CN116750792A - Flame-retardant solid electrolyte material, and preparation method and application thereof - Google Patents
Flame-retardant solid electrolyte material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116750792A CN116750792A CN202311019168.2A CN202311019168A CN116750792A CN 116750792 A CN116750792 A CN 116750792A CN 202311019168 A CN202311019168 A CN 202311019168A CN 116750792 A CN116750792 A CN 116750792A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- flame
- electrolyte material
- retardant solid
- tetragonal
- Prior art date
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- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 197
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 70
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011975 tartaric acid Substances 0.000 claims abstract description 27
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 36
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 34
- 229910052726 zirconium Inorganic materials 0.000 claims description 34
- 229910052746 lanthanum Inorganic materials 0.000 claims description 33
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 230000008707 rearrangement Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 230000008569 process Effects 0.000 description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100440696 Caenorhabditis elegans cor-1 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a flame-retardant solid electrolyte material, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries. The flame-retardant solid electrolyte material promotes tetragonal Li by adding tartaric acid 7 La 3 Zr 2 O 12 Li of material forming cubic phase in atomic rearrangement 7 La 3 Zr 2 O 12 After the material, cubic phase Li 7 La 3 Zr 2 O 12 Li in the material + Then with H in tartaric acid + Exchange to obtain cubic phase flame-retardant solid electrolyte material Li 7‑x H x La 3 Zr 2 O 12 (0 < x.ltoreq.4.48). When heated, li 7‑ x H x La 3 Zr 2 O 12 (0＜x4.48) H in the structure + Will be combined with O 2‑ Forming water (H) 2 O) is removed, thereby playing a role in flame retardance. And the flame-retardant solid electrolyte material is applied to a battery diaphragm, so that the ionic conductivity and the electrochemical performance of the battery can be improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a flame-retardant solid electrolyte material, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, low self-discharge rate and the like, is one of the most advanced battery technologies at present, and is dominant in the fields of high-energy application such as mobile electronic equipment, electric tools, electric traffic and the like. The four main materials of the lithium ion battery are: positive electrode material, negative electrode material, separator and electrolyte. The membrane is a film with a micropore structure, is a key inner layer component with the most technical barriers in the lithium ion battery industry chain, and has the cost accounting for about 10-20% in the power battery. The diaphragm mainly plays roles of isolating positive and negative electrodes to prevent short circuits and providing micro channels to support lithium ion migration in the lithium battery, and has great influence on battery safety, rate capability and cycle performance.
The thermal stability of the membrane can be improved by coating the membrane of polyolefin with nano materials such as alumina, boehmite and the like. In the prior art of diaphragm application, the inorganic substance is usually coated on one side or on both sides, and commonly used inorganic ceramic particles comprise Al 2 O 3 Boehmite, siO 2 、TiO 2 Etc. However, the inorganic ceramic particles described above do not improve the flame retardant properties of polyolefin separators.
A flame retardant lithium ion battery separator and a method for preparing the same are disclosed in patent CN 111211274 a. The patent mentions that the hydrotalcite intercalation structural material can play a role in flame retardance when being heated, and structural water, laminate hydroxyl and interlayer anions are separated out in the form of water and carbon dioxide. However, since the hydrotalcite-like intercalation structure material itself has no lithium ion conductivity, the hydrotalcite-like intercalation material increases the specific resistance of the separator after coating the polyolefin separator, resulting in an increase in internal resistance and a decrease in battery performance. In patent CN115863909a, a technical solution of coating a separator with an aramid and garnet type solid electrolyte material is disclosed. Although garnet-type solid electrolyte materials are used in the technical scheme, the garnet-type solid electrolyte materials cannot achieve the flame-retardant effect because of the non-flame-retardant function.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a flame-retardant solid electrolyte material, and a preparation method and application thereof. The flame-retardant solid electrolyte material Li 7-x H x La 3 Zr 2 O 12 And has flame retardance and high ionic conductivity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a flame-retardant solid electrolyte material, the chemical formula of which is Li 7-x H x La 3 Zr 2 O 12 ；
Wherein x is more than 0 and less than or equal to 4.48;
Li 7-x H x La 3 Zr 2 O 12 is of a cubic phase structure.
The Li is 7-x H x La 3 Zr 2 O 12 The particle diameter of (C) is preferably 50-150 nm.
Preferably, said x is selected from 1 or 1.5 or 1.75 or 3.5 or 4 or 4.48.
