CN114497710B - Cubic garnet type solid electrolyte material, composite solid electrolyte, solid lithium battery and preparation methods thereof - Google Patents
Cubic garnet type solid electrolyte material, composite solid electrolyte, solid lithium battery and preparation methods thereof Download PDFInfo
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- CN114497710B CN114497710B CN202111591983.7A CN202111591983A CN114497710B CN 114497710 B CN114497710 B CN 114497710B CN 202111591983 A CN202111591983 A CN 202111591983A CN 114497710 B CN114497710 B CN 114497710B
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- solid electrolyte
- electrolyte material
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- lithium
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 206
- 239000000463 material Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 85
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000007787 solid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002223 garnet Substances 0.000 title abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000002001 electrolyte material Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 70
- 239000012528 membrane Substances 0.000 description 48
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 28
- 229910001416 lithium ion Inorganic materials 0.000 description 28
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 description 13
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 12
- 239000006230 acetylene black Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000002349 favourable effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000007790 scraping Methods 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 229910012888 LiNi0.6Co0.1Mn0.3O2 Inorganic materials 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 238000009837 dry grinding Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 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 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-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
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- NCOYDQIWSSMOEW-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;lanthanum(3+) Chemical compound [La+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NCOYDQIWSSMOEW-UHFFFAOYSA-K 0.000 description 1
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004898 kneading Methods 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
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- 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 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- 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
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Abstract
The invention relates to the technical field of lithium batteries, and discloses a cubic garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof. The crystal structure of the solid electrolyte material satisfies: i (422) Maximum peak value, I (422)/ I (211) >1.05，1.05≤I (422) /I (420) Less than or equal to 1.3. The crystal structure characteristics of the solid electrolyte material enable the solid electrolyte material to have higher ionic conductivity and stability.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a cubic garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof.
Background
The positive electrode, electrolyte and negative electrode of a solid state lithium battery are all composed of solid state materials, wherein the solid state electrolyte conducts lithium ions but is electronically insulating. The solid electrolyte is high temperature resistant, nonflammable, corrosion-free and nonvolatile, and the risk of spontaneous combustion of the battery can be basically eliminated. The solid electrolyte has a high Young's modulus, can suppress the formation of lithium dendrites, and can use metallic lithium with a high specific capacity as a negative electrode. In addition, the solid electrolyte has a wider electrochemical window, can bear higher oxidation potential, and is matched with a positive electrode with high specific capacity. Therefore, the solid-state lithium battery with high safety and high energy density has great promise for solving the pain points of frequent safety problems and mileage anxiety of new energy automobiles.
In all potential solid state electrolytes, cubic garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) at its relatively high room temperature ionic conductivity (> 10) -4 S/cm), a relatively wide electrochemical window (. Gtoreq.5.5V/Li) + Li), and excellent chemical and electrochemical stability to lithium metal negative electrodes, etc., are one of the most promising solid electrolytes. However, storage of LLZO under normal environmental conditions is highly challenging, especially with respect to structural and stoichiometric instability. Moisture in the air can easily induce lithium and proton exchange mechanisms, resulting in lithium defect stoichiometry (i.e., li 7-x H x La 3 Zr 2 O 12 ) And formation of LiOH and Li 2 CO 3 And (5) impurities.
CN108511797a discloses a kind of Li 7 La 3 Zr 2 O 12 The preparation method of the solid electrolyte comprises the steps of adopting ethanol as a solvent to synthesize LLZO electrolyte precursor by a non-hydrolytic sol-gel method, and then grinding and sintering to obtain LLZO electrolyte material, wherein XRD results show more impurity phases; the dilute nitric acid introduced in the process contains nitrogen oxide groups, and toxic and harmful nitrogen oxide compounds can be produced in the subsequent sintering process, so that the dilute nitric acid is harmful to human bodies, equipment and environment.
CN109935901a discloses a Nb, ta co-doped garnet type LLZO solid electrolyte and a preparation method thereof, wherein a lanthanum source is required to be pre-sintered to remove moisture in the process of synthesizing the LLZO solid electrolyte material, so that the sintering activity of lanthanum oxide is reduced, and further, the difficulty of sintering is reduced by performing wet ball milling and mixing by using isopropanol as a medium.
Therefore, research and development of a solid electrolyte material and a low-cost preparation method thereof are of great significance.
Disclosure of Invention
The invention aims to overcome the defect of low ionic conductivity of solid electrolyte in the prior art, and aims to solve the problems of difficult synthesis of cubic garnet type solid electrolyte materials, high wet ball milling cost by taking isopropanol as a medium and high surface LiOH and Li 2 CO 3 Defect problem of more impurities, provides a cubic garnet type solid electrolyte material, a composite solid electrolyte, a solid lithium battery and a preparation method thereof, wherein the solid electrolyte materialThe crystal structure features make it have higher ionic conductivity and stability.
In order to achieve the above object, a first aspect of the present invention provides a cubic phase garnet-type solid electrolyte material, wherein the crystal structure of the solid electrolyte material satisfies: i (422) Maximum peak value, I (422)/ I (211) >1.05，1.05≤I (422) /I (420) ≤1.3。
The second aspect of the present invention provides a method for preparing the solid electrolyte material, wherein the method comprises the following steps:
(1) Mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M 'source and an M' source to obtain a mixture;
(2) And under a dry atmosphere, carrying out gradient sintering on the mixture, and then crushing, sieving and deironing to obtain the solid electrolyte material.
The third aspect of the present invention provides a composite solid electrolyte, wherein the composite solid electrolyte comprises the solid electrolyte material, a binder, a monomer and a lithium salt.
The fourth aspect of the present invention provides a method for preparing the composite solid electrolyte, wherein the method comprises the following steps:
(1) Mixing a solid electrolyte material, a binder, a monomer and lithium salt;
(2) And (3) carrying out hot pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
A fifth aspect of the present invention provides a solid state lithium battery comprising a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte is the composite solid state electrolyte described above.
