CN114464960A - Lithium battery composite diaphragm and preparation method and application thereof - Google Patents
Lithium battery composite diaphragm and preparation method and application thereof Download PDFInfo
- Publication number
- CN114464960A CN114464960A CN202210248783.XA CN202210248783A CN114464960A CN 114464960 A CN114464960 A CN 114464960A CN 202210248783 A CN202210248783 A CN 202210248783A CN 114464960 A CN114464960 A CN 114464960A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- lithium
- battery
- oxide solid
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 116
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 119
- 239000002245 particle Substances 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011247 coating layer Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000002562 thickening agent Substances 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 91
- -1 polyoxyethylene nonyl phenyl ether Polymers 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000007756 gravure coating Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- INBMQYRWBRXTJA-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCC)[Na] Chemical compound C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCC)[Na] INBMQYRWBRXTJA-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- VMMVQEIZBCZSNG-UHFFFAOYSA-N buta-1,3-diene prop-1-enylbenzene Chemical compound C=CC=C.CC=CC1=CC=CC=C1 VMMVQEIZBCZSNG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 7
- 238000011056 performance test Methods 0.000 description 61
- 238000007600 charging Methods 0.000 description 30
- 238000002156 mixing Methods 0.000 description 16
- 238000005245 sintering Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000011265 semifinished product Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010280 constant potential charging Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000391 smoking effect Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011076 safety test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 1
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical compound FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 description 1
- MHFMYGHRYRSFIG-UHFFFAOYSA-L dilithium;dihydroxide Chemical compound [Li+].[Li+].[OH-].[OH-] MHFMYGHRYRSFIG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- 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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
-
- 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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing 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
- H01M50/489—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium battery composite diaphragm and a preparation method and application thereof. The lithium battery composite diaphragm comprises a base film and an oxide solid electrolyte coating layer; the oxide solid electrolyte coating layer includes oxide solid electrolyte particles. Adding a dispersing agent into a solvent, fully stirring, then adding oxide solid electrolyte particles, uniformly grinding to obtain slurry A, then continuously adding a thickening agent, a binder and a wetting agent, and fully stirring to obtain slurry B; and coating the slurry B on a base film, baking to form an oxide solid electrolyte coating, and rolling to obtain the composite diaphragm. According to the invention, the oxide solid electrolyte layer is coated on the surface of the base film to form the composite diaphragm, and the composite diaphragm is adopted during battery assembly, so that the safety performance and the electrochemical performance of the battery can be improved simultaneously.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery composite diaphragm and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, good cycle performance, long service life, low self-discharge, no memory effect and the like, gradually occupies a larger application market in the aspects of energy storage, power batteries, 3C electronics and the like, and has wide application prospects.
However, with the large-scale popularization and application of electric vehicles, safety accidents happen sometimes, and the safety of lives and properties of drivers and passengers is damaged. Safety accidents have become fatal hidden dangers for the development of electric automobiles. The essence of the electric automobile safety accident is the thermal runaway of the power battery. Thermal runaway of a power battery refers to a phenomenon in which the temperature of the battery suddenly rises at an uncontrollable rate in a short time due to dangerous exothermic side reactions inside the battery, and is usually accompanied by phenomena such as smoking, burning on fire, and even explosion. Thermal runaway is a chain reaction, and in the thermal runaway process, side reactions of a battery cathode begin to be carried out firstly, wherein the side reactions comprise Solid Electrolyte Interphase (SEI) film decomposition (at 70-130 ℃), reaction of a lithium-intercalated graphite cathode and a solvent (at 120-200 ℃), and the like. When the temperature rises to about 200 ℃, the cathode material begins to decompose and release oxygen, and the decomposition temperature depends on the composition and lithium intercalation state of the cathode, such as the higher the nickel content is, the lower the decomposition temperature of the cathode is for a commonly used nickel-cobalt-manganese ternary cathode (NCM). At high temperature, the anode material and oxygen generated by the anode material have strong redox reaction with electrolyte and a cathode, release a large amount of heat, trigger severe temperature rise of the battery, further trigger reactions such as adhesive reaction, electrolyte combustion and the like, and cause thermal runaway of the battery. Particularly, for a high-capacity positive electrode, oxygen-containing free radicals and oxygen are generated at high temperature, and severe redox reactions are generated with an electrolyte and a negative electrode, so that the high-capacity positive electrode is a main heat source for thermal runaway of a battery. The triggering reasons causing the thermal runaway of the lithium ion battery are divided into 3 modes of mechanical abuse triggering, electrical abuse triggering and thermal abuse triggering. The mechanical abuse can cause the deformation or the rupture of a battery diaphragm, so that the direct contact short circuit of the anode and the cathode in the battery is caused, and the electrical abuse is caused; and the heat production such as electric abuse lower joule heat and the like is increased, so that the temperature of the battery is increased, the battery is developed into heat abuse, and further chain type heat production side reaction in the battery is triggered, and finally the thermal runaway of the battery is caused. Therefore, in order to solve the thermal runaway problem of the battery, it is necessary to improve the safety stability of the battery material and system overall.
The existing method for improving the safety performance of the battery through coating the diaphragm comprises the following steps:
in patent CN109167001A, at least one side of the separator is coated with inorganic particulate materials such as nano alumina and burm stone, so as to improve the high temperature resistance of the separator, reduce thermal shrinkage when the battery is heated, delay thermal runaway when the battery is short-circuited, and improve the thermal runaway threshold of the battery;
in patent CN111509168A, when inorganic particles are coated on the surface of the separator, a high temperature resistant binder is used to replace a common binder, so as to further reduce the thermal shrinkage of the separator and improve the thermal runaway threshold of the battery;
however, the above type of coated separator has some problems: in the thermal runaway process of the battery, the continuous reaction of the negative electrode and the electrolyte is an induction factor of the thermal runaway, and the oxygen evolution of the positive electrode material is diffused to the negative electrode and generates a violent reaction, so that the positive electrode material is a main source for violent release of heat in the thermal runaway process of the battery. However, in the above method for modifying the surface coating of the separator material, measures are taken to prevent the battery from further heat release after the violent heat release process. At this time, the battery material is already damaged by the heat cumulatively released from the inside of the battery, and the battery safety is difficult to ensure.