The Li is 7-x H x La 3 Zr 2 O 12 The material may be Li 6 HLa 3 Zr 2 O 12 Or Li (lithium) 5.5 H 1.5 La 3 Zr 2 O 12 Or Li (lithium) 5.25 H 1.75 La 3 Zr 2 O 12 Or Li (lithium) 3.5 H 3.5 La 3 Zr 2 O 12 Or Li (lithium) 3 H 4 La 3 Zr 2 O 12 Or Li (lithium) 2.52 H 4.48 La 3 Zr 2 O 12 。
The invention relates to a flame-retardant solidState electrolyte material Li 7-x H x La 3 Zr 2 O 12 H in the crystal structure when heated + Will be combined with O 2- Forming water (H) 2 O) is removed, thereby playing a role in flame retardance.
The preparation method of the flame-retardant solid electrolyte material comprises the following steps:
1) Mixing a lithium source, a zirconium source and a lanthanum source by a dry method or a wet method to prepare a precursor material, and sintering to obtain tetragonal Li 7 La 3 Zr 2 O 12 A material;
2) Li of the tetragonal phase 7 La 3 Zr 2 O 12 Mixing the material, tartaric acid and solvent, and grinding to perform phase transformation to obtain cubic-phase flame-retardant solid electrolyte material Li 7-x H x La 3 Zr 2 O 12 。
In the present invention, li of the tetragonal phase 7 La 3 Zr 2 O 12 During the grinding process of the material, the mechanical force promotes Li 7 La 3 Zr 2 O 12 Atomic rearrangement in the lattice of the material, li forming a cubic phase 7 La 3 Zr 2 O 12 A material. The addition of tartaric acid causes cubic phase Li 7 La 3 Zr 2 O 12 Li in the material + And H is + Exchange to obtain cubic phase material Li 7-x H x La 3 Zr 2 O 12 (0＜x≤4.48)。
Too strong acidity of tartaric acid causes cubic phase Li 7 La 3 Zr 2 O 12 The decomposition of the material, therefore, the addition amount of tartaric acid needs to be controlled, thereby effectively controlling Li + And H is + The larger the amount of tartaric acid added, the more Li + And H is + The higher the degree of exchange.
Preferably, the tetragonal Li in step 2) 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is (10-40) 1. In some embodiments of the invention, L of the tetragonal phasei 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is preferably 10:1 or 15:1 or 20:1 or 30:1 or 40:1.
Preferably, the solvent in the step 2) is selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetonitrile and cyclohexane.
Preferably, the tetragonal Li in step 2) 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent is 1: (5-10). In some embodiments of the invention, the tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of material to solvent is preferably 1:5 or 1:8.
Preferably, the grinding in step 2) is performed in a high-energy ball mill.
Preferably, the grinding rotating speed of the high-energy ball mill is 500-650 r/min.
Preferably, the grinding time of the high-energy ball mill is 5-10 hours.
By the preparation method, cubic phase Li with the particle size ranging from 50nm to 150nm is obtained 7-x H x La 3 Zr 2 O 12 (0 < x is less than or equal to 4.48).
In the invention, the tetragonal Li prepared in the step 1) is 7 La 3 Zr 2 O 12 The material belongs to garnet type.
In the above preparation method, the dry or wet mixing and sintering process in the step 1) is specifically as follows:
the dry mixing process comprises the following steps: using a high-speed mixer, mixing for 5-30 min at a rotating speed of 500-1000 r/min to obtain dry-mixed tetragonal Li 7 La 3 Zr 2 O 12 A material precursor.
The wet mixing process comprises the following steps: weighing a lithium source, a zirconium source and a lanthanum source according to stoichiometric ratio, and then feeding deionized water and the raw materials into grinding mixing equipment according to the mass ratio of (3-5) preferably 1. The rotation speed of the equipment is preferably 300-500 r/min, and the mixing time is preferably 1-5 h.
Drying the ground and mixed slurry to obtain wet mixed tetragonal Li 7 La 3 Zr 2 O 12 A material precursor.
The milling and mixing device is preferably a planetary ball mill or a circulation stirring ball mill.
The sintering process comprises the following steps: li of tetragonal phase to be dry-mixed or wet-mixed 7 La 3 Zr 2 O 12 Placing the material precursor into a sintering furnace, heating to 900-1200 ℃ at a speed of 0.5-2 ℃/min, and preserving heat for 4-12 h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
In the preferred embodiment of the present invention, the molar ratio of the lithium source, the zirconium source and the lanthanum source in the step 1) is (6 to 7.5): (1.6-2.1): (2.8-3.3). In some embodiments of the invention, the molar ratio of the lithium source, zirconium source, lanthanum source is preferably 7:2:3.