Through the technical scheme, the invention has the following advantages:
(1) Through the technical scheme of the invention, the crystal characteristics of the garnet type solid electrolyte material can be effectively regulated and controlled, and I in the crystal structure (422) Strongest, I (422)/ I (211) >1.05，1.05≤I (422) /I (420) Less than or equal to 1.3, is favorable for lithium ion transmission and has high ion conductivity;
(2) The garnet type solid electrolyte material provided by the invention is easy to form a cubic phase, has a stable structure, has basically no impurities such as lithium carbonate on the surface, and is beneficial to improving the stability of the garnet type solid electrolyte material in air and NMP solvents (N-methylpyrrolidone is also called 1-methyl 2-pyrrolidone, which is called NMP for short);
(3) The monomer in the composite solid electrolyte provided by the invention can effectively activate a lithium ion transmission channel, and reduce the interface impedance between an electrode and the electrolyte;
(4) The composite solid electrolyte provided by the invention adopts a solvent-free mode, so that the dispersion uniformity of garnet electrolyte materials in the composite solid electrolyte can be effectively improved, the formation of lithium dendrites can be well inhibited, and the battery cycle performance is improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of a garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic-phase standard card PDF# 80-0457;
FIG. 2 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in example 1;
FIG. 3 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in comparative example 1;
FIG. 4 is a scanning electron microscope image of the composite solid electrolyte prepared in example 1;
FIG. 5 is a scanning electron microscope image of the composite solid electrolyte prepared in comparative example 1;
fig. 6 is a cycle schematic of the solid lithium batteries prepared in example 1 and comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a cubic phase garnet-type solid electrolyte material, wherein the crystal structure of the solid electrolyte material satisfies: i (422) Maximum peak value, I (422)/ I (211) >1.05，1.05≤I (422) /I (420) ≤1.3。
The inventors of the present invention found that: when I in the crystal structure (422) The peak value is larger, satisfy I (422) /I (211) >1.05，1.05≤ I(422) / I(420) When the concentration of lithium ions in the crystal is less than or equal to 1.3, the crystal structure has stable cubic phase and high ion conductivity at the same time of the optimal balance point of the lithium ion concentration and the lithium ion transmission channel.
According to the present invention, preferably, the crystal structure of the solid electrolyte material satisfies: i is not less than 1.1 (422)/ I (211) ≤1.4，1.05≤I (422) /I (420) Less than or equal to 1.25; more preferably, 1.14.ltoreq.I (422)/ I (211) ≤1.34，1.09≤I (422) /I (420) Less than or equal to 1.20; the crystal characteristics are more favorable for lithium ion transmission, the ion conductivity is higher, and the stability is better.
According to the present invention, the solid electrolyte material comprises cubic garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) and metals and/or non-metals doped therein, in the present invention, the chemical formula of the solid electrolyte material is:
Li 7-δ M’ α La 3-β M” β Zr 2-γ M”’ γ O 12 ；
wherein, -1< delta <2 >, 0< alpha <1 >, 0< beta <3 >, 0< gamma <2;
wherein M' is selected from Mg, ca, al, ga, sm, tm or Y;
wherein M' is selected from Bi, ce, er, gd or Ho;
wherein M' "is selected from Zn, cu, ce, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb or Ta.
According to the invention, preferably, -0.5.ltoreq.delta.ltoreq.1, 0.ltoreq.alpha.ltoreq.0.5, 0.ltoreq.beta.ltoreq.1.5, 0.ltoreq.gamma.ltoreq.1.
According to the invention, more preferably, 0.ltoreq.delta.ltoreq. 0.6,0.ltoreq.alpha.ltoreq.0.2, 0.ltoreq.beta.ltoreq. 0.2,0.1.ltoreq.gamma.ltoreq.0.3.
According to the present invention, it is still further preferred that at least one of α or β is 0.
According to the invention, M' is preferably selected from Mg or Al; m' is selected from Bi or Er; m' "is selected from Co, hf, mn, ti, sn or Nb.
According to the present invention, more preferably, the solid electrolyte material includes: li (Li) 6.6 Mg 0.2 La 3 Zr 1.8 Nb 0.2 O 12 、Li 6.6 Mg 0.2 La 3 Zr 1.7 Hf 0.3 O 12 、Li 6.4 Al 0.2 La 3 Zr 1.7 Ti 0.1 O 12 、Li 6.4 Al 0.2 La 3 Zr 1.7 Ti 0.1 O 12 、Li 7 La 2.8 Er 0.2 Zr 1.9 Sn 0.2 O 12 And Li (lithium) 6.9 La 2.8 Bi 0.2 Zr 1.7 Nb 0.3 O 12 One or more of the following.
In the present invention, the inventors have found that the incorporation of M ', M ' and M ' in the multi-element positive electrode material is to obtain the above ratio I having peak intensity (422)/ I (211) >1.05，1.05≤I (422) /I (420) And 1.3 or less. Of course, the person skilled in the art can also satisfy the above conditions by other means of the ratio of the peak intensities of the resulting solid electrolyte material, which is not limited in the present invention, but the ratio of the peak intensities I (422)/ I (211) >1.05，1.05≤I (422) /I (420) Solid electrolyte materials less than or equal to 1.3 are within the scope of the invention.
The introduction of M ', M ' and/or M ' elements into the compounds of the chemical expression of the invention can carry out iso/homovalence on Li, la or/and Zr in garnet type solid electrolyte materials The element doping is substituted to adjust the Li content and the unit cell parameters, so as to reach the optimal balance point of the lithium ion concentration and the lithium ion transmission channel, and I in the crystal structure (422) Maximum peak value, I (422) /I (211) >1.05，1.05≤ I(422) / I(420) The ion conductivity is less than or equal to 1.3, and the stable cubic phase is obtained at the same time. In particular, under the synergistic effect of doping substitution elements at Li, la or/and Zr, tetrahedra [ Li ] in the crystal structure can be improved 1 O 4 ]And octahedron [ Li ] 2 O 6 ]The coplanarity reduces the distance between Li and Li, obviously improves the lithium ion conductivity of the garnet type solid electrolyte material, reduces the side reaction between the garnet type solid electrolyte material and water and carbon dioxide in the air, and improves the stability.