Therefore, a method with simple steps and cost advantages is still required to be found to improve the safety performance of the battery.
Disclosure of Invention
Aiming at the limitations existing in the prior art, the invention provides a lithium battery composite diaphragm and a preparation method and application thereof. According to the invention, the oxide solid electrolyte layer is coated on the surface of the base film to form the composite diaphragm, and the composite diaphragm with the solid electrolyte layer is adopted during battery assembly, so that the safety performance and the electrochemical performance of the battery can be improved simultaneously.
One of the objects of the present invention is to provide a composite separator for a lithium battery, the composite separator including a base film and an oxide solid electrolyte coating layer;
the oxide solid electrolyte coating layer includes oxide solid electrolyte particles;
the oxide solid electrolyte particles are selected from lithium-containing materials or a mixture of lithium-containing materials and aluminum phosphate;
the lithium-containing material comprises a compound consisting of lithium, hydrogen, aluminum, phosphorus, halogen and oxygen elements.
Preferably, the lithium-containing material has the chemical formula of Li1+xH1-xAl(PO4)O1-yM2yWherein 0 is less than or equal to x<1，0<y<0.1, M is a halogen element,
m is preferably selected from any one of F, Cl, Br or I; preferably the lithium-containing material is reacted with AlPO4The mass ratio of (A) to (B) is 1-4: 1;
more preferably, the lithium-containing material is selected from LiHAl (PO)4)O1-yM2yAt least one of (1), most preferably LiHAl (PO)4)O0.96F0.08、LiHAl(PO4)O0.95F0.1、LiHAl(PO4)O0.94Cl0.12Or LiHAl (PO)4)O0.94Br0.12At least one of;
the crystal form of the aluminum phosphate is one or more of quartz type, tridymite type or cristobalite type.
Preferably, the preparation method of the lithium-containing material comprises the following steps:
correspondingly weighing lithium salt, an aluminum-containing material, a phosphorus-containing material and a halogen-containing material according to the composition of the lithium-containing material, and uniformly mixing to obtain a mixture;
and (2) sintering the mixture, and optionally crushing to obtain the lithium-containing material.
Preferably, the lithium salt is selected from at least one of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate;
the aluminum-containing material is selected from at least one of aluminum oxide, aluminum hydroxide or aluminum sulfate;
the phosphorus-containing material is at least one of phosphorus pentoxide, phosphoric acid, phosphate or phosphine;
the halogen-containing material is selected from at least one of lithium hexafluorophosphate, hydrogen fluoride or phosphorus fluoride.
Preferably, the molar ratio of Li, Al, P and halogen in the lithium salt, the aluminum-containing material, the phosphorus-containing material and the halogen-containing material is 10-20: 10-20: 10-20: 1, mixing and batching;
in the step (1), the mixing is carried out in a stirring and mixing mode, preferably, the mixing time is 10 s-30 min, and the stirring speed is 200 rpm-2000 rpm;
in the step (2), the sintering treatment temperature is 300-1000 ℃, and the sintering time is 5-256 hours; the sintering atmosphere is air atmosphere or inert gas atmosphere;
when the material is crushed, firstly, the semi-finished product lithium-containing material is poured into crushing equipment for primary crushing treatment, and then the material after the primary crushing treatment is put into the crushing equipment for crushing, so that the lithium-containing material is finally obtained.
Preferably, the lithium-containing material prepared by the invention has a characteristic diffraction peak at 15-35 degrees of measured 2 theta angle when subjected to X-ray diffraction.
Preferably, when the oxide solid state electrolyte particles are a mixture of a lithium-containing material and aluminum phosphate, the oxide solid state electrolyte particles are prepared by:
and uniformly mixing the lithium-containing material and the aluminum phosphate to obtain uniformly mixed powder, carrying out heat treatment on the uniformly mixed powder under the protection of inert gas, cooling and crushing to obtain the material for improving the safety of the battery.
Preferably, the lithium-containing material has a particle size in the range of 0.5 to 100 μm;
the inert gas comprises one or more of nitrogen, helium or argon;
the heat treatment condition is that the temperature is kept for 1 to 20 hours at 100 to 1000 ℃, and the temperature is preferably raised to 100 to 1000 ℃ at the speed of 1 to 20 ℃/min;
the temperature is reduced to room temperature at a rate of 1-20 deg.C/min.
Preferably, when the lithium-containing material is uniformly mixed with the aluminum phosphate, the mixing equipment comprises: one of a double-motion mixer, a three-dimensional mixer, a V-shaped mixer, a single-cone double-helix mixer, a trough-type ribbon mixer or a horizontal non-gravity mixer.
Preferably, the heat treatment apparatus comprises one of a box furnace, a tube furnace, a roller kiln, a pusher kiln or a rotary furnace.
Preferably, a crushing device is used for finely crushing the powder or block-shaped mixed material obtained after heat treatment and temperature reduction; the crushing apparatus includes: one or more of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher and a roller crusher, a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact crusher, an expansion crusher, a ball mill crusher, a high-speed rotation projection crusher or a high-speed rotation impact crusher.
Preferably, the first and second electrodes are formed of a metal,
the size of the oxide solid electrolyte particles is 10nm-10um, preferably 100nm-1 um;
the oxide solid electrolyte coating layer is coated on one side or two sides of the base film;
the thickness of the oxide solid electrolyte coating layer is 0.3-20 mu m, preferably 800 nm-4 mu m;
preferably, the first and second electrodes are formed of a metal,
the oxide solid electrolyte coating layer further includes a thickener, a binder, a wetting agent, and a dispersant.
The base membrane is a polymer porous membrane or a polymer porous membrane loaded with a high-temperature resistant ceramic particle coating layer.