Preferably, the lithium source in the step 1) is selected from one or more of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium nitrate, lithium acetate, lithium oxalate and lithium nitrite; more preferably one or more of lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate.
Preferably, the zirconium source is selected from one or more of zirconium oxide, zirconium acetate, zirconyl nitrate, zirconium hydroxide and zirconium basic carbonate; more preferably one or more of zirconia, zirconium acetate, zirconyl nitrate.
Preferably, the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum acetate and lanthanum carbonate; more preferably one or more of lanthanum oxide, lanthanum hydroxide, lanthanum acetate.
Preferably, the sintering temperature in the step 1) is 900-1200 ℃; more preferably 900 to 1100 ℃. In some embodiments of the invention it is preferred to be 900 c or 1100 c.
Preferably, the temperature rising rate of the sintering is 0.5-2 ℃/min; more preferably 0.5-2 ℃/min; further preferably 0.5℃or 1℃per minute.
Preferably, the sintering time is 4-12 hours.
Flame-retardant solid electrolyte material Li 7-x H x La 3 Zr 2 O 12 The coating on the surface of the base film not only can achieve the flame-retardant effect, but also can improve the ion conductivity of the diaphragm, reduce the internal resistance of the battery and improve the performance of the battery.
The invention also provides a diaphragm material which consists of a base film and a diaphragm coating coated on the surface of the base film.
Preferably, the membrane coating is prepared by drying a solution composed of the flame-retardant solid electrolyte material prepared by the preparation method of the flame-retardant solid electrolyte material, a dispersing agent and deionized water.
Preferably, the thickness of the diaphragm coating is 0.5-5 mu m; more preferably 1 to 3 μm; further preferably 1 μm, 2 μm or 3 μm.
Preferably, the base film is selected from polyolefin separator films.
The polyolefin separator specifically includes, but is not limited to, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polypropylene (PP), and the like.
Preferably, the base film is selected from Polyethylene (PE) or polypropylene (PP).
Preferably, the thickness of the base film is 3-30 μm; more preferably, the thickness of the base film is 5-20 μm. Further preferably 7 μm, 9 μm or 12 μm.
In the preparation of the diaphragm material, the mass ratio of the dispersing agent to the flame-retardant solid electrolyte material is preferably (0.1-5) 100; more preferably, (1 to 3): 100. in some embodiments of the invention the mass ratio of the dispersant to the flame retardant solid electrolyte material is 1:100.
Preferably, the dispersant includes, but is not limited to, polyacrylic acid, ammonium citrate, polyethylene glycol, methylcellulose, triethanolamine, ammonium polymethacrylate, polyvinylpyrrolidone, polyethylene oxide, sodium alginate, polyethyleneimine, ammonium polyacrylate, polymethacrylic acid, and the like.
The invention also provides a battery, which comprises the separator material.
The battery has good flame retardant property and good ion conductivity.
The invention relates to Li with cubic phase structure of the flame-retardant solid electrolyte material 7-x H x La 3 Zr 2 O 12 Ion conductivity performance tests were performed. The results show that H + In Li 7-x H x La 3 Zr 2 O 12 The content of the material is increased, the ion conductivity is reduced, so that the content of the tartaric acid is increased to cause Li 7-x H x La 3 Zr 2 O 12 The conductivity of the material decreases.
The invention also carries out thermal stability and ignition point test on the membrane material prepared by the method. The results show that the coating with Li according to the present invention 7-x H x La 3 Zr 2 O 12 The diaphragm made of the material (x is more than 0 and less than or equal to 4.48) has better heat stability and higher ignition point.
The invention also relates to the Li containing the preparation method 7-x H x La 3 Zr 2 O 12 The electrochemical performance of the battery made of the materials (0 < x is less than or equal to 4.48). The results show that Li according to the present invention will be coated 7-x H x La 3 Zr 2 O 12 When the separator made of the material (x is more than 0 and less than or equal to 4.48) is applied to a battery, the capacity retention rate of the battery is higher, and the chemical performance of the battery is more stable.
