N of organic solvent described in above-mentioned step of preparation process (a) ?methyl-2-pyrrolidone, N, at least one in N ?dimethyl formamide, trichloromethane, tetrahydrofuran (THF), and according to the organic solvent of solubleness difference≤1.7-2 of similar compatibility principle and polyvinyl formal or its homologue; Diisocyanates material described in above-mentioned step of preparation process (b) preferably 4,4 ’ ?diphenylmethanediisocyanate, Jia Ben ?2,4 ?vulcabond, toluene 2,6 ?at least one in vulcabond, hexamethylene diisocyanate, PPDI, isophorone diisocyanate; At least one in the preferred deionized water of non-solvent described in above-mentioned step of preparation process (c), anhydrous methanol, dehydrated alcohol; Drying step described in above-mentioned step of preparation process (e) for to carry out forced air drying or vacuum-drying at 30 ℃-60 ℃.
Above-mentioned polymer porous film can be applicable in gel polymer electrolyte, and polymer porous film adsorbs swelling electrolytic solution, realizes gelation, forms gel polymer electrolyte.Wherein, the main component of electrolytic solution is lithium salts, organic solvent.
Apply the gel polymer electrolyte that above-mentioned polymer porous film forms, can assemble lithium ion battery.In described lithium-ion battery system, positive pole is to be selected from least one of following material: iron lithium phosphate, nickel-cobalt-manganese ternary material, spinel lithium manganate, the lithium-rich manganese-based material of heavy body, negative pole is to be selected from least one of following material: graphite, hard carbon, lithium titanate, silicon base compound and alloy.
In the electrolytic solution using in described lithium-ion battery system, lithium salts is to be selected from least one of following material: LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiAlCl
4, LiCF
3sO
3, LiN (SO
2cF
3)
2, LiBOB, LiSbF
6, LiSCN, LiSnF
6, LiGeF
6, LiTaF
6.
In the electrolytic solution using in described lithium-ion battery system, organic solvent is to be selected from least one of following material: NSC 11801, propylene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, γ ?butyrolactone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, methyl-formiate, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran (THF), 2 ?methyltetrahydrofuran, tetrahydropyrans, dioxolane, 1, 2 ?glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, methyl-sulphoxide, acetone, N, N ?dimethyl formamide, tetramethylene sulfone, dimethyl sulfone.
The assemblies such as gel polymer electrolyte layer that described lithium ion battery is mainly formed by polymer porous film of the present invention, anode pole piece, cathode pole piece, positive pole ear, negative lug form, the assembling mode of battery can be convoluted or laminated type, be that the manufacture method that lithium ion battery generally adopts is all suitable for, its structural representation as shown in Figure 1.
The present invention has the following advantages:
Constituent polyvinyl acetal and the derivative thereof of polymer porous film of the present invention are non-stimulated, nontoxic, environmental friendliness, nonflammable, safe.Polymer porous film prepared by the technology of the present invention is through chemically crosslinked, and chemical stability is good, can not be dissolved in the organic solvents such as carbonic ether chemical stability.The open pore of polymer porous film can be very fast absorption electrolytic solution, as material of main part with support and form the steady in a long-term gel polymer electrolyte existing, there is essential distinction in the gelatinization process that this and polyvinyl acetal and derivative thereof cause other systems as jelling agent.Polymer porous film of the present invention can not dissolve in the electrolyte system comprising take carbonic ether as primary solvent, and mechanical property and being all improved with the consistency of electrode.Therefore high chemical stability and physical strength are that battery process brings more convenience, do not need to utilize the barrier film of liquid electrolytic plastome or other battery systems as support, avoid the use of now widely used gel polymer lithium ion battery septation parts, effectively reduce the number of interfaces in lithium ion battery structure, approached the mean value 10 of liquid electrolyte
?3s/cm.
Accompanying drawing explanation
Fig. 1 is the electric core structure of lithium battery schematic diagram that adopts the gel polymer electrolyte layer of polymer porous film formation of the present invention.