Preferably, the mass ratio of the oxide solid electrolyte particles, the dispersing agent, the thickening agent, the binder and the wetting agent is 100 (0.3-0.8): (1-9): 3-10): 0.4-1.2.
In the invention, the proportion of the oxide solid electrolyte particles, the dispersing agent, the thickening agent, the binder and the wetting agent belongs to the conventional proportion, and the stable slurry can be formed by self-adjusting according to the use requirement.
Preferably, the dispersant is selected from at least one of sodium polyacrylate, ammonium polyacrylate copolymer and polyvinyl alcohol;
the thickening agent is selected from at least one of sodium carboxymethyl cellulose, carboxyethyl cellulose, sodium alginate, polyacrylamide or polyvinyl alcohol;
the binder is selected from at least one of polymethacrylic acid, methyl styrene-butadiene rubber, styrene-acrylic emulsion, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate and polyurethane, or a copolymer formed by methyl methacrylate and one or more monomers of methacrylic acid, ethacrylic acid, ethyl acrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate;
the wetting agent is selected from at least one of sodium perfluorooctanoate, nonylphenol polyoxyethylene ether, fluoroalkyl methoxy alcohol ether, polyoxyethylene alkylamine, butyl sodium naphthalene sulfonate, aryl sodium naphthalene sulfonate, sodium dodecyl benzene sulfonate or sodium alkyl sulfate.
Preferably, the polymer porous membrane is selected from at least one of polyethylene, polypropylene, polyimide or polyethylene terephthalate;
the high-temperature resistant ceramic particle coating layer is selected from an aluminum oxide, boehmite, magnesium oxide or silicon dioxide coating layer;
the thickness of the high-temperature resistant ceramic particle coating layer is 1-5 mu m;
the high-temperature resistant ceramic particle coating layer is coated on one side or two sides of the polymer porous membrane.
The second purpose of the invention is to provide a preparation method of the lithium battery composite diaphragm,
(1) adding a dispersing agent into a solvent, fully stirring, then adding oxide solid electrolyte particles, uniformly grinding to obtain slurry A, then continuously adding a thickening agent, a binder and a wetting agent, and fully stirring to obtain slurry B;
(2) and coating the slurry B on a base film, baking to form an oxide solid electrolyte coating, and rolling to obtain the composite diaphragm.
Preferably, in the step (1),
the solvent comprises water system or oil system solvent, preferably at least one of water, ethanol, N-methyl pyrrolidone, tetrahydrofuran, cyclohexane, petroleum ether, acetone, dimethyl acetamide or N, N-dimethylformamide;
in the step (1), the step (c),
stirring for 10-60 min;
in the step (2),
the coating method comprises a micro-gravure coating method and a spray coating method;
the baking temperature is 30-80 ℃ and the baking time is 0.5-30 min.
The invention also provides the application of the lithium battery composite diaphragm in the lithium battery.
The oxide solid electrolyte layer is coated on the surface of the diaphragm, and the oxide solid electrolyte layer faces to the negative side or the positive side when the battery is assembled, so that the safety performance and the electrochemical performance of the battery can be improved simultaneously.
The technical principle is as follows: firstly, the oxide solid electrolyte has a heat absorption effect, can absorb a part of heat, relieves electrode overheating, and improves the heat shrinkage performance of the diaphragm; secondly, halogen elements in the material can participate in the formation of CEI/SEI of the electrode, so that the bonding degree of an electrode/diaphragm interface is improved; further, Li — X (X ═ F, Cl, Br, I) such as LiF is formed at the anode; the composition can improve the stability of the CEI/SEI on the surface of the pole piece, and inhibit the reaction of anode oxygen loss, cathode and electrolyte, cathode and oxygen during thermal runaway, thereby preventing the battery from releasing heat in the early and later stages of the thermal runaway process of the battery and improving the safety performance of the battery. The solution to improve the thermal safety of the battery is superior to the prior art, since it can function early on in thermal runaway.
The doping of the hydrogen element changes the polarization property and the surface energy of the solid electrolyte material, so that the solid electrolyte material is compatible with the CEI/SEI generated by the decomposition of the existing electrolyte, and is beneficial to generating more stable CEI/SEI, thereby improving the interface stability of the solid electrolyte material.
Because the separator coating participates in the formation of the CEI/SEI, the stability of the CEI/SEI is improved, and the electrode/separator interface is more uniform, lithium ion transport is faster in the CEI/SEI and the electrode/separator interface. This is why the electrochemical performance, particularly the rate performance, of the battery is also improved after the separator is used.
Compared with the prior art, the invention at least has the following advantages and prominent effects:
the oxide solid electrolyte particles added into the oxide solid electrolyte coating layer have low halogen content, the material synthesis difficulty is low, and the situations of halogen element segregation and uneven distribution are not easy to occur; and they are phosphate structures, and compared with the existing perovskite structure and garnet structure solid electrolyte, the phosphate structure solid electrolyte material has better stability.
The oxide solid electrolyte particles added into the oxide solid electrolyte coating layer mainly contain elements such as lithium aluminum phosphorus oxygen and the like, and do not contain Ti or Ge elements which are easy to reduce at a negative electrode, and SEI/CEI formed on the surface of the negative electrode/positive electrode is more stable.
Halogen elements in the oxide solid electrolyte particles added into the oxide solid electrolyte coating layer can participate in the formation of CEI/SEI, such as LiF formed on the negative electrode, so that the stability of CEI/SEI is improved, the reactions of the positive electrode oxygen evolution, the negative electrode and electrolyte, and the negative electrode and oxygen are inhibited, and the safety performance of the battery is improved.
Unlike general solid electrolyte materials, the present invention innovatively uses doping of hydrogen elements to change the polarization properties and surface energy of the solid electrolyte material, so that it is compatible with the CEI/SEI generated by the decomposition of the existing electrolyte, and helps to generate more stable CEI/SEI, thus improving the interfacial stability of the solid electrolyte material. The oxide solid electrolyte coating layer disclosed by the invention is high in chemical stability, the pH range after dispersion in water is 6-9, the diaphragm slurry mixing and coating effects are not influenced, the current mainstream preparation process of the diaphragm is not changed, and the oxide solid electrolyte coating layer has the advantages of high stability and low cost and is suitable for large-scale application.