Compared with the prior art, the chemical formula of the flame-retardant solid electrolyte material provided by the invention is Li 7- x H x La 3 Zr 2 O 12 Wherein x is more than 0 and less than or equal to 4.48, li 7-x H x La 3 Zr 2 O 12 Is of a cubic phase structure. The flame-retardant solid electrolyte material promotes tetragonal Li by adding tartaric acid 7 La 3 Zr 2 O 12 The material has atomic weightLi arranged to form a cubic phase 7 La 3 Zr 2 O 12 After the material, cubic phase Li 7 La 3 Zr 2 O 12 Li in the material + Then with H in tartaric acid + Exchange to obtain cubic phase flame-retardant solid electrolyte material Li 7-x H x La 3 Zr 2 O 12 (0 < x.ltoreq.4.48). When heated, li 7-x H x La 3 Zr 2 O 12 H in the structure (0 < x.ltoreq.4.48) + Will be combined with O 2- Forming water (H) 2 O) is removed, thereby playing a role in flame retardance. And the flame-retardant solid electrolyte material is applied to a battery diaphragm, so that the ionic conductivity and the electrochemical performance of the battery can be improved.
Drawings
FIG. 1 is tetragonal phase Li prepared in example 1 7 La 3 Zr 2 O 12 With standard tetragonal phase Li 7 La 3 Zr 2 O 12 An X-ray diffraction (XRD) contrast pattern of (JCPDS#154-5087);
FIG. 2 is a cubic phase Li prepared in example 1 6 HLa 3 Zr 2 O 12 (x=1) cubic phase Li of material and standard 7 La 3 Zr 2 O 12 X-ray diffraction (XRD) contrast pattern of (JCPDS#80-0457).
Detailed Description
In order to further illustrate the present invention, the following describes in detail a flame retardant solid electrolyte material, a preparation method and application thereof, provided by the present invention, with reference to examples.
Example 1
1. Dry process for preparing garnet type tetragonal solid electrolyte Li 7 La 3 Zr 2 O 12 Material
According to the stoichiometric ratio, 258.62g lithium carbonate is used as a lithium source, 246.44g zirconium oxide is used as a zirconium source, and 569.78g lanthanum hydroxide is used as a lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a dry method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 Material, productThe rate was 62%.
The dry mixing process comprises the following steps: and (3) using a high-speed mixer with the rotating speed of 500r/min, and mixing for 20 min to obtain the dry-mixed precursor. The sintering process comprises the following steps: placing the dry mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
For the sample tetragonal Li prepared above 7 La 3 Zr 2 O 12 The material was subjected to XRD testing, the test results are shown in figure 1. FIG. 1 shows that tetragonal Li obtained by the above preparation process 7 La 3 Zr 2 O 12 Material and standard tetragonal phase Li 7 La 3 Zr 2 O 12 The spectrum of (JCPLDS#154-5087) was better compared, so that tetragonal Li prepared in example 1 was obtained 7 La 3 Zr 2 O 12 Is a pure tetragonal phase LLZO material (lithium lanthanum zirconium oxide material).
2. Preparation of Li 6 HLa 3 Zr 2 O 12 (x=1) material
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 The materials 500g and 2500g solvent isopropanol, 12.5 g tartaric acid are fed into a high-energy ball mill, the rotating speed is 500r/min, and after grinding for 10 hours, cubic phase Li with the median particle diameter range of 50-150 nm can be obtained 6 HLa 3 Zr 2 O 12 (x=1) material.
Li of the tetragonal phase 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent isopropanol is 1:5; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 40:1.
For the sample cubic phase Li prepared as described above 6 HLa 3 Zr 2 O 12 (x=1) the material was subjected to XRD testing, and the test results are shown in fig. 2. FIG. 2 shows that Li 6 HLa 3 Zr 2 O 12 (x=1) diffraction pattern of material and standard cubic phase Li 7 La 3 Zr 2 O 12 The map of (JCPLDS#80-0457) corresponds well, and therefore Li 6 HLa 3 Zr 2 O 12 The material belongs to a pure cubic phase, which indicates H in tartaric acid + To cubic phase Li 7 La 3 Zr 2 O 12 Li in (III) + And does not alter the crystal structure of the material.
3. Diaphragm coating
The Li is as described above 6 HLa 3 Zr 2 O 12 Material 100 g was added to deionized water, and Li was added as described above 6 HLa 3 Zr 2 O 12 Polyacrylic acid with the total mass of 1. 1 wt percent of the solid mass of the material is used as a dispersing agent, 600W is subjected to ultrasonic dispersion for 30 minutes, and then the evenly dispersed membrane coating solution can be obtained.
The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. The flame-retardant diaphragm material with flame retardance and high ionic conductivity can be obtained.