Fig. 2 be embodiment 1 prepare through 4,4 ’ ?the microstructure figure of polyvinyl formal (PVFM) polymer porous film of diphenylmethanediisocyanate (MDI) polyurethane-reinforcement chemically crosslinked processing.
Fig. 3 is the microstructure figure of polyvinyl butyral acetal (PVB) polymer porous film of the MDI chemically crosslinked processing prepared of embodiment 2.
Fig. 4 is the microstructure figure of polyvinyl formal (PVFM) polymer porous film prepared of comparative example 1.
Fig. 5 is that polymer porous film prepared by embodiment 1 causes as after gel polymer electrolyte, the electrochemical stability window result of testing by linear sweep voltammetry.
Fig. 6 is the charge and discharge cycles test result of the lithium ion battery prepared of embodiment 8, voltage range 2.5V～4.25V, charge-discharge magnification 0.1C.
Embodiment
Parametric measurement of the present invention is described below:
The mensuration of pick up
PVFM porous-film through MDI chemically crosslinked can be realized gelation.In gelation process, electrolytic solution immerses the inside of polymer porous film gradually, makes polymers swell, and the film of white presents transparence gradually.In electrolytic solution, soak after 30min, established gelatin polymer porous-film is taken out, drained from electrolytic solution, and blot the residual electrolytic solution of gelatin polymer porous film surface with filter paper, measure pick up.
Pick up=(liquid absorption/porous-film quality) × 100%
Wherein, liquid absorption is that porous-film soaks the poor of quality before and after electrolytic solution.
The method of calculation of specific conductivity
Clamp gel polymer electrolyte to be measured with stainless steel substrates, the battery of composition ┃ stainless steel ┃ GPE ┃ stainless steel ┃ structure, measures its electrochemical interface impedance, ionic conductivity σ that according to the following formula can calculated for gel polymeric film:
σ=L/AR
Wherein, the thickness that L is polymeric film, A is the contact area of film and stainless steel working electrode, the solution resistance that R is gel polymer electrolyte.
By 0.1015g polyvinyl formal (PVFM) be dissolved in 1.0125g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVFM, in solution, add 0.0300g4,4 ’ ?diphenylmethanediisocyanate (MDI), at 75 ℃, stir 30min, drip again the non-solvent of 0.1295g deionized water as polyvinyl acetal and polyurethane-reinforcement product thereof, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.Fig. 2 is the microstructure of the PVFM polymer porous film prepared of embodiment 1, and high pick up 593% has been brought in equally distributed open pore.PVFM polymer porous film prepared by embodiment 1 has high pick up and high chemical stability, is to form stable gel electrolyte system, and obtains prerequisite and the basis of high conductance.The specific conductivity that PVFM polymer porous film prepared by embodiment 1 forms stable gel electrolyte system is 1.25 × 10
?3s/cm, the mean value 10 of a little higher than liquid electrolyte specific conductivity
?3s/cm.And the linear sweep voltammetry test result of Fig. 5 shows, the electrochemical stability window that PVFM polymer porous film prepared by embodiment 1 forms stable gel electrolyte system is within the scope of 2.0V～5.0V, higher than the electrochemical stability window 2.0V～4.3V of liquid electrolyte, electrochemical stability is better than liquid electrolyte.
By 0.1049g polyvinyl butyral acetal (PVB) be dissolved in 1.9975g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVB, in solution, add 0.0111g4,4 ’ ?diphenylmethanediisocyanate (MDI), stir 30min at 75 ℃, then drip 0.0971g deionized water, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.Fig. 3 be embodiment 2 prepare the microstructure of PVB polymer porous film, high pick up 610% has been brought in equally distributed open pore.The high pick up of PVB polymer porous film and high chemical stability, be to form stable gel electrolyte system, and obtain prerequisite and the basis of high conductance.PVB polymer porous film prepared by embodiment 2 forms the specific conductivity 1.33 × 10 of stable gel electrolyte system
?3s/cm, the mean value 10 of a little higher than liquid electrolyte specific conductivity
?3s/cm.