The oxide solid electrolyte coating layer has certain ion conductivity, and the introduction of the oxide solid electrolyte does not obviously hinder the ion transport capability in the negative electrode within the content range of the solid electrolyte. Even as lithium ion transport is faster in the CEI/SEI and electrode/separator interfaces, battery electrochemical performance, especially rate performance, is improved after use of the separator.
The lithium battery assembled on the basis of the composite negative plate has the effect of simultaneously improving the safety performance and the rate performance of the battery, the battery can smoothly pass a needling test, and other safety performance test results are improved.
Drawings
FIG. 1 is a composite separator made according to one embodiment of the present invention;
FIG. 2 is a composite separator made according to another embodiment of the present invention;
FIG. 3 is a composite separator made according to another embodiment of the present invention;
FIG. 4 is a composite separator made according to another embodiment of the present invention;
FIG. 5 is a composite separator made according to another embodiment of the present invention;
fig. 6 is an XRD pattern of the lithium-containing material prepared in example 1 of the present invention;
fig. 7 is an XRD pattern of the lithium-containing material prepared in example 2 of the present invention;
fig. 8 is an XRD pattern of the lithium-containing material prepared in example 3 of the present invention;
fig. 9 is an XRD pattern of the lithium-containing material prepared in example 4 of the present invention.
Description of reference numerals:
11-a high-molecular porous membrane layer, 21-a high-temperature resistant ceramic particle coating layer with the coating facing the negative electrode, 22-a high-temperature resistant ceramic particle coating layer with the coating facing the positive electrode, 31-an oxide solid electrolyte coating layer with the coating facing the negative electrode, and 32-an oxide solid electrolyte coating layer with the coating facing the positive electrode.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The electrochemical performance test method of the lithium battery comprises the following steps:
1. cycle performance test
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) discharging the battery at a constant current of 1C until the battery reaches a discharge termination voltage, stopping discharging, and recording the discharge capacity; thus completing the cycle of one week;
c) repeating steps a and b until the discharge capacity is lower than 80% of the first week discharge capacity, and recording the total cycle number of the battery at the moment.
2. Multiplying power test
a) Charging the battery at 23 +/-2 ℃ by multiplying power of 0.1C, 0.2C, 0.33C, 1C, 2℃ and 3C to the charge termination voltage, converting the battery into the same multiplying power to discharge to the discharge termination voltage, and circulating the same multiplying power for 4 times;
b) recording discharge capacity conditions with different multiplying powers;
c) the ratio of the 3C discharge capacity to the 0.33C discharge capacity was calculated and recorded as 3C/0.33C, and the rate performance was evaluated.
3. High temperature cycle
a) Charging at 45 ℃ with a constant current of 1C until the charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, and stopping charging;
b) standing the battery for 5h at 45 ℃;
c) discharging the battery at a constant current of 1C at a high temperature of 45 ℃ until the discharge termination voltage is reached, stopping discharging, and recording the discharge capacity; thus completing the cycle of one week;
d) repeating the steps a-c until the discharge capacity is lower than 80% of the first week discharge capacity, and recording the discharge capacity of the battery and the total cycle number at the moment.
The safety performance test method of the lithium battery comprises the following steps:
1. overcharge
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) and (4) continuously charging at a constant current of 1C until the thermal runaway of the battery occurs, and recording the voltage value of the battery when the thermal runaway begins to occur.
2. Hot box
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) the cell was placed in a test chamber. Heating the test chamber at a temperature rise rate of 5 ℃/min, keeping the temperature constant for 1h after the temperature in the test chamber reaches 160 +/-2 ℃;
the battery can pass through the battery without smoking, fire or explosion, or not pass through the battery.
3. Falling down
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) falling freely on the concrete slab according to the falling height of 1 m; each surface of the soft package battery falls once respectively, and six tests are carried out in total; after six experiments, the battery passes without smoking, fire or explosion, otherwise, the battery does not pass.
4. Impact of heavy object
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) placing the battery on the surface of the platform, transversely placing a metal rod with the diameter of 15.8mm +/-0.2 mm on the upper surface of the geometric center of the battery, adopting a weight with the mass of 9.1kg +/-0.1 kg to impact the surface of the battery with the metal rod in a free falling state from a high position with the mass of 610mm +/-25 mm, observing for 6 hours, and determining that the battery passes through the battery without smoking, igniting or exploding, or else, determining that the battery does not pass through the battery.
5. Acupuncture and moxibustion
a) Charging at a constant current of 1C at a temperature of 23 +/-2 ℃ until a charging termination voltage is reached, then converting to constant voltage charging until the charging current multiplying power is reduced to 0.05C, stopping charging, and standing for 1 h;
b) a high-temperature-resistant steel needle with the diameter of 8mm (the conical angle of the needle tip is 45 degrees, the surface of the needle is smooth and clean and has no rust, oxide layer and oil stain) penetrates through the battery plate at the speed of 25mm/s from the direction vertical to the battery plate, the penetrating position is the geometric center of the punctured surface, and the steel needle stays in the storage battery;
c) observing for 1 h; the battery can pass through the battery without smoking, fire or explosion, or not pass through the battery.
Example 1
A method for preparing a composite diaphragm of a lithium battery,
(1) adding 0.5 weight part of dispersant sodium polyacrylate into solvent water, stirring, and adding 100 weight parts of oxide solid electrolyte particles LiHAl (PO)4)O0.95F0.1The particle size is 600nm, the ball milling is uniform, slurry A is prepared, then 1 weight part of thickener carboxymethylcellulose sodium, 5 weight parts of binder polyacrylate and 0.4 weight part of wetting agent sodium perfluorooctanoate are continuously added, the solid electrolyte accounts for 94 wt%, and the slurry B is prepared after the full stirring;
(2) and (3) taking the slurry B, performing scraping coating on a polyethylene base film with aluminum oxide coatings on two sides through a micro-gravure coating machine, baking for 2 minutes at 40 ℃ to form an oxide solid electrolyte coating, and rolling to obtain the composite diaphragm, wherein the structural schematic diagram is shown in figure 1.