4. Performance testing
1. Ion conductivity test: 1 to g of the above Li 6 HLa 3 Zr 2 O 12 A material. Using a die with the diameter of 10 mm, applying pressure of 10 MPa in a table type powder tablet press, maintaining the pressure for 10 min, and demoulding to obtain the sheet. The above flakes were placed in a sintering furnace, heated to 900 ℃ at 2 ℃ and kept at 20 h. I.e. Li 6 HLa 3 Zr 2 O 12 A ceramic sheet of material. The surface of the ceramic wafer is lightly polished by 1000-mesh sand paper wetted by alcohol according to a crisscross method, so that surface impurities are removed, and the thickness uniformity of each position of the electrolyte is ensured. Thickness L of the ceramic sheet was measured using a vernier caliper, jin Zusai electrode was vapor deposited using an ion sputtering apparatus, and Li was measured using an AC impedance test 6 HLa 3 Zr 2 O 12 Ionic conductivity of the material.
2. Thermal stability test: the thermal shrinkage of the separator at different temperatures was recorded. Specifically, a separator was taken 100mm×100mm (md×td), MD being the separator longitudinal direction, and TD being the separator transverse direction. The heat shrinkage test temperature was 150 ℃/h.
3. Fire point test: and (3) using a fire point tester, placing the diaphragm sample into a hole of a copper ingot furnace, covering a cover, and adjusting a certain temperature. And the flame was placed over the holes, if there was no continuous 5s flame over the nozzles of the holes within five minutes, the furnace temperature was raised by 5 ℃. Taking a new sample for re-experiment until a flame with more than 5 seconds is detected above the nozzle, and recording the temperature at the moment as the ignition point.
4. Electrochemical performance test of flame retardant separator:
assembling 2032 button cell in a glove box filled with argon, controlling the water oxygen value in the glove box to be less than 0.01ppm, taking a ternary material as a positive electrode, using a diaphragm with a double-sided coated flame-retardant solid electrolyte material, taking foam nickel as a structural support and conducting, and taking a metallic lithium sheet as a negative electrode. 1M LiPF 6 And (3) dissolving a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (EMC) (the volume ratio is 1:1:1) as an electrolyte, assembling the half-cell, then adopting a sealing machine to press and seal the cell, and after standing for a period of time, starting to test the electrochemical performance, the test cycle number and the capacity retention rate.
Example 2
1. Wet process for preparing garnet solid electrolyte Li 7 La 3 Zr 2 O 12 Material
258.62g of lithium carbonate as lithium source, 246.44g of zirconium oxide as zirconium source, and 569.78g of lanthanum hydroxide as lanthanum source were weighed according to the stoichiometric ratio. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 A material.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 3:1. The rotation speed of the equipment is 300r/min, and after mixing for 4 hours, the ground and mixed slurry is dried, so that the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12 hours to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 60%.
2. Preparation of Li 6 HLa 3 Zr 2 O 12 (x=1) material
The same as in example 1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Example 3
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
167.64g of lithium hydroxide as lithium source, 246.44g of zirconium oxide as zirconium source, and 488.71g of lanthanum oxide as lanthanum source were weighed according to the stoichiometric ratio. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 60%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 3:1. The rotation speed of the equipment is 300r/min, and after mixing for 4 hours, the ground and mixed slurry is dried, so that the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12 hours to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Preparation of Li 5.5 H 1.5 La 3 Zr 2 O 12 Material
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 The material 500g and 2500g solvent methanol, 16.66 g tartaric acid are fed into a high-energy ball mill, the rotating speed is 600r/min, and after grinding for 10 hours, cubic phase Li with the median particle diameter range of 50-150 nm can be obtained 5.5 H 1.5 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent methanol is 1:5; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 30:1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Example 4
Preparation of Li 5.25 H 1.75 La 3 Zr 2 O 12
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
356.65g of lithium oxalate as lithium source, 246.44g of zirconia as zirconium source, and 488.71g of lanthanum oxide as lanthanum source were weighed according to the stoichiometric ratio. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 61%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 3:1. The rotation speed of the equipment is 300r/min, and after mixing for 4 hours, the ground and mixed slurry is dried, so that the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12 hours to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Preparation of Li 5.25 H 1.75 La 3 Zr 2 O 12 Material
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 The materials 500g and 2500g solvent isopropanol, 25 g tartaric acid are fed into a high-energy ball mill, the rotating speed is 600r/min, and after grinding 10h, cubic phase Li with the median particle diameter range of 50-150 nm can be obtained 5.25 H 1.75 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent is 1:5; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 20:1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Example 5