By 0.1012g polyvinyl formal (PVFM) be dissolved in 1.0343g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVFM, in solution, add 0.0315g4,4 ’ ?diphenylmethanediisocyanate (MDI), stir 30min at 75 ℃, then drip 0.0114g deionized water, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.Synthetic PVFM polymer porous film prepared by embodiment 3 has high pick up 411% and high chemical stability, for the formation of stable gel electrolyte system and the acquisition of high conductance provide precondition.Embodiment 3 prepare the PVFM polymer porous film specific conductivity that forms the specific conductivity of stable gel electrolyte system be 1.03 × 10
?3s/cm, close to the mean value 10 of liquid electrolyte specific conductivity
?3s/cm.
By 0.0989g polyvinyl formal (PVFM) be dissolved in 0.9987g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVFM, in solution, add 0.0319g4,4 ’ ?diphenylmethanediisocyanate (MDI), stir 30min at 75 ℃, then drip 0.1010g dehydrated alcohol, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion dehydrated alcohol, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.PVFM polymer porous film prepared by embodiment 4 has high pick up 352% and high chemical stability, for the formation of stable gel electrolyte system and the acquisition of high conductance provide precondition.The specific conductivity that PVFM polymer porous film prepared by embodiment 1 forms the specific conductivity of stable gel electrolyte system is 0.97 × 10
?3s/cm, close to the mean value 10 of liquid electrolyte specific conductivity
?3s/cm.
By 0.1018g polyvinyl formal (PVFM) be dissolved in 0.7857g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVFM, in solution, add 0.0305g4,4 ’ ?diphenylmethanediisocyanate (MDI), stir 30min at 75 ℃, then drip 0.1016g deionized water, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.The chemical stability that PVFM polymer porous film prepared by embodiment 5 is high and high-liquid absorbing rate 00% have promoted the formation of stable gel electrolyte system, the specific conductivity 1.28 × 10 of system
?3s/cm, the mean value 10 of a little higher than liquid electrolyte specific conductivity
?3s/cm.
By 0.0977g polyvinyl formal (PVFM) be dissolved in 0.9805g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of magnetic agitation are all dissolved to PVFM, in solution, add 0.0306g4,4 ’ ?diphenylmethanediisocyanate (MDI), stir 30min at 75 ℃, then drip 0.0230g deionized water, separate out white micelle, separate out white micelle solubilized through stirring, continue magnetic agitation 30min, mixing solutions is prepared complete.In mixing solutions film, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.The method of dry porous-film for example may be, but not limited to,, and porous-film is placed at 30 ℃-60 ℃, by forced air drying or vacuum-drying.The high chemical stability of PVFM polymer porous film prepared by embodiment 6, and high-liquid absorbing rate 485% has promoted the formation of stable gel electrolyte system, the specific conductivity 1.12 × 10 of system
?3s/cm, the mean value 10 of a little higher than liquid electrolyte specific conductivity
?3s/cm.