The solid electrolyte material is obtained by the synergistic doping of multi-point elements; in addition, the sintering temperature and the sintering time are controlled in the preparation process; preferably, the temperature of the first sintering is 300-750 ℃, the heating rate is 0.5-10 ℃/min, and the heat preservation time is 0.5-5h; the temperature of the second sintering is 800-1200 ℃, the temperature rising rate is 0.5-10 ℃/min, and the heat preservation time is 5-24h.
The second aspect of the present invention provides a method for preparing the solid electrolyte material, wherein the method comprises the following steps:
(1) Mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M 'source and an M' source to obtain a mixture;
(2) And under a dry atmosphere, carrying out gradient sintering on the mixture, and then crushing, sieving and deironing to obtain the solid electrolyte material.
The inventors of the present invention found that: and grinding by adopting a dry method or a wet method, and grinding the single raw materials or the mixed raw materials together to obtain the mixture with matched granularity. In the sintering process, garnet electrolyte materials with specific crystal structures and narrow particle size distribution are prepared through the coordinated doping of multi-point elements, the sintering temperature and the sintering time control. The electrolyte material is easy to form a cubic phase, stable in structure, basically free of impurities such as lithium carbonate on the surface, more stable to air and NMP solvents, and low in industrialization cost, and can adopt water as a wet grinding medium. The garnet electrolyte material with the specific crystal structure and narrow particle size distribution is favorable for subsequent sintering to obtain the oxide solid electrolyte sheet with high density and ion conductivity.
According to the invention, the M 'source, the M "source, the M'" source are each independently selected from one or more of the group consisting of oxides, hydroxides, carbonates, oxalates, acetates, and citrates of M ', M ", M'";
According to the invention, the M ' source, the M ' source and the M ' source are all preferably nano-scale, and the specific surface area is more than or equal to 20M 2 /g; in a more preferred aspect of the present invention,
according to the invention, the M ' source, the M ' source, the D of the M ' source 50 The same or different, each 20-200nm, and the specific surface area of 50-500m 2 /g。
According to the invention, D of the mixture after grinding and drying 50 1-5 μm, D of the mixture 100 4-10 μm.
According to the present invention, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide and lithium nitrate. In the present invention, the ratio of the actual amount of the lithium salt to the stoichiometric amount is 1 to 1.2 to compensate for lithium volatilization during sintering.
According to the invention, the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, lanthanum oxalate, lanthanum acetate and lanthanum citrate.
According to the invention, the zirconium source is selected from one or more of zirconium oxide, zirconium hydroxide, zirconium carbonate, zirconium oxalate, zirconium acetate and zirconium citrate.
According to the invention, the gradient sintering comprises a first sintering and a second sintering.
According to the invention, the temperature of the first sintering is 300-750 ℃, the heating rate is 0.5-10 ℃/min, and the heat preservation time is 0.5-5h; the temperature of the second sintering is 800-1200 ℃, the temperature rising rate is 0.5-10 ℃/min, and the heat preservation time is 5-24h.
According to the invention, preferably, the temperature of the first sintering is 400-600 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-3h; the second sintering temperature is 900-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 6-12h.
According to the present invention, the dry atmosphere may be formed of dry air, dry oxygen, dry nitrogen, or the like.
According to the present invention, the specific operations of mixing (blending), grinding, crushing, sieving, and iron removal are not particularly limited as long as the requirements are satisfied. In the invention, the mixing can be realized by a high-speed mixer, a V-shaped mixer, a double-cone mixer or a coulter mixer; the grinding can be realized by adopting a stirred ball mill, a planetary ball mill or a sand mill; the crushing can be realized by adopting a double-roller crushing mode, a ball mill mode, an air flow mill mode or a mechanical grinding mode; the screening can be performed by adopting an ultrasonic vibration screen; the iron removal can be performed by an electromagnetic iron removal machine.
The third aspect of the present invention provides a composite solid electrolyte, wherein the composite solid electrolyte comprises the solid electrolyte material, a binder, a monomer and a lithium salt.
According to the present invention, the solid electrolyte material is contained in an amount of 60 to 90 wt%, the binder is contained in an amount of 2 to 20 wt%, the monomer is contained in an amount of 3 to 60 wt%, and the lithium salt is contained in an amount of 5 to 60 wt%, based on the total weight of the composite solid electrolyte.
According to the present invention, it is preferable that the solid electrolyte material is contained in an amount of 70 to 80% by weight, the binder is contained in an amount of 5 to 10% by weight, the monomer is contained in an amount of 5 to 40% by weight, and the lithium salt is contained in an amount of 10 to 40% by weight, based on the total weight of the composite solid electrolyte.
According to the invention, the binder is selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, polyethylene oxide, polyether, polymethyl methacrylate, polyacrylonitrile, polyethylene carbonate and polypropylene carbonate.
According to the invention, the monomer is selected from one or more of unsaturated carbonates and their halides with a dielectric constant of more than 10, phosphates with a dielectric constant of more than 10, carboxylic acid esters with a dielectric constant of 2-10 and ethers with a dielectric constant of 5-10. In the invention, the monomer in the composite solid electrolyte provided by the invention can effectively activate a lithium ion transmission channel, and reduce the interface impedance between the electrode and the electrolyte.
According to the present invention, preferably, the carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and halides thereof.
According to the present invention, preferably, the phosphate is selected from one or more of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and halides thereof.
According to the present invention, preferably, the carboxylic acid ester is selected from one or more of γ -butyrolactone, methyl formate, methyl acetate, methyl butyrate and ethyl propionate.
According to the present invention, preferably, the ethers are selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxy ether, 1, 2-dimethoxyethane, diglyme and 12-crown-4 ether.
According to the present invention, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, and lithium trifluoromethanesulfonate.
According to the invention, the particle size D of the solid electrolyte material 50 0.05-5 μm.