Preparation of Li 3.5 H 3.5 La 3 Zr 2 O 12
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
The lithium oxalate 356.65g was weighed in stoichiometric ratio as lithium source, the 246.44g zirconia as zirconium source, and the lanthanum oxide 488.71g as lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 60%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 3:1. The rotation speed of the equipment is 300r/min, after mixing 4h, the slurry after grinding and mixing is dried, and then the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Preparation of Li 3.5 H 3.5 La 3 Zr 2 O 12 Material
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 The materials 500g and 4000 g solvent n-butanol and 33.33 g tartaric acid are fed into a high-energy ball mill, the rotation speed is 650r/min, and the materials can be ground for 10 hoursTo obtain cubic phase Li with median particle diameter in 50-150 nm 3.5 H 3.5 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent n-butanol is 1:8; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 15:1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Example 6
Preparation of Li 3 H 4 La 3 Zr 2 O 12
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
The lithium oxalate 356.65g was weighed in stoichiometric ratio as lithium source, the 246.44g zirconia as zirconium source, and the lanthanum oxide 488.71g as lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 63%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 3:1. The rotation speed of the equipment is 500r/min, after mixing 4h, the slurry after grinding and mixing is dried, and then the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 900 ℃ at 0.5 ℃/min, and preserving heat for 12h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Preparation of Li 3 H 4 La 3 Zr 2 O 12 Material
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 Materials 500g and 4000 g solvent ethanol50 g tartaric acid, feeding into a high-energy ball mill, grinding at a rotation speed of 650r/min and 8h to obtain cubic phase Li with a median particle diameter of 50-150 nm 3 H 4 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent ethanol is 1:8; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 10:1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Example 7
Preparation of Li 2.52 H 4.48 La 3 Zr 2 O 12
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
The lithium acetate 65.98 g was weighed in stoichiometric ratio as lithium source, the 246.44g zirconia as zirconium source and the lanthanum oxide 488.71g as lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 60%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 4:1. The rotation speed of the equipment is 500r/min, after mixing 4h, the slurry after grinding and mixing is dried, and then the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 1100 ℃ at a speed of 1 ℃/min, and preserving heat for 8h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Preparation of Li 2.52 H 4.48 La 3 Zr 2 O 12 Material
The first step is carried out to prepareTetragonal Li 7 La 3 Zr 2 O 12 The materials 500g and 4000 g solvent ethanol and 50 g tartaric acid are fed into a high-energy ball mill, the rotating speed is 650r/min, and after grinding for 8 hours, cubic phase Li with the median particle diameter range of 50-150 nm can be obtained 2.52 H 4.48 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent ethanol is 1:8; tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is 10:1.
3. Diaphragm coating
The same as in example 1.
4. Performance testing
The same as in example 1.
Comparative example 1
1. Preparation of garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 Material
The lithium acetate 65.98 g was weighed in stoichiometric ratio as lithium source, the 246.44g zirconia as zirconium source and the lanthanum oxide 488.71g as lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 60%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 4:1. The rotation speed of the equipment is 500r/min, after mixing 4h, the slurry after grinding and mixing is dried, and then the wet mixed precursor can be obtained. The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 1100 ℃ at a speed of 1 ℃/min, and preserving heat for 8h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
2. Diaphragm coating
The tetragonal phase Li is mixed with 7 La 3 Zr 2 O 12 Adding material 100 g into deionized water, addingInto tetragonal phase Li 7 La 3 Zr 2 O 12 Polyacrylic acid accounting for 1 percent wt percent of the total mass of the material solid is taken as a dispersing agent, and 600W ultrasonic dispersion is carried out for 30 minutes, thus obtaining the evenly dispersed membrane coating solution.
The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. Can obtain Li with tetragonal phase 7 La 3 Zr 2 O 12 Material coated separator material.
3. Performance testing
The same as in example 1.
Comparative example 2
1. Preparation of cubic solid electrolyte Li 7 La 3 Zr 2 O 12 Material
The lithium acetate 65.98 g was weighed in stoichiometric ratio as lithium source, the 246.44g zirconia as zirconium source and the lanthanum oxide 488.71g as lanthanum source. Mixing a lithium source, a zirconium source and a lanthanum source by a wet method to obtain a precursor material, and sintering the precursor to obtain tetragonal Li 7 La 3 Zr 2 O 12 The material was found to have a yield of 61%.
The wet mixing process comprises the following steps: and feeding a lithium source, a zirconium source, a lanthanum source and deionized water into a grinding and mixing device by using a planetary ball mill according to a mass ratio of 4:1. The rotation speed of the equipment is 500r/min, after mixing 4h, the slurry after grinding and mixing is dried, and then the wet mixed precursor can be obtained.