It should be noted that, although only provided employing polyvinyl formal in embodiment and polyvinyl butyral acetal is prepared polymer porous film of the present invention, those skilled in the art should know, polyvinyl formal and homologue thereof all have as in specification sheets summary of the invention, set forth (1) ?(4) basic structural unit, primary structure feature similarity, all there is certain oh group simultaneously, can form the chemically crosslinked structure of the polyurethane-reinforcement of the polymer porous film of the present invention of listing in summary of the invention part, therefore can adopt other homologues of polyvinyl formal to prepare polymer porous film of the present invention.Although the embodiment of the present invention only described employing N ?methyl-2-pyrrolidone (NMP) dissolve polyvinyl alcohol formal or its homologue, the preferred N of organic solvent ?methyl-2-pyrrolidone, N, at least one in N ?dimethyl formamide, trichloromethane, tetrahydrofuran (THF), those skilled in the art should know according to the solubleness difference of similar compatibility principle and polyvinyl formal or its homologue≤1.7-2 organic solvent is also feasible.Except 4,4 ’ ?outside diphenylmethanediisocyanate (MDI), the diisocyanate resin class material that can also use any other with polyvinyl formal or its homologue generation chemically crosslinked.Except preferred deionized water, anhydrous methanol, these non-solvents cheap and easy to get of dehydrated alcohol, can also in the solution of polyvinyl formal or its homologue and diisocyanates configuration, drip other polyvinyl formal or the non-solvent of its homologue polyurethane-reinforcement product.The mass ratio of polyvinyl formal or its homologue and its organic solvent can be 1:5 ?any one ratio between 1:20.The mass ratio of polyvinyl formal or its homologue and diisocyanates can be 10:1 ?arbitrary ratio between 2:1.The mass ratio of the non-solvent of polyvinyl formal or its homologue and polyvinyl acetal and chemically crosslinked product thereof is the arbitrary ratio between 10:1-1:1.
Comparative example 1
By 0.1953g polyvinyl formal (PVFM) be dissolved in 2.0156g N ?in methyl-2-pyrrolidone (NMP), 45 ℃ of lower magnetic forces are stirred to PVFM and all dissolve, in solution, add 0.1980g deionized water, separate out white micelle, at 45 ℃, continue magnetic agitation, treat that precipitate dissolves.By in above-mentioned solution coating, immersion deionized water, make porous membrane, the dry 1h of porous-film obtaining.Fig. 4 is the microstructure figure for preparing polymer porous film, and porous-film presents porous honeycomb, has the macrovoid that diameter is about 25 μ m, forms on macroporous polymer wall also to distribute comparatively evenly, and diameter is about the fine porosity of 1 ?2 μ m.PVFM polymer porous film without chemically crosslinked can be dissolved in rapidly in the electrolytic solution that comprises organic solvent as LiPF
6/ EC+DMC (3:7in Vol.), cannot form stable gel electrolyte system.
Pick up and Conductivity Ratio are
| Sample | Pick up | |
| Embodiment | ||
| 1 | 593% | 1.25×10 ‐3 |
| |
610% | 1.33×10 ‐3 |
| |
411% | 1.03×10 ‐3 |
| |
352% | 0.97×10 ‐3 |
| |
600% | 1.28×10 ‐3 |
| |
485% | 1.12×10 ‐3 |
| Comparative example 1 | Dissolve | ‐ |
By relatively finding, the constituent of polymer porous film of the present invention is through chemically crosslinked, and chemical stability is good, and polymer porous film can not be dissolved in the Elements in Organic Solvents of electrolytic solution.The open pore of porous-film can be very fast absorption electrolytic solution, form after gel polymer electrolyte, effectively prevent the omission of electrolytic solution.Gel polymer electrolyte specific conductivity is high simultaneously, reaches and approach the mean value 1.12 × 10 of liquid electrolyte specific conductivity
?3.
Embodiment 7
The polymer porous film that embodiment 1 is prepared is immersed in 1mol/L LiPF
6be dissolved in EC:DMC=3:7 (V/V) electrolytic solution, or drip several lithium-ion battery electrolytes to polymer porous film surface.Porous-film adsorbs after swelling electrolytic solution, obtains gel polymer electrolyte, avoids using the diaphragm element that must place in gel polymer lithium ion battery in the past, has effectively reduced the number of interfaces in lithium ion battery structure, is conducive to improve ionic conductivity.Test by linear sweep voltammetry, the electrochemical stability window 2.0V～5.0V of known this kind of gel polymer electrolyte, its result is as shown in Figure 5; By ac impedance measurement, solution resistance is 5.0 Ω, and calculating specific conductivity according to aforementioned formula is 1.25 × 10
?3s/cm.The main component of the electrolytic solution using is lithium salts and organic solvent.Lithium salts is selected from least one in following material: LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiAlCl
4, LiCF
3sO
3, LiN (SO
2cF
3)
2, LiBOB, LiSbF
6, LiSCN, LiSnF
6, LiGeF
6, LiTaF
6.Organic solvent is selected from least one in following material: NSC 11801, propylene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, γ ?butyrolactone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, methyl-formiate, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran (THF), 2 ?methyltetrahydrofuran, tetrahydropyrans, dioxolane, 1, 2 ?glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, methyl-sulphoxide, acetone, N, N ?dimethyl formamide, tetramethylene sulfone, dimethyl sulfone.