The lithium battery composite diaphragm prepared by the method comprises a base film and an oxide solid electrolyte coating layer;
the thickness of the base film is 13 mu m;
the thickness of the oxide solid electrolyte coating layer is 1 μm;
the lithium battery composite diaphragm prepared by the method is used for assembling a lithium battery, the battery structure is an LFP (linear Linear Power pack) graphite soft package battery, a solid electrolyte coating faces to the positive electrode side, the prepared lithium battery is subjected to the working steps of liquid injection, formation, capacity grading and the like, and then electrochemical test and safety test are carried out, and the specific electrochemical performance test result is shown in table 1; the specific lithium battery safety performance test results are shown in table 2.
LiHAl (PO) containing lithium material4)O0.95F0.1The preparation method comprises the following steps:
uniformly stirring and mixing lithium salt lithium hydroxide, aluminum-containing material aluminum hydroxide, phosphorus-containing material phosphoric acid and halogen-containing material hydrogen fluoride according to a molar ratio of Li to Al to P to halogen of 10: 10: 10:1, mixing time is 10min, and stirring speed is 500 rpm; obtaining a mixture;
sintering the mixture at 1000 ℃ for 5 h; and the sintering atmosphere is air atmosphere to obtain a semi-finished product lithium-containing material, then the semi-finished product lithium-containing material is poured into crushing equipment for primary crushing treatment, then the material subjected to the primary crushing treatment is put into crushing equipment for crushing, and after the crushing treatment, the lithium-containing material with the particle size of 600nm is obtained.
The lithium-containing material prepared by the method comprises hydrogen, aluminum, phosphorus, halogen and oxygen, and has a chemical formula of LiHAl (PO)4)O0.95F0.1(ii) a When the lithium-containing material is subjected to X-ray diffraction, the measured 2 theta angle has a characteristic diffraction peak at 15-35 degrees, and the corresponding XRD is shown in figure 6.
Example 2
Solid electrolyte particles were replaced with lihai (PO)4)O0.96F0.08The cell structure is LCO graphite, other parametersThe same as example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
LiHAl (PO) containing lithium material4)O0.96F0.08The preparation method comprises the following steps:
uniformly stirring and mixing lithium salt lithium carbonate, aluminum-containing material aluminum oxide, phosphorus pentoxide as a phosphorus-containing material and halogen-containing material hydrogen fluoride according to a molar ratio of Li, Al, P and halogen of 12.5: 12.5: 12.5: 1, mixing time is 30min, and stirring speed is 200 rpm; obtaining a mixture;
sintering the mixture, wherein the sintering temperature is 300 ℃, and the sintering time is 200 h; and the sintering atmosphere is nitrogen atmosphere to obtain a semi-finished product lithium-containing material, then the semi-finished product lithium-containing material is poured into crushing equipment for primary crushing treatment, then the material subjected to the primary crushing treatment is put into crushing equipment for crushing, and after the crushing treatment, the lithium-containing material with the particle size of 600nm is obtained.
The lithium-containing material prepared by the method comprises hydrogen, aluminum, phosphorus, halogen and oxygen, and has a chemical formula of LiHAl (PO)4)O0.96F0.08(ii) a When the lithium-containing material is subjected to X-ray diffraction, the measured 2 theta angle has a characteristic diffraction peak at 15-35 degrees, and the corresponding XRD is shown in figure 7.
Example 3
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Cl0.12The battery structure is NCM graphite, and other parameters are the same as those in embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
LiHAl (PO) containing lithium material4)O0.94Cl0.12The preparation method comprises the following steps:
uniformly stirring and mixing lithium acetate, aluminum hydroxide containing an aluminum material, phosphine containing a phosphorus material and phosphorus chloride containing a halogen material according to a lithium salt, wherein the molar ratio of Li to Al to P to halogen is 16.6: 16.6: 16.6: 1, mixing time is 1min, and stirring speed is 1800 rpm; obtaining a mixture;
sintering the mixture, wherein the sintering temperature is 500 ℃, and the sintering time is 100 h; and the sintering atmosphere is nitrogen atmosphere to obtain a semi-finished product lithium-containing material, then the semi-finished product lithium-containing material is poured into crushing equipment for primary crushing treatment, then the material subjected to the primary crushing treatment is put into crushing equipment for crushing, and after the crushing treatment, the lithium-containing material with the particle size of 600nm is obtained.
The lithium-containing material prepared by the method comprises hydrogen, aluminum, phosphorus, halogen and oxygen, and has a chemical formula of LiHAl (PO)4)O0.94Cl0.12(ii) a When the lithium-containing material is subjected to X-ray diffraction, the measured 2 theta angle has a characteristic diffraction peak at 15-35 degrees, and the corresponding XRD is shown in figure 8.
Example 4
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Br0.12The battery structure is NCM graphite, the solid electrolyte coating faces to the negative side, and other parameters are the same as those in embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
LiHAl (PO) containing lithium material4)O0.94Br0.12The preparation method comprises the following steps:
uniformly stirring and mixing lithium acetate, aluminum hydroxide containing aluminum material, phosphine containing phosphorus material and phosphorus bromide containing halogen material according to the molar ratio of Li to Al to P to halogen of 16.6: 16.6: 16.6: 1, mixing time is 10min, and stirring speed is 1000 rpm; obtaining a mixture;
sintering the mixture at 800 ℃ for 50 h; and the sintering atmosphere is nitrogen atmosphere to obtain a semi-finished product lithium-containing material, then the semi-finished product lithium-containing material is poured into crushing equipment for primary crushing treatment, then the material subjected to the primary crushing treatment is put into crushing equipment for crushing, and after the crushing treatment, the lithium-containing material with the particle size of 600nm is obtained.