The sintering process comprises the following steps: placing the dry-mixed or wet-mixed precursor into a sintering furnace, heating to 1100 ℃ at a speed of 1 ℃/min, and preserving heat for 8h to obtain tetragonal phase Li 7 La 3 Zr 2 O 12 A material.
Tetragonal phase Li prepared in the first step 7 La 3 Zr 2 O 12 Feeding 500-g and 2500g of ethanol into a high-energy ball mill, grinding at a rotating speed of 650-r/min and 10-h to obtain cubic phase Li with a median particle diameter of 50-150 nm 7 La 3 Zr 2 O 12 A material.
Tetragonal Li 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent is 1:5.
2. Diaphragm coating
The cubic phase Li is 7 La 3 Zr 2 O 12 Adding 100 g of the material into deionized water, adding 1 wt% polyacrylic acid of the total mass of the solid as a dispersing agent, and performing ultrasonic dispersion for 30min at 600W to obtain a uniformly dispersed membrane coating solution.
The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. Thus obtaining Li with cubic phase 7 La 3 Zr 2 O 12 Material coated separator material.
3. Performance testing
The same as in example 1.
Comparative example 3
1. Diaphragm coating
Adding 100 g of aluminum oxide material into deionized water, adding 1-wt% of polyacrylic acid of the total mass of the solids as a dispersing agent, and performing ultrasonic dispersion for 30min at 600-W to obtain a uniformly-dispersed membrane coating solution. The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. A separator material with an alumina coating can be obtained.
2. Performance testing
The same as in example 1.
Comparative example 4
1. Diaphragm coating
Adding boehmite 100 g into deionized water, adding polyacrylic acid which is 1-wt% of the total mass of the solid as a dispersing agent, and performing ultrasonic dispersion for 30min at 600-W to obtain the uniformly-dispersed membrane coating solution. The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. A separator material having boehmite coating can be obtained.
2. Performance testing
The same as in example 1.
Comparative example 5
1. Diaphragm coating
Adding 100 g of magnesium hydroxide material into deionized water, adding polyacrylic acid with the total mass of 1-wt% of the solid as a dispersing agent, and performing ultrasonic dispersion for 30min at 600-W to obtain the uniformly-dispersed membrane coating solution. The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. The separator material with magnesium hydroxide coating can be obtained.
2. Performance testing
The same as in example 1.
Comparative example 6
1. Diaphragm coating
Adding hydrotalcite material 100 g into deionized water, adding polyacrylic acid which is 1 wt percent of the total mass of the solid as a dispersing agent, and performing ultrasonic dispersion for 30 minutes at 600W to obtain a uniformly dispersed membrane coating solution. The above separator coating solution was double-coated on a 7 μm PE base film with a coating thickness of 2 μm. The separator material with hydrotalcite coating can be obtained.
2. Performance testing
The same as in example 1.
The performance test data for examples 1-7 and comparative examples 1-6 are as follows:
table 1 ion conductivity test data for examples 1 to 7 and comparative examples 1 to 6
| Ion conductivity (mS/cm) | Ion conductivity (mS/cm) | ||
| Example 1 | 0.651 | Comparative example 1 | 0.364 |
| Example 2 | 0.656 | Comparative example 2 | 0.783 |
| Example 3 | 0.582 | Comparative example 3 | 0 |
| Example 4 | 0.574 | Comparative example 4 | 0 |
| Example 5 | 0.420 | Comparative example 5 | 0 |
| Example 6 | 0.359 | Comparative example 6 | 0 |
| Example 7 | 0.272 |
The results show that: comparative example 1 and comparative example 2 each use tetragonal Li 7 La 3 Zr 2 O 12 Li with cubic phase 7 La 3 Zr 2 O 12 A material. Li of cubic phase 7 La 3 Zr 2 O 12 The ionic conductivity of the material is the highest and can reach 0.783 mS/cm, tetragonal Li 7 La 3 Zr 2 O 12 The ionic conductivity of the material is lower than that of cubic phase Li 7 La 3 Zr 2 O 12 A material. In the occurrence of Li + And H is + After exchange, cubic phase Li 7 La 3 Zr 2 O 12 The ionic conductivity of the material is reduced. H + In the cubic phase Li 7 La 3 Zr 2 O 12 The more present, the lower the ionic conductivity. As can be seen from examples 2 to 7, with H + In the cubic phase Li 7 La 3 Zr 2 O 12 The greater the content in the material, the lower the ionic conductivity tends to be. The dry and wet methods used in examples 1 and 2, respectively, are used to prepare the precursors, which have little effect on the ionic conductivity of the materials.