Embodiment 8
With LiFePO
4for positive pole, Li is negative pole, assembling half-cell.Battery adopts CR2032 button cell.In battery, do not add diaphragm element, replace, adopt the prepared polymer porous film of embodiment 1.In assembling process, drip a small amount of electrolytic solution polymer porous film and electrode materials are infiltrated mutually, and swelling electrolytic solution makes its gelation.Adopt the prepared polymer porous film of embodiment 1 to be applied to gel polymer electrolyte, and the half-cell that adopts iron lithium phosphate to assemble as positive battery, through charge-discharge test, result as shown in Figure 6 shows that the chemical stability that adopts the prepared polymer porous film of embodiment 1 to be applied to gel polymer electrolyte is good, the cyclical stability excellence of battery, circulating battery 80 times, capability retention reaches 95.4%, approach and adopt liquid electrolyte circulation 80 times, the effect of capability retention 97.6%, has reached the application requiring in battery system.
Can also be by polymer porous film prepared embodiment 1 for be formed the lithium ion battery of positive and negative electrode by other materials.The positive pole of for example lithium ion battery is to be selected from least one of following material: iron lithium phosphate, nickel-cobalt-manganese ternary material, spinel lithium manganate, the lithium-rich manganese-based material of heavy body, negative pole is to be selected from least one of following material: graphite, hard carbon, lithium titanate, silicon base compound and alloy.
Fig. 1 illustrates an embodiment who adopts the battery core structure of lithium-ion battery that obtains as gel polymer electrolyte of polymer porous film of the present invention.This lithium ion battery cell is laminated type or convoluted, comprises anode pole piece 1, is welded on positive pole ear 2, the cathode pole piece 3 of one end of anode pole piece 1 and is welded on negative lug 4 on cathode pole piece 3 and positive pole ear 2 identical one end and the gel polymer electrolyte layer 5 being formed by polymer porous film of the present invention between positive and negative electrode pole piece.It will be appreciated by those skilled in the art that the structure that solid state electrolyte lithium ion battery generally adopts is all applicable to the lithium ion battery that adopts polymer porous film of the present invention to obtain as gel polymer electrolyte.
Adopt lithium ion battery that polymer porous film of the present invention obtains as gel polymer electrolyte in discharge process, lithium ion deintercalation from the structure of cathode pole piece 3 active materials, on the interface of cathode pole piece 3 active materials and gel polymer electrolyte layer 5, there is solvation, in gel polymer electrolyte layer 5, migration reaches anode pole piece 1 one sides, process desolvation on the interface of anode pole piece 1 active material and gel polymer electrolyte layer 5, be embedded into again in the structure of anode pole piece 1 material, and electronics arrives positive pole ear 2 by negative lug 4 via external circuit, the displacement that forms electronics is electric current.In process of charging, contrary with said process, lithium ion deintercalation from anode pole piece 1 active substance, after passing through the interface of gel polymer electrolyte layer 5 and anode pole piece 1 and cathode pole piece 3, is embedded in the structure of cathode pole piece 3 active substances.