The fourth aspect of the present invention provides a method for preparing the composite solid electrolyte, wherein the method comprises the following steps:
(1) Mixing a solid electrolyte material, a binder, a monomer and lithium salt;
(2) And (3) carrying out hot pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
According to the preparation method of the composite solid electrolyte, the preparation method is solvent-free, the uniform degree of the garnet electrolyte material dispersed in the composite solid electrolyte can be effectively improved by adopting a solvent-free mode, the formation of lithium dendrite can be well inhibited, and the battery cyclicity is improved.
According to the invention, the mixing conditions include: at a temperature of 0.5-2T m The method comprises the steps of carrying out a first treatment on the surface of the Wherein T is m Is the melting point of the binder; the mixing time is that the torque of the mixing machine reaches a steady state.
According to the present invention, the conditions of the hot pressing include: at a temperature of 0.5-2T m The method comprises the steps of carrying out a first treatment on the surface of the Wherein T is m Is the melting point of the binder; the hot pressing pressure can be adjusted according to the required electrolyte membrane thickness.
According to the present invention, the composite solid electrolyte is in the form of a film having a thickness of 2 to 20. Mu.m, preferably 4 to 15. Mu.m.
A fifth aspect of the present invention provides a solid state lithium battery comprising a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte is the composite solid state electrolyte described above.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
phase and crystal structure analysis was performed using an X-ray automatic diffractometer manufactured by Rigaku corporation of Japan;
Observing the morphology by using an S-4800 type scanning electron microscope manufactured by Hitachi corporation;
particle size distribution testing was performed using a Mastersizer 2000 laser particle sizer from Malvern, where only material D was characterized 50 ；
Adopting CT-3008 of Xinwei electronic limited company to carry out charge-discharge and cycle test on the solid-state battery;
ac impedance and electrochemical window testing was performed using the SP-150 electrochemical workstation from Bio-logic, france.
The raw materials mentioned in the invention are all commercial products meeting the relevant national standard or industry standard.
Example 1
This example is presented to illustrate solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared using the methods of the present invention (Li-site 2-valent doping, zr-site aliovalent doping, dry mixing, one-stage firing).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：Nb 2 O 5 =3.465: 1.5:1.8:0.2:0.1 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Is not required, mgO and Nb 2 O 5 D of (2) 50 All 50nm, and the specific surface area is 150m 2 /g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 mu m;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 Mg 0.2 La 3 Zr 1.8 Nb 0.2 O 12 。
FIG. 1 is an X-ray diffraction pattern of a garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic-phase standard card PDF# 80-0457; as shown in FIG. 1, the X-ray diffraction pattern of example 1 has a crystal structure consistent with that of the standard card PDF#80-0457, i.e., a cubic garnet type crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.21，I (422) /I (420) ＝1.16。
FIG. 2 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in example 1; as shown in fig. 2, the garnet-type solid electrolyte material has no residual impurities such as lithium carbonate on the surface, is favorable for lithium ion transmission and has high stability.
FIG. 4 is a scanning electron microscope image of the composite solid electrolyte prepared in example 1; as shown in fig. 4, the garnet-type solid electrolyte material is uniformly dispersed in the composite solid electrolyte. Using stainless Steel Sheet (SS) as electrode, assembling SS composite solid electrolyte film SS test system, AC impedance testing at 25deg.C, 10mV disturbance voltage and frequency range of 1 MHz-1 Hz, and measuringCalculated ion conductivity was 2.6X10 -3 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.7V.
(3) According to 80:5:5:10 weight ratio of cubic garnet-type solid electrolyte material, binder polyethylene oxide, monomer ethylene carbonate and lithium salt lithium bistrifluoromethylsulfonylimide in the step (2) are respectively weighed, and then are mixed at 80 ℃ and hot-pressed at 100 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 27 omega.
Fig. 6 is a cycle schematic of the solid state lithium batteries prepared in example 1 and comparative example 1, as shown in fig. 6, the solid state lithium battery in example 1 has a specific capacity of 192.2mAh/g at a first cycle discharge of 3.0-4.3V, 0.2C, 25 ℃; the capacity retention after 80 weeks of circulation was 81.1%.
Example 2
This example is presented to illustrate solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared using the methods of the present invention (Li site 2-doped, zr site homovalent doped, wet mixed, one-stage fired).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：HfO 2 = 3.399:1.5:1.7:0.2:0.3 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Is not required, mgO and HfO 2 D of (2) 50 All 50nm, proportion tableArea of 150m 2 /g; putting into a ball mill, performing wet ball milling by taking water as a medium, and finally drying; after ball milling and drying, D of the mixture 50 1.5 μm, D 100 4.7 μm;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 440 ℃ at a speed of 1 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 Mg 0.2 La 3 Zr 1.7 Hf 0.3 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction diagram obtained by the test is consistent with the cube phase standard card PDF#80-0457, namely the cube phase garnet type crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.14，I (422) /I (420) ＝1.12。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has basically no impurities such as residual lithium carbonate and the like on the surface, is favorable for lithium ion transmission and has high stability.
(3) According to 80:5:5:10 weight ratio the cubic garnet-type solid electrolyte material, polyvinylidene fluoride, gamma-butyrolactone and lithium bistrifluoromethylsulfonylimide in step (2) were weighed respectively, and then kneaded at 100 ℃ and hot-pressed at 160 ℃ to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and in the frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 3.1 multiplied by 10 -3 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.8V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.7 Co 0.1 Mn 0.2 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylideneThe mass ratio of the difluoroethylene is 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 26 omega.
In addition, the first-week discharge specific capacity of the solid-state lithium battery reaches 196.3mAh/g at 3.0-4.3V, 0.2C and 25 ℃; the capacity retention after 80 weeks of circulation was 87.3%.