Table 2 thermal stability test data for examples 1-7 and comparative examples 1-6
Note that: MD means machine direction stretching, TD means transverse direction stretching, and shrinkage means the shrinkage ratio of the area after stretching.
The results show that: li (Li) 7-x H x La 3 Zr 2 O 12 After the material (x is more than 0 and less than or equal to 4.48) is coated on the diaphragm, the thermal shrinkage rate of the diaphragm is lower. Tetragonal Li 7 La 3 Zr 2 O 12 Li of cubic phase 7 La 3 Zr 2 O 12 The material has higher heat shrinkage rate after coating the diaphragm. Thus using Li according to the present invention 7-x H x La 3 Zr 2 O 12 After the material (x is more than 0 and less than or equal to 4.48) is coated on the diaphragm, the diaphragm has better thermal stability and is not easy to deform, because the smaller the thermal shrinkage rate is, the better the dimensional stability of the diaphragm is after being heated.
Table 3 ignition point test data for examples 1 to 7 and comparative examples 1 to 6
The results show that: compared with tetragonal phase Li 7 La 3 Zr 2 O 12 With cubic phase Li 7 La 3 Zr 2 O 12 The ignition point improving effects of the examples 1 to 7 are remarkable.
Table 4 electrochemical performance test data for examples 1 to 7 and comparative examples 1 to 6
The results show that: li (Li) 7-x H x La 3 Zr 2 O 12 The materials (0 < x.ltoreq.4.48) (examples 1 to 7) have certain ionic conductivity, and after coating the separator, the materials are applied to batteries, and the materials are superior to alumina (comparative example 3), boehmite (comparative example 4), magnesium hydroxide (comparative example 5) and hydrotalcite (comparative example 6) without ionic conductivity in capacity retention rate.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. A flame-retardant solid electrolyte material is characterized in that the chemical formula is Li 7-x H x La 3 Zr 2 O 12 ；
Wherein x is more than 0 and less than or equal to 4.48;
Li 7-x H x La 3 Zr 2 O 12 is of a cubic phase structure.
2. The method for preparing a flame retardant solid electrolyte material according to claim 1, comprising the steps of:
1) Mixing a lithium source, a zirconium source and a lanthanum source by a dry method or a wet method to prepare a precursor material, and sintering to obtain tetragonal Li 7 La 3 Zr 2 O 12 A material;
2) Li of the tetragonal phase 7 La 3 Zr 2 O 12 Mixing the material, tartaric acid and solvent, and grinding to perform phase transformation to obtain cubic-phase flame-retardant solid electrolyte material Li 7-x H x La 3 Zr 2 O 12 。
3. The method for producing a flame retardant solid electrolyte material according to claim 2, wherein the tetragonal Li in step 2) is 7 La 3 Zr 2 O 12 The mass ratio of the material to the tartaric acid is (10-40) 1.
4. The method for preparing a flame retardant solid electrolyte material according to claim 2, wherein the solvent in the step 2) is one or more selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetonitrile and cyclohexane.
5. The method for producing a flame retardant solid electrolyte material according to claim 4, wherein said tetragonal Li in step 2) is 7 La 3 Zr 2 O 12 The mass ratio of the material to the solvent is 1: (5-10).
6. The method for producing a flame retardant solid electrolyte material according to claim 2, wherein the grinding in step 2) is performed in a high-energy ball mill;
the grinding rotating speed of the high-energy ball mill is 500-650 r/min;
the grinding time of the high-energy ball mill is 5-10 hours.
7. The method for preparing a flame-retardant solid electrolyte material according to claim 2, wherein the molar ratio of the lithium source, the zirconium source and the lanthanum source in the step 1) is (6-7.5): (1.6-2.1): (2.8-3.3).
8. The diaphragm material is characterized by comprising a base film and a diaphragm coating coated on the surface of the base film;
the diaphragm coating is prepared by drying a solution composed of the flame-retardant solid electrolyte material prepared by the preparation method of the flame-retardant solid electrolyte material or any one of claims 2-7, a dispersing agent and deionized water.
9. The separator material according to claim 8, wherein the mass ratio of the dispersant to the flame-retardant solid electrolyte material is (0.1-5): 100.
10. A battery comprising a separator material according to any one of claims 8 to 9.
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