Different from liquid electrolyte lithium ion battery, for gel polymer lithium ion battery, due to adopted have certain physical strength polymer porous film Xi Fu ?the swelling gel polymer electrolyte forming after electrolytic solution, avoid using barrier film, multiple interfaces and the obstruction of barrier film to its generation in lithium ion transition process are reduced, more be conducive to the migration of lithium ion, reduced lithium ion battery internal resistance.The shape of battery is not subject to the restriction of liquid electrolyte simultaneously, can make according to design requirements.
Claims (17)
1. a polymer porous film, is characterized in that, component is at least one polyurethane-reinforcement product in polyvinyl formal or its homologue, with porous-film form stable existence.
2. a kind of polymer porous film according to claim 1, the chemically crosslinked structure of its polyurethane-reinforcement is as follows:
(wherein: R=H, methyl, ethyl or propyl group)
3. a preparation method for polymer porous film, is characterized in that, the following processing step of preparation process of this polymer porous film:
(1) polyvinyl formal or its homologue are dissolved in to organic solvent by a certain percentage, are configured to solution;
(2) in the solution of above-mentioned configuration, add a certain proportion of diisocyanates material that makes polyvinyl formal or its homologue generation chemically crosslinked, be stirred to its dissolving;
(3) to the non-solvent that adds a certain proportion of polyvinyl acetal and polyurethane-reinforcement product thereof in the solution of above-mentioned configuration, separate out white micelle, through stirring, micelle is dissolved;
(4), after solution formulated above-mentioned steps is evenly applied, the non-solvent that is immersed in polyvinyl acetal and polyurethane-reinforcement product thereof is bathed or the mixing in bath of its solvent and non-solvent, separates out white film;
(5) by the dry white film polymer porous film that obtains.
4. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, the preferred N of organic solvent ?methyl-2-pyrrolidone, N, N ?at least one in dimethyl formamide, trichloromethane, tetrahydrofuran (THF), and according to the organic solvent of solubleness difference≤1.7-2 of similar compatibility principle and polyvinyl formal or its homologue, and the mass ratio of polyvinyl formal or its homologue and organic solvent is 1:5-1:20.
5. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, diisocyanates material preferably 4,4 ’ ?diphenylmethanediisocyanate, Jia Ben ?2,4 ?vulcabond, toluene 2,6 ?at least one in vulcabond, hexamethylene diisocyanate, PPDI, isophorone diisocyanate, and other diisocyanates material, the mass ratio of polyvinyl formal or its homologue and diisocyanates material is 10:1-2:1.
6. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, at least one in the preferred deionized water of non-solvent, anhydrous methanol, dehydrated alcohol, the mass ratio of the non-solvent of polyvinyl formal or its homologue and polyvinyl acetal and chemically crosslinked product thereof is 10:1-1:1.
7. a kind of preparation method of polymer porous film according to claim 3, is characterized in that, described drying step for to carry out forced air drying or vacuum-drying at 30 ℃-60 ℃.
8. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, organic solvent comprise N ?methyl-2-pyrrolidone, N, N ?dimethyl formamide, trichloromethane, tetrahydrofuran (THF), and according to the organic solvent of solubleness difference≤1.7-2 of similar compatibility principle and polyvinyl formal or its homologue, and the mass ratio of polyvinyl formal or its homologue and organic solvent is 1:5-1:20.
9. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, diisocyanates material comprises 4,4 ’ ?diphenylmethanediisocyanate, Jia Ben ?2,4 ?vulcabond, toluene 2,6 ?vulcabond, hexamethylene diisocyanate, PPDI, isophorone diisocyanate, and other diisocyanates material, the mass ratio of polyvinyl formal or its homologue and diisocyanates material is 10:1-2:1.
10. a kind of preparation method of polymer porous film according to claim 3, it is characterized in that, non-solvent comprises deionized water, anhydrous methanol, dehydrated alcohol, and the mass ratio of the non-solvent of polyvinyl formal or its homologue and polyvinyl acetal and chemically crosslinked product thereof is 10:1-1:1.