The lithium-containing material prepared by the method comprises hydrogen, aluminum, phosphorus, halogen and oxygen, and has a chemical formula of LiHAl (PO)4)O0.94Br0.12(ii) a When the lithium-containing material is subjected to X-ray diffraction, the measured 2 theta angle has a characteristic diffraction peak at 15-35 degrees, and the corresponding XRD is shown in figure 9.
Example 5
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.96F0.08The battery structure is NCM (negative ion exchange) SiOC450, the solid electrolyte coating faces to the negative side, and other parameters are the same as those in embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 6
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Cl0.12The battery structure is LFP | Si, the solid electrolyte coating faces to the negative side, and other parameters are the same as those of the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 7
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Br0.12The solid electrolyte coating is double-sided, and faces to the positive electrode side and the negative electrode side at the same time, and other parameters are the same as those in example 1; the structure of the composite diaphragm is schematically shown in FIG. 2; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 8
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Br0.12The battery structure is NCM (national center of the university) SiOC450, the two sides of the solid electrolyte coating face to the negative electrode side, and the other parameters are the same as those in the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 9
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Br0.12And AlPO4The slurry B was coated on a polyethylene-based film having a 3 μm alumina coating layer on one side (toward the positive electrode side) and a solid electrolyte coating layer toward the negative electrode side, with the same other parameters as in example 1, composite separatorThe structure is schematically shown in FIG. 3; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 10
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.95F0.1And AlPO4The mixture of (1: 1) and the other parameters are the same as in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 11
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.96F0.08And AlPO4The slurry B was coated on a polyethylene-based film having a 2 μm alumina coating on one side (toward the positive electrode side) with both sides of the solid electrolyte coating facing the negative electrode side, with the same other parameters as in example 1 (mass ratio 2: 1); the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 12
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.95F0.1With AlPO4The slurry B was coated on a polyethylene-based film without an alumina coating, the solid electrolyte coating was directed to the negative electrode side, the other parameters were the same as in example 1, and the structure of the composite separator is schematically shown in fig. 4; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 13
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Cl0.12And AlPO4Coating the slurry B on a polyethylene base film without an alumina coating, wherein the two sides of the solid electrolyte coating face the positive electrode side and the negative electrode side, the other parameters are the same as those of the example 1, and the structure of the composite diaphragm is shown in FIG. 5; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 14
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.94Cl0.12And AlPO4The mixture (mass ratio 1:1) of (1), the solid electrolyte particle size was 100nm, the thickness of the oxide solid electrolyte coating layer was 2 μm, the solid electrolyte coating layer faced the negative electrode side, and the other parameters were the same as in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 15
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.95F0.1With LiHAl (PO)4)O0.94Br0.12And AlPO4The mixture of (1: 1:1 by mass), the solid electrolyte particle size was 1 μm, the oxide solid electrolyte coating layer thickness was 2 μm, the solid electrolyte coating layer faced the negative electrode side, and the other parameters were the same as in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 16
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.96F0.08With LiHAl (PO)4)O0.94Br0.12And AlPO4The thickness of the oxide solid electrolyte coating layer is 2 μm, the battery structure is NCM graphite, the solid electrolyte coating layer faces to the negative electrode side, and other parameters are the same as those of example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 17
Replacement of solid electrolyte particles with LiHAl (PO)4)O0.96F0.08With LiHAl (PO)4)O0.94Br0.12And AlPO4The thickness of the oxide solid electrolyte coating layer is 800n m, the battery structure is NCM graphite, the solid electrolyte coating layer faces to the negative pole side, and other parameters are the same as those of the mixture of the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 18
Solid electrolyte particles are replaced with lihai: (PO4)O0.96F0.08With LiHAl (PO)4)O0.94Br0.12And AlPO4The thickness of the oxide solid electrolyte coating layer is 4 μm, the battery structure is NCM graphite, the solid electrolyte coating layer faces to the negative electrode side, and other parameters are the same as those of example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 19
The mass ratio of the oxide solid electrolyte particles, the dispersing agent, the thickening agent, the binder and the wetting agent is 100:0.3:1:3:0.4, and other parameters are the same as those in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Example 20
The mass ratio of the oxide solid electrolyte particles, the dispersing agent, the thickening agent, the binder and the wetting agent is 100:0.8:9:10:1.2, and other parameters are the same as those in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 1
No solid electrolyte coating, only polyethylene-based film with alumina coating on both sides is used, and other parameters are the same as those in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 2
Without solid electrolyte coating, only a polyethylene-based film with a 3 μm alumina coating on one side (towards the positive side) was used, the cell structure was LCO | | graphite, and the other parameters were the same as in example 2.
Comparative example 3
The cell structure was NCM graphite with no solid electrolyte coating and only a polyethylene based film with a 2 μm alumina coating on one side (towards the positive side) was used, the other parameters being the same as in example 3.
Comparative example 4
The cell structure was NCM | | | SiOC450, without solid electrolyte coating, using only polyethylene based film without alumina coating, and other parameters were the same as in example 5.
Comparative example 5
The battery has no solid electrolyte coating, only uses a polyethylene base film without an alumina coating, has a battery structure of LFP I Si, and has the same other parameters as the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 6
Magnesium oxide particles are used for replacing solid electrolyte particles, the battery structure is NCM graphite, the magnesium oxide coating faces to the negative pole side, and other parameters are the same as those of the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 7
Replacement of solid electrolyte particles with Li1.5Al0.5Ge1.5(PO4)3The battery structure is NCM (negative ion exchange) SiOC450, the solid electrolyte coating faces to the negative side, and other parameters are the same as those in embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 8
Replacement of solid electrolyte particles with Li1.5Al0.5Ti1.5(PO4)3The battery structure is NCM | | | Si, the solid electrolyte coating faces to the negative pole side, and other parameters are the same as those of the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 9
Replacement of solid electrolyte particles with Li0.5La0.5TiO3The battery structure is NCM graphite, the solid electrolyte coating faces to the negative side, and other parameters are the same as those in embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 10
Replacement of solid electrolyte particles with 1 wt% F-doped Li7La3Zr2O12The battery structure is NCM (negative ion exchange) SiOC450, the solid electrolyte coating faces to the negative side, and other parameters are the same as those in embodiment 1; specific electrochemistry of lithium battery preparedThe results of the performance tests are shown in Table 1, and the results of the safety tests are shown in Table 2.