Example 3
This example is presented to illustrate solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared using the methods of the present invention (Li site 3-valent doping, zr site homovalent doping, wet mixing, one-stage firing).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：Al 2 O 3 ：TiO 2 = 3.296:1.5:1.7:0.1:0.3 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Is not required to have a particle size of Al 2 O 3 And TiO 2 D of (2) 50 All 30nm, and the specific surface area is 270m 2 /g; putting into a ball mill, performing wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture 50 1.2 μm, D 100 4.3 μm;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 500 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 7 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.4 Al 0.2 La 3 Zr 1.7 Ti 0.3 O 12 。
The crystal structure in the X-ray diffraction diagram obtained by the test is consistent with the cube phase standard card PDF#80-0457, namely the cube phase crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.34，I (422) /I (420) ＝1.18。
In addition, the garnet type solid electrolyte material has basically no impurities such as lithium carbonate and the like remained on the surface, is favorable for lithium ion transmission and has high stability.
(3) According to 80:5:5:10 weight ratio of garnet-type solid electrolyte material, polytetrafluoroethylene, diglyme and lithium bistrifluoromethylsulfonylimide in the step (2) were weighed respectively, and then kneaded at 170 ℃ and hot-pressed at 170 ℃ to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 9.3 multiplied by 10 -4 S/cm, an SS|composite solid electrolyte membrane|Li test system was assembled, and electrochemical window testing was performed at 25℃at a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.7V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.7 Co 0.1 Mn 0.2 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 31 omega.
In addition, the first-week discharge specific capacity of the solid-state lithium battery reaches 194.9mAh/g at 3.0-4.3V, 0.2C and 25 ℃; the capacity retention after 80 weeks of circulation was 88.9%.
Example 4
This example is presented to illustrate solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared using the methods of the present invention (wet mix, two-stage bake).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：Al 2 O 3 ：TiO 2 = 3.296:1.5:1.7:0.1:0.3 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 The grain size of (3) is not required, al 2 O 3 And TiO 2 D of (2) 50 All 30nm, and the specific surface area is 270m 2 And/g. Li is mixed with 2 CO 3 、La 2 O 3 、ZrO 2 And Al 2 O 3 Putting into a ball mill, performing wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture 50 1.2 μm, D 100 4.3 μm;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 600 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 1h, heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 10h, and naturally cooling to about 100 ℃ along with a furnace body; then with weighed TiO 2 Putting into a ball mill, performing wet ball milling by taking water as a medium, and finally drying. After ball milling and drying, D of the mixture 50 1.2 μm, D 100 4.3 μm. Placing the mixture into a roller kiln, heating to 960 ℃ at a speed of 5 ℃/min in a dry air atmosphere, preserving heat for 9 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.4 Al 0.2 La 3 Zr 1.7 Ti 0.3 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction diagram obtained by the test has the same duration as that of a standard card PDF#80-0457 of a cubic phase, namely, the crystal structure of a cubic phase garnet type, I (422) Maximum peak value, I (422)/ I (211) ＝1.33，I (422) /I (420) ＝1.20。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has basically no impurities such as residual lithium carbonate and the like on the surface, is favorable for lithium ion transmission and has high stability.
(3) According to 80:5:5:10 weight ratio of garnet-type solid electrolyte material, polytetrafluoroethylene, diglyme and lithium bistrifluoromethylsulfonylimide in the step (2) were weighed respectively, and then kneaded at 170 ℃ and hot-pressed at 170 ℃ to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 4.3 multiplied by 10 -3 S/cm, an SS|composite solid electrolyte membrane|Li test system was assembled, and electrochemical window testing was performed at 25℃at a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.8V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.83 Co 0.07 Mn 0.1 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 35 omega.
In addition, the first-week discharge specific capacity of the solid-state lithium battery reaches 205.4mAh/g at 3.0-4.3V, 0.2C and 25 ℃; the capacity retention after 80 weeks of circulation was 85.8%.
Example 5
This example is directed to solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared using the methods of the present invention (La site homovalence doping, zr site homovalence doping, one-stage sintering).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：Er 2 O 3 ：SnO 2 =3.64: 1.2:1.8:0.3:0.2 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 The grain size of Er is not required 2 O 3 And SnO 2 D of (2) 50 All 80nm, and the specific surface area is 100m 2 /g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 mu m;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 550 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 1h, heating to 1050 ℃ at a speed of 3 ℃/min, preserving heat for 10h, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 7 La 2.4 Er 0.6 Zr 1.8 Sn 0.2 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction diagram obtained by the test is consistent with the cube phase standard card PDF#80-0457, namely the cube phase garnet type crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.15，I (422) /I (420) ＝1.09。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has basically no impurities such as residual lithium carbonate and the like on the surface, is favorable for lithium ion transmission and has high stability.
(3) According to 80:5:5:10 weight ratio the garnet-type solid electrolyte material, vinylidene fluoride-hexafluoropropylene copolymer, fluoroethylene carbonate and lithium bistrifluoromethylsulfonylimide in step (2) were weighed separately, and then kneaded at 120℃and hot-pressed at 150℃to obtain a composite solid electrolyte membrane having a thickness of 15. Mu.m.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and ion conductivity is calculated to be 8.8x10 -4 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.9V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.95 Co 0.02 Mn 0.03 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 26 omega.
In addition, the specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 224.1mAh/g; the capacity retention after 80 weeks of circulation was 83.4%.
Example 6
This example is directed to solid electrolyte materials and composite solid electrolytes and solid lithium batteries prepared by the methods of the present invention (La site homovalence doping, zr site heterovalence doping, one-stage sintering).
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：Bi 2 O 3 ：Nb 2 O 5 =3.465: 1.4:1.6:0.1:0.2 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 The grain size of Bi is not required 2 O 3 And Nb (Nb) 2 O 5 D of (2) 50 All 20nm, and the specific surface area is 370m 2 /g; mixing materials in a dry method; d of the mixture after mixing 50 4.2 μm, D 100 Is 10 mu m;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 560 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 990 ℃ at a speed of 3 ℃/min, preserving heat for 9 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 La 2.8 Bi 0.2 Zr 1.6 Nb 0.4 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction diagram obtained by the test is consistent with the cube phase standard card PDF#80-0457, namely the cube phase garnet type crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.25，I (422) /I (420) ＝1.14。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has basically no impurities such as residual lithium carbonate and the like on the surface, is favorable for lithium ion transmission and has high stability.
(3) According to 80:5:5:10 weight ratio of garnet-type solid electrolyte material, vinylidene fluoride-hexafluoropropylene copolymer, fluoroethylene carbonate and lithium bistrifluoromethylsulfonylimide in the second step, respectively, and then kneading at 120 ℃ and hot-pressing at 150 ℃ to obtain a composite solid electrolyte membrane with a thickness of 15 μm.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 3.2 multiplied by 10 -3 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.8V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.95 Co 0.02 Mn 0.03 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 32Ω.
In addition, the specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 223.6mAh/g; the capacity retention after 80 weeks of circulation was 83.1%.
Example 7
A solid electrolyte material was prepared in the same manner as in example 1, except that: the amounts of the main doping elements are different, specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：Nb 2 O 5 =2.94: 1.5:1.8:0.6:0.1 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Not requiring the particle size of MgO and Nb 2 O 5 D of (2) 50 All 50nm, and the specific surface area is 150m 2 /g; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 μm.
(2) Placing the mixture in the step (1) into a roller kiln, heating to 970 ℃ at a speed of 3 ℃/min in a dry air atmosphere, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 5.6 Mg 0.6 La 3 Zr 1.8 Nb 0.2 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction pattern is consistent with the cube phase standard card PDF#80-0457, namely the cube phase garnet crystal structure, I (422) Maximum peak value, I (422)/ I (211) ＝1.17，I (422) /I (420) ＝1.13。
(3) According to 80:5:5:10 weight ratio the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonylimide in the step (2) are respectively weighed, and then are mixed at 80 ℃ and hot-pressed at 100 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 3.1 multiplied by 10 -3 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 5.7V.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 35 omega.
The specific capacity of the solid-state lithium battery at 3.0-4.3V, 0.2C and 25 ℃ for first week reaches 185.6mAh/g; the capacity retention after 80 weeks of circulation was 78.8%.
Comparative example 1
A solid electrolyte material was prepared in the same manner as in example 1, except that: mainly without doping; specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 =3.675: 1.5:2 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 The particle size of the particles is not required, and the mixture is put into the mixture for dry mixing; d of the mixture after mixing 50 4.2 μm, D 100 Is 10 μm.
(2) Placing the mixture in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain the garnet type solid electrolyte material.
FIG. 1 is an X-ray diffraction pattern of a garnet-type solid electrolyte material prepared in example 1 and comparative example 1 and a cubic-phase standard card PDF# 80-0457; as shown in FIG. 1, the X-ray diffraction pattern of comparative example 1 has a large number of cleavage peaks, i.e., tetragonal phase crystal structure, I (422)/ I (211) ＝0.89，I (422) /I (420) ＝0.97。
In addition, fig. 3 is a scanning electron microscope image of the garnet-type solid electrolyte material prepared in comparative example 1, and as shown in fig. 3, a large amount of impurities such as lithium carbonate exist on the surface of the garnet-type solid electrolyte material, which is unfavorable for lithium ion transport and has poor stability.
(3) The garnet-type solid electrolyte material, polyethylene oxide, ethylene carbonate and lithium bistrifluoromethylsulfonylimide in the step (2) were weighed according to a weight ratio of 80:5:5:10, and then kneaded and hot-pressed at 80 ℃ to obtain a composite solid electrolyte membrane with a thickness of 15 μm.
Fig. 5 is a scanning electron microscope image of the composite solid electrolyte prepared in comparative example 1, and as shown in fig. 5, the dispersion uniformity of the garnet-type solid electrolyte material in the composite solid electrolyte is lower than that in example 1 (fig. 4).
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 2.3 multiplied by 10 -5 S/cm, an SS|composite solid electrolyte membrane|Li test system was assembled, and electrochemical window testing was performed at 25℃at a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 4.5V. This is because it is difficult for the tetragonal garnet-type solid electrolyte material to transport lithium ions.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Dispersing acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride in N-methyl-2-pyrrolidone according to a mass ratio of 80:5:5:10, doctor-coating the mixture on aluminum foil, drying the aluminum foil, punching the aluminum foil, and vacuum drying the aluminum foil at 120 ℃ for 12 hours; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 83 omega.
Fig. 6 is a cycle schematic of the solid lithium batteries prepared in example 1 and comparative example 1; as shown in fig. 6, the solid-state lithium battery in comparative example 1 has a specific capacity of 175.9mAh/g at a first-week discharge of 3.0-4.3V, 0.2C, 25 ℃; the capacity retention after 80 weeks of circulation was 61.0%.
Comparative example 2
A solid electrolyte material was prepared in the same manner as in example 1, except that: the doping amount is mainly out of the limit of the invention, specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：Nb 2 O 5 : mgo=2.415: 1.5:1:0.2 molar ratio of Li 2 CO 3 、La 2 O 3 Is not required, nb 2 O 5 D of (2) 50 All are 2 μm; then carrying out dry grinding and mixing; d of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 μm.
(2) Placing the mixture in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 4.6 Mg 0.2 La 3 Nb 2 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: i in the crystal structure of the X-ray diffraction diagram obtained by testing (422)/ I (211) ＝0.96，I (422) /I (420) ＝0.77。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has a large amount of impurities such as lithium carbonate on the surface base, which is unfavorable for lithium ion transmission and has poor stability.
(3) According to 80:5:5:10 weight ratio garnet-type solid electrolyte material, polyethylene oxide, ethylene carbonate and lithium bistrifluoromethylsulfonylimide in the second step are weighed respectively, and then mixed and hot-pressed at 80 ℃ to obtain a composite solid electrolyte membrane with a thickness of 15 mu m.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and in the frequency range of 1 MHz-1 Hz, and ion calculation is carried outConductivity of 4.2X10 -5 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 4.5V. This is because the garnet-type solid electrolyte material has excessive lattice distortion and is difficult to transport lithium ions.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
The interface impedance of the solid-state lithium battery is 76 omega through an alternating current impedance test.
The specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 184.1mAh/g; the capacity retention after 80 weeks of circulation was 75.8%.