11. 1 kinds of lithium ion batteries that use polymer porous film according to claim 1, in described lithium-ion battery system, positive pole is to be selected from least one of following material: iron lithium phosphate, nickel-cobalt-manganese ternary material, spinel lithium manganate, the lithium-rich manganese-based material of heavy body, negative pole is to be selected from least one of following material: graphite, hard carbon, lithium titanate, silicon base compound and alloy.
12. application of a kind of polymer porous film in gel polymer electrolyte according to claim 1, is characterized in that, polymer porous film adsorbs swelling electrolytic solution, realize gelation, form gel polymer electrolyte, wherein, the main component of electrolytic solution is lithium salts and organic solvent.
13. application according to claim 12, is characterized in that, lithium salts is to be selected from least one of following material: LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiAlCl
4, LiCF
3sO
3, LiN (SO
2cF
3)
2, LiBOB, LiSbF
6, LiSCN, LiSnF
6, LiGeF
6, LiTaF
6.
14. application as claimed in claim 12, it is characterized in that, organic solvent is to be selected from least one of following material: NSC 11801, propylene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, gamma-butyrolactone, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, methyl-formiate, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran (THF), 2 ?methyltetrahydrofuran, tetrahydropyrans, dioxolane, 1, 2 ?glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, methyl-sulphoxide, acetone, N, N ?dimethyl formamide, tetramethylene sulfone, dimethyl sulfone.
15. 1 kinds have used the battery core of the lithium ion battery of polymer porous film according to claim 1, and described battery core comprises:
Anode pole piece and the positive pole ear welding on anode pole piece;
Cathode pole piece and the negative lug of welding on cathode pole piece;
Gel polymer electrolyte layer between anode pole piece and cathode pole piece, described gel polymer electrolyte layer adopts polymer porous film claimed in claim 1 to form.
16. lithium ion batteries according to claim 15, the battery core of wherein said lithium ion battery is laminated type or convoluted.
17. 1 kinds comprise the lithium ion battery of the battery core described in power 15 or 16.
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| PCT/IB2013/002452 WO2014072789A2 (en) | 2012-11-09 | 2013-11-05 | Porous polymer membrane, preparation method therefor, and use of same in gel polymer electrolyte |
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| CN105161759A (en) * | 2015-08-21 | 2015-12-16 | 北京科技大学 | Composite electrolyte of lithium-air battery and preparation method of composite electrolyte |
| CN108352569A (en) * | 2016-09-02 | 2018-07-31 | 株式会社Lg化学 | Gel polymer electrolyte and lithium secondary battery including the gel polymer electrolyte |
| CN108701861A (en) * | 2016-02-25 | 2018-10-23 | 株式会社Lg化学 | Composition for a gel polymer electrolyte and lithium secondary battery including the composition |
| CN114725500A (en) * | 2022-04-11 | 2022-07-08 | 万向一二三股份公司 | Polymer composite solid electrolyte and preparation method thereof |
| CN117374515A (en) * | 2023-12-06 | 2024-01-09 | 天津力神电池股份有限公司 | Separator with lithium ion capacity compensation function, preparation method thereof and battery |
| WO2024168812A1 (en) * | 2023-02-17 | 2024-08-22 | 宁德时代新能源科技股份有限公司 | Aldehyde-ketone polymer, electrode sheet and related battery cell, battery, and electric device |
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| CN106374139B (en) * | 2016-11-04 | 2018-08-28 | 北京大学 | A kind of gel electrolyte materials monomer, polymer, preparation method and applications |
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| CN117374515A (en) * | 2023-12-06 | 2024-01-09 | 天津力神电池股份有限公司 | Separator with lithium ion capacity compensation function, preparation method thereof and battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014072789A3 (en) | 2014-11-20 |
| CN103804892B (en) | 2019-01-18 |
| WO2014072789A2 (en) | 2014-05-15 |
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