Comparative example 11
Replacement of solid electrolyte particles with Li3OF, the battery structure is LFP Si, the solid electrolyte coating faces to the negative side, and other parameters are the same as those OF the embodiment 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Comparative example 12
Replacement of solid electrolyte particles with AlPO4Other parameters are the same as those in example 1; the specific electrochemical performance test results of the prepared lithium battery are shown in table 1, and the safety performance test results are shown in table 2.
Table 1 shows electrochemical performance data of lithium batteries prepared in examples of the present invention or comparative examples, which are as follows:
TABLE 1
Table 2 shows data on the safety performance of the lithium batteries prepared in the examples of the present invention or the comparative examples, which are as follows:
TABLE 2
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A lithium battery composite diaphragm is characterized in that:
the composite separator comprises a base film and an oxide solid electrolyte coating layer;
the oxide solid electrolyte coating layer includes oxide solid electrolyte particles;
the oxide solid electrolyte particles are selected from lithium-containing materials or a mixture of lithium-containing materials and aluminum phosphate;
the lithium-containing material comprises a compound consisting of lithium, hydrogen, aluminum, phosphorus, halogen and oxygen elements.
2. The lithium battery composite separator according to claim 1, wherein:
the lithium-containing material has a chemical formula of Li1+xH1-xAl(PO4)O1-yM2yWherein 0 is less than or equal to x<1，0<y<0.1, M is a halogen element,
m is preferably selected from any one of F, Cl, Br or I;
preferably the lithium-containing material is reacted with AlPO4The mass ratio of (A) to (B) is 1-4: 1;
more preferably, the lithium-containing material is selected from LiHAl (PO)4)O1-yM2yAt least one of (1), most preferably LiHAl (PO)4)O0.96F0.08、LiHAl(PO4)O0.95F0.1、LiHAl(PO4)O0.94Cl0.12Or LiHAl (PO)4)O0.94Br0.12At least one of;
the crystal form of the aluminum phosphate is one or more of quartz type, tridymite type or cristobalite type.
3. The lithium battery composite separator according to claim 1, wherein:
the size of the oxide solid electrolyte particles is 10nm-10um, preferably 100nm-1 um;
the oxide solid electrolyte coating layer is coated on one side or two sides of the base film;
the thickness of the oxide solid electrolyte coating layer is 0.3-20 mu m, preferably 800 nm-4 mu m.
4. The lithium battery composite separator according to claim 1, wherein:
the oxide solid electrolyte coating layer further comprises a thickening agent, a binder, a wetting agent and a dispersing agent;
the base membrane is a polymer porous membrane or a polymer porous membrane loaded with a high-temperature resistant ceramic particle coating layer.
5. The lithium battery composite separator according to claim 4, wherein:
the mass ratio of the oxide solid electrolyte particles, the dispersing agent, the thickening agent, the binder and the wetting agent is 100 (0.3-0.8): (1-9): (3-10): 0.4-1.2).
6. The lithium battery composite separator according to claim 4, wherein:
the dispersing agent is selected from at least one of sodium polyacrylate, polyacrylic ammonium salt copolymer or polyvinyl alcohol;
the thickening agent is selected from at least one of sodium carboxymethyl cellulose, carboxyethyl cellulose, sodium alginate, polyacrylamide or polyvinyl alcohol;
the binder is selected from at least one of polymethacrylic acid, methyl styrene-butadiene rubber, styrene-acrylic emulsion, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate and polyurethane, or a copolymer formed by methyl methacrylate and one or more monomers of methacrylic acid, ethacrylic acid, ethyl acrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate;
the wetting agent is selected from at least one of sodium perfluorooctanoate, polyoxyethylene nonyl phenyl ether, fluoroalkyl methoxy alcohol ether, polyoxyethylene alkylamine, butyl sodium naphthalene sulfonate, aryl sodium naphthalene sulfonate, sodium dodecyl benzene sulfonate or alkyl sodium sulfate.
7. The lithium battery composite separator according to claim 4, wherein:
the polymer porous membrane is selected from at least one of polyethylene, polypropylene, polyimide or polyethylene terephthalate;
the high-temperature resistant ceramic particle coating layer is selected from an aluminum oxide, boehmite, magnesium oxide or silicon dioxide coating layer;
the thickness of the high-temperature resistant ceramic particle coating layer is 1-5 mu m;
the high-temperature resistant ceramic particle coating layer is coated on one side or two sides of the polymer porous membrane.
8. The method for preparing a composite separator for a lithium battery as claimed in any one of claims 1 to 7, comprising the steps of:
adding a dispersing agent into a solvent, fully stirring, adding oxide solid electrolyte particles, uniformly grinding to obtain slurry A, continuously adding a thickening agent, a binder and a wetting agent, and fully stirring to obtain slurry B;
and (2) coating the slurry B on a base film, baking to form an oxide solid electrolyte coating, and rolling to obtain the composite diaphragm.
9. The method for preparing a lithium battery composite separator according to claim 8, wherein:
in the step (1), the step (c),
the solvent comprises water system or oil system solvent, preferably at least one of water, ethanol, N-methyl pyrrolidone, tetrahydrofuran, cyclohexane, petroleum ether, acetone, dimethyl acetamide or N, N-dimethylformamide;
in the step (2),
the coating method comprises a micro-gravure coating method and a spray coating method;
the baking temperature is 30-80 ℃ and the baking time is 0.5-30 min.