Comparative example 3
A solid electrolyte material was prepared in the same manner as in example 1, except that: mainly without ethylene carbonate; specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：Nb 2 O 5 =3.465: 1.5:1.8:0.2:0.1 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 The particle size of (3) is not required; mgO and Nb 2 O 5 D of (2) 50 All 50nm, and the specific surface area is 150m 2 /g; and then dry grinding and mixing are carried out. D of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 mu m;
(2) Placing the mixture in the step (1) into a roller kiln, heating to 420 ℃ at a rate of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, and then heating to 970 ℃ at a rate of 3 ℃/minPreserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 Mg 0.2 La 3 Zr 1.8 Nb 0.2 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: i in the crystal structure of the X-ray diffraction diagram obtained by testing (422)/ I (211) ＝0.86，I (422) /I (420) ＝1.52。
In addition, from the scanning electron microscope, it can be derived that: the garnet type solid electrolyte material has no residual lithium carbonate and other impurities on the surface, and is favorable to lithium ion transmission.
(3) According to 80:10:10 weight ratio the garnet-type solid electrolyte material, polyethylene oxide and lithium bistrifluoromethylsulfonylimide in step (2) were weighed separately, and then kneaded and hot-pressed at 80 c to obtain a composite solid electrolyte membrane having a thickness of 15 μm.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and ion conductivity is calculated to be 1.1X10 -5 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 4.6V. This is because it is difficult to transport lithium ions due to the lack of a monomer that activates the lithium ion transport channel.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 326 omega.
In addition, the specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 150.7mAh/g; the capacity retention after 80 weeks of circulation was 50.6%.
Comparative example 4
A solid electrolyte material was prepared in the same manner as in example 1, except that: in step (1), the particle size of each material is mainly out of the range defined by the present invention, specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：Nb 2 O 5 =3.465: 1.5:1.8:0.2:0.1 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Is not required, mgO and Nb 2 O 5 D of (2) 50 All 50nm, and the specific surface area is 150m 2 /g; and then dry grinding and mixing are carried out. D of the mixture after grinding and mixing 50 8.5 μm, D 100 30 μm.
(2) Placing the mixture in the step (1) into a roller kiln, heating to 420 ℃ at a speed of 2 ℃/min in a dry air atmosphere, preserving heat for 2 hours, heating to 970 ℃ at a speed of 3 ℃/min, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 Mg 0.2 La 3 Zr 1.8 Nb 0.2 O 12 。
Further, from the X-ray diffraction pattern, it can be derived that: the crystal structure in the X-ray diffraction diagram is consistent with the cube phase standard card PDF#80-0457, namely the cube phase crystal structure, I (422)/ I (211) ＝0.86，I (422) /I (420) ＝0.8。
(3) According to 80:5:5:10 weight ratio the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonylimide in the step (2) are respectively weighed, and then are mixed at 80 ℃ and hot-pressed at 100 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
Stainless Steel Sheet (SS) is used as electrode to assemble SS composite solid electrolyte A membrane I SS test system is used for carrying out alternating current impedance test at 25 ℃ and 10mV disturbance voltage and in the frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 2.7X10 -5 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 4.5V. This is due to I (422) Lower, unfavorable for lithium ion transport.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 68 omega.
In addition, the specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 175.1mAh/g; the capacity retention after 80 weeks of circulation was 61.8%.
Comparative example 5
A solid electrolyte material was prepared in the same manner as in example 1, except that: in step (2), the gradient sintering conditions are mainly different, specifically:
(1) According to Li 2 CO 3 ：La 2 O 3 ：ZrO 2 ：MgO：Nb 2 O 5 =3.465: 1.5:1.8:0.2:0.1 molar ratio of Li 2 CO 3 、La 2 O 3 And ZrO(s) 2 Is not required, mgO and Nb 2 O 5 D of (2) 50 Are 50nm, mgO and Nb 2 O 5 D of (2) 50 All 50nm, and the specific surface area is 150m 2 /g; and then dry grinding and mixing are carried out. D of the mixture after grinding and mixing 50 4.2 μm, D 100 Is 10 μm.
(2) Placing the mixture in the step (1) into a roller kiln, heating to 970 ℃ at a speed of 3 ℃/min in a dry air atmosphere, preserving heat for 8 hours, and naturally cooling to about 100 ℃; crushing, sieving and deironing to obtain garnet type solid electrolyte material Li 6.6 Mg 0.2 La 3 Zr 1.8 Nb 0.2 O 12 。
The crystal structure in the X-ray diffraction diagram is consistent with the cube phase standard card PDF#80-0457, namely the cube phase crystal structure, I (422)/ I (211) ＝0.9，I (422) /I (420) ＝1.6。
(3) According to 80:5:5:10 weight ratio the garnet-type solid electrolyte material, the binder polyethylene oxide, the monomer ethylene carbonate and the lithium salt lithium bistrifluoromethylsulfonylimide in the step (2) are respectively weighed, and then are mixed at 80 ℃ and hot-pressed at 100 ℃ to obtain the composite solid electrolyte membrane with the thickness of 15 mu m.
A stainless Steel Sheet (SS) is taken as an electrode, an SS|composite solid electrolyte membrane|SS test system is assembled, alternating current impedance test is carried out at 25 ℃ and 10mV disturbance voltage and a frequency range of 1 MHz-1 Hz, and the ion conductivity is calculated to be 3.3 multiplied by 10 -5 S/cm; an ss|composite solid electrolyte membrane|li test system was assembled and electrochemical window testing was performed at 25 ℃, a scan rate of 10mV and a voltage range of-1V to 6V, with an oxidation potential of 4.5V. This is due to I (422) Lower, I (420) Higher, not favorable to lithium ion transmission.
(4) The nickel cobalt lithium manganate positive electrode active material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) Acetylene black, lithium bis (trifluoromethylsulfonyl) imide and polyvinylidene fluoride according to the mass ratio of 80:5:5:10 are dispersed in N-methyl-2-pyrrolidone, are coated on aluminum foil in a scraping way and are dried, and then are punched into tablets and are dried for 12 hours at 120 ℃ in vacuum; and assembling the anode, the composite solid electrolyte membrane and the lithium metal cathode into a glove box filled with argon, wherein the water content and the oxygen content of the glove box are less than 5 ppm.
Through an alternating current impedance test, the interface impedance of the solid-state lithium battery is 83 omega.
In addition, the specific capacity of the solid-state lithium battery at the first week discharge of 3.0-4.3V, 0.2C and 25 ℃ reaches 177.1mAh/g; the capacity retention after 80 weeks of circulation was 56.8%.
From the above results, it can be seen that:
(1) In the crystal structure of the solid electrolyte material of the invention I (422) Maximum peak value, I (422)/ I (211) >1.05，1.05≤I (422) /I (420) Less than or equal to 1.3, is favorable for lithium ion transmission and has high ion conductivity; the structure is stable, and the surface is basically free of impurities such as lithium carbonate and the like;
(2) The monomer in the composite solid electrolyte provided by the invention can effectively activate a lithium ion transmission channel, and reduce the interface impedance between an electrode and the electrolyte;
(3) The invention can effectively improve the dispersion uniformity of garnet electrolyte materials in the composite solid electrolyte, can well inhibit the formation of lithium dendrites and improve the battery cycle performance;
(4) The cubic phase garnet type solid electrolyte material has higher ionic conductivity (more than 10) -4 S/cm), higher oxidation potential.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A cubic phase garnet-type solid electrolyte material, characterized in that the crystal structure of the solid electrolyte material satisfies: i (422) The peak value is maximum, and the ratio of peak intensity is 1.1 to less than or equal to I (422)/ I (211) ≤1.4，1.09≤I (422) /I (420) ≤1.3；
The chemical expression of the solid electrolyte material is as follows: li (Li) 7-δ M’ α La 3-β M’’ β Zr 2-γ M’’’ γ O 12 ；
Wherein, -1< delta <2 >, 0< alpha <1 >, 0< beta <3 >, 0< gamma <2;
M' is selected from Mg, ca, al, ga, sm, tm or Y;
m '' is selected from Ce, er, gd or Ho;
m' "is selected from Zn, cu, ce, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb or Ta; one of α or β is 0.
2. The solid state electrolyte material of claim 1 wherein the crystal structure of the solid state electrolyte material satisfies: i is more than or equal to 1.14 (422)/ I (211) ≤1.34，1.09≤I (422) /I (420) ≤1.20。
3. The solid state electrolyte material of claim 1 wherein-0.5.ltoreq.δ.ltoreq.1, 0.ltoreq.α.ltoreq.0.5, 0.ltoreq.β.ltoreq.1.5, 0.ltoreq.γ.ltoreq.1.
4. The solid electrolyte material of claim 3, wherein 0.ltoreq.δ.ltoreq. 0.6,0.ltoreq.α.ltoreq.0.2, 0.ltoreq.β.ltoreq. 0.2,0.1.ltoreq.γ.ltoreq.0.3.
5. The solid state electrolyte material of claim 1 wherein M' is selected from Mg or Al;
m '' is selected from Er;
m' "is selected from Co, hf, mn, ti, sn or Nb.
6. A method of preparing a solid electrolyte material according to any one of claims 1 to 5, comprising:
(1) Mixing, grinding and drying a lithium source, a lanthanum source, a zirconium source, an M '' source and an M '' source to obtain a mixture;
(2) And under a dry atmosphere, carrying out gradient sintering on the mixture, and then crushing, sieving and deironing to obtain the solid electrolyte material.
7. The method of claim 6, wherein the M 'source, the M "source, the M'" source are each independently selected from one or more of an oxide, hydroxide, carbonate, oxalate, acetate, and citrate of M ', M ", M'";
the M ' source, the M ' ' source and the M ' ' source are all nano-scale, and the specific surface area is more than or equal to 20M 2 /g；
D of the M 'source, M' '' source 50 The same or different, each 20-200nm, and the specific surface area of 50-500m 2 /g；
In step (1), D of the mixture 50 1-5 μm, D of the mixture 100 4-10 μm.
8. The method of manufacturing of claim 6, wherein the gradient sintering comprises a first sintering and a second sintering;
wherein the temperature of the first sintering is 300-750 ℃, the heating rate is 0.5-10 ℃/min, and the heat preservation time is 0.5-5h; the temperature of the second sintering is 800-1200 ℃, the temperature rising rate is 0.5-10 ℃/min, and the heat preservation time is 5-24h.
9. The preparation method of claim 8, wherein the temperature of the first sintering is 400-600 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-3h; the second sintering temperature is 900-1100 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 6-12h.
10. A composite solid electrolyte comprising the solid electrolyte material of any one of claims 1-5, a binder, a monomer, and a lithium salt.
11. The composite solid electrolyte of claim 10, wherein the solid electrolyte material is present in an amount of 60-90 wt%, the binder is present in an amount of 2-20 wt%, the monomer is present in an amount of 3-60 wt%, and the lithium salt is present in an amount of 5-60 wt%, based on the total weight of the composite solid electrolyte;
the monomer is one or more selected from unsaturated carbonic ester with dielectric constant more than 10 and halogenated compound thereof, phosphate with dielectric constant more than 10, carboxylic ester with dielectric constant between 2 and 10 and ether with dielectric constant between 5 and 10;
particle size D of the solid electrolyte material 50 0.05-5 μm.
12. A method of preparing the composite solid electrolyte of claim 10 or 11, comprising:
(1) Mixing a solid electrolyte material, a binder, a monomer and lithium salt;
(2) And (3) carrying out hot pressing treatment on the mixture obtained in the step (1) to obtain the composite solid electrolyte.
13. The method of claim 12, wherein the mixing conditions include: at a temperature of 0.5-2T m ；
The hot pressing conditions include: at a temperature of 0.5-2T m ；
Wherein T is m Is the melting point of the binder;
the composite solid electrolyte is in a film shape, and the thickness of the film is 2-20 mu m.
14. A solid state lithium battery comprising a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte is the composite solid state electrolyte of claim 10 or 11.
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