10. Use of the lithium battery composite separator according to any one of claims 1 to 7 in a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210248783.XA CN114464960B (en) | 2022-03-14 | 2022-03-14 | Lithium battery composite diaphragm and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210248783.XA CN114464960B (en) | 2022-03-14 | 2022-03-14 | Lithium battery composite diaphragm and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114464960A true CN114464960A (en) | 2022-05-10 |
| CN114464960B CN114464960B (en) | 2024-06-21 |
Family
ID=81416666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210248783.XA Active CN114464960B (en) | 2022-03-14 | 2022-03-14 | Lithium battery composite diaphragm and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114464960B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114696040A (en) * | 2022-06-01 | 2022-07-01 | 沧州明珠隔膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN116404247A (en) * | 2023-06-09 | 2023-07-07 | 西北工业大学 | PE-based polymer solid electrolyte and preparation method and application thereof |
| CN116505058A (en) * | 2023-06-27 | 2023-07-28 | 河南师范大学 | Negative electrode interface modification method of solid-state lithium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112201845A (en) * | 2020-10-21 | 2021-01-08 | 江苏厚生新能源科技有限公司 | Ultra-stable interface semi-solid electrolyte battery composite diaphragm and preparation process thereof |
| CN113745515A (en) * | 2021-08-19 | 2021-12-03 | 湖州南木纳米科技有限公司 | Lithium-containing material |
| CN113921986A (en) * | 2021-10-13 | 2022-01-11 | 珠海冠宇电池股份有限公司 | Composite diaphragm and battery comprising same |
| DE102021107940A1 (en) * | 2020-07-14 | 2022-01-20 | GM Global Technology Operations LLC | BATTERY SEPARATORS WITH HYBRID SOLID STATE ELECTROLYTE COATINGS |
-
2022
- 2022-03-14 CN CN202210248783.XA patent/CN114464960B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102021107940A1 (en) * | 2020-07-14 | 2022-01-20 | GM Global Technology Operations LLC | BATTERY SEPARATORS WITH HYBRID SOLID STATE ELECTROLYTE COATINGS |
| CN112201845A (en) * | 2020-10-21 | 2021-01-08 | 江苏厚生新能源科技有限公司 | Ultra-stable interface semi-solid electrolyte battery composite diaphragm and preparation process thereof |
| CN113745515A (en) * | 2021-08-19 | 2021-12-03 | 湖州南木纳米科技有限公司 | Lithium-containing material |
| CN113921986A (en) * | 2021-10-13 | 2022-01-11 | 珠海冠宇电池股份有限公司 | Composite diaphragm and battery comprising same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114696040A (en) * | 2022-06-01 | 2022-07-01 | 沧州明珠隔膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN114696040B (en) * | 2022-06-01 | 2022-08-30 | 沧州明珠隔膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN116404247A (en) * | 2023-06-09 | 2023-07-07 | 西北工业大学 | PE-based polymer solid electrolyte and preparation method and application thereof |
| CN116505058A (en) * | 2023-06-27 | 2023-07-28 | 河南师范大学 | Negative electrode interface modification method of solid-state lithium battery |
| CN116505058B (en) * | 2023-06-27 | 2024-02-13 | 河南师范大学 | Negative electrode interface modification method of solid-state lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114464960B (en) | 2024-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114464960B (en) | Lithium battery composite diaphragm and preparation method and application thereof | |
| CN110048153B (en) | Solid metal lithium battery and preparation method thereof | |
| US11177475B2 (en) | Ternary positive electrode material, and lithium ion battery | |
| CN109004265B (en) | Solid electrolyte positive electrode and solid battery comprising same | |
| WO2021083197A1 (en) | Silicon-oxygen composite negative electrode material and method for preparation thereof and lithium-ion battery | |
| JP6329745B2 (en) | Lithium ion secondary battery and method for producing positive electrode active material for lithium ion secondary battery | |
| CN111916664B (en) | Positive plate, preparation method and battery | |
| CN111430687B (en) | Carbon-coated lithium iron phosphate composite material, preparation method thereof and lithium ion battery | |
| CN114639868B (en) | Negative plate for lithium battery and preparation method and application thereof | |
| KR20170048184A (en) | Negative electrode material for secondary battery, method for preparing the same and secondary battery having the same | |
| WO2023174301A1 (en) | Inorganic solid-state electrolyte layer of lithium battery, composite negative electrode plate for lithium battery and preparation method therefor, and lithium battery | |
| CN104966814B (en) | A kind of lithium anode of high security and preparation method thereof | |
| CN111584827A (en) | Lithium battery negative pole piece and preparation method and application thereof | |
| CN111048770A (en) | Ternary doped silicon-based composite material and preparation method and application thereof | |
| CN110943206A (en) | Positive active material, method for preparing same, and battery comprising same | |
| CN106099083A (en) | The cladded type nickel ion doped material of a kind of hydro-thermal method surface modification, lithium battery and preparation method thereof | |
| CN113764658A (en) | Anion-cation co-doped high-nickel single crystal ternary cathode material and preparation method and application thereof | |
| CN105336939A (en) | Coating modification method of lithium titanate and lithium ion battery thereof | |
| CN113394406A (en) | Current collector, electrode plate and lithium ion battery | |
| CN101504981B (en) | Lithium iron phosphate/carbon composite electrode material and preparation method thereof | |
| US20230420660A1 (en) | Silicon-based anode material and preparation method thereof | |
| CN110085870B (en) | Alkali metal composite cathode, preparation method thereof and application of alkali metal composite cathode in preparation of solid-state alkali metal battery | |
| WO2023143516A1 (en) | Positive electrode sheet having high rate capability, long cycle, and high safety for use in lithium battery, and preparation method therefor and application thereof | |
| CN115642292B (en) | Zero strain all-solid-state lithium aluminum battery | |
| WO2023143390A2 (en) | Functionalized lithium battery separator, and manufacturing method therefor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |