CN115101806A - Oxide solid electrolyte, preparation method thereof, lithium battery and battery pack - Google Patents
Oxide solid electrolyte, preparation method thereof, lithium battery and battery pack Download PDFInfo
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- CN115101806A CN115101806A CN202210708674.1A CN202210708674A CN115101806A CN 115101806 A CN115101806 A CN 115101806A CN 202210708674 A CN202210708674 A CN 202210708674A CN 115101806 A CN115101806 A CN 115101806A
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- lanthanum zirconium
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 82
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 74
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 32
- 239000002345 surface coating layer Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 37
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- QMTITMYAGTWBKM-UHFFFAOYSA-N [O].[Zr].[La] Chemical compound [O].[Zr].[La] QMTITMYAGTWBKM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 19
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 229910052788 barium Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052691 Erbium Inorganic materials 0.000 claims description 10
- 229910052689 Holmium Inorganic materials 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 229910052772 Samarium Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910052706 scandium Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052781 Neptunium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052767 actinium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052713 technetium Inorganic materials 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000010304 firing Methods 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 claims 2
- -1 M 3 Compound Chemical class 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 239000010416 ion conductor Substances 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000010936 titanium Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- 239000004576 sand Substances 0.000 description 27
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 24
- 229910001928 zirconium oxide Inorganic materials 0.000 description 21
- 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 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 description 20
- 239000011777 magnesium Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 150000002500 ions Chemical group 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 3
- AREPHAPHABGCQP-UHFFFAOYSA-N 1-(dimethylamino)-3-[2-[2-(4-methoxyphenyl)ethyl]phenoxy]propan-2-ol Chemical compound C1=CC(OC)=CC=C1CCC1=CC=CC=C1OCC(O)CN(C)C AREPHAPHABGCQP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 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
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000010401 Prunus avium Nutrition 0.000 description 1
- 241001290151 Prunus avium subsp. avium Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- SLODBEHWNYQCRC-UHFFFAOYSA-N [La+3].[O-2].[Zr+4] Chemical compound [La+3].[O-2].[Zr+4] SLODBEHWNYQCRC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- WRWOVDSMUMEITO-UHFFFAOYSA-N actinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Ac+3].[Ac+3] WRWOVDSMUMEITO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the field of oxide solid electrolytes, in particular to an oxide solid electrolyte, a preparation method thereof, a lithium battery and a battery pack. The oxide solid electrolyte includes: the device comprises a substrate and a surface coating layer for coating the substrate; the chemical composition of the matrix satisfies the chemical formula Li 7‑x M 1 x La 3‑y M 2 y Zr 2‑z M 3 z O 12‑u X u The chemical composition of the surface coating layer satisfies the chemical formula Li v E w G h O l By defining M 1 、M 2 、M 3 X, E and G and the numerical range of x, y, z, u, v, w, h and l, can realize multi-site element doping, form a uniform ion conductor coating layer on the surface of primary particles of the electrolyte, and greatly improve the ion conductivity and junction of the lithium lanthanum zirconium oxygen solid electrolyteStability of structure and surface.
Description
Technical Field
The invention relates to the field of oxide solid electrolytes, in particular to an oxide solid electrolyte, a preparation method thereof, a lithium battery and a battery pack.
Background
With the rapid development of the power battery and energy storage battery markets, people put higher requirements on the energy density and the safety performance of the lithium ion battery. The traditional lithium ion battery has larger hidden danger in safety performance due to the use of electrolyte in the structure, and is limited to the use of a cathode without metal lithium, and the improvement space of the energy density of the battery is close to the bottleneck. The solid-state battery adopts the solid electrolyte to replace the traditional electrolyte, so that the safety problem of the battery can be fundamentally solved, and the metal lithium-containing negative electrode replaces the traditional graphite or silicon carbon negative electrode, so that the energy density of the battery can be further improved, and the solid-state battery becomes the development direction of the acknowledged next-generation lithium battery.
In solid-state battery systems, one of the most critical materials at present is the solid-state electrolyte. The solid electrolyte includes an oxide solid electrolyte, a sulfide solid electrolyte, a polymer solid electrolyte, and an organic-inorganic composite solid electrolyte. Lithium lanthanum zirconium oxide, as one of the oxide solid electrolytes, is one of the most industrialized solid electrolytes due to its advantages of high conductivity, good thermal stability, wide electrochemical window, etc.
The lithium lanthanum zirconium oxygen solid electrolyte has two structures of tetragonal phase and cubic phase, wherein the ionic conductivity of a tetragonal phase sample is lower and is only 10 -6 S/cm, has no practical value; the cubic phase samples have high ionic conductivity, typically up to 10 -4 -10 -3 S/cm is an object which is focused on and developed by people. In the actual preparation process, the cubic-phase lithium lanthanum zirconium oxide is unstable in structure at normal temperature and is easy to convert into a tetragonal-phase structure; when the lithium lanthanum zirconium oxide is stored and used in the air atmosphere, the lithium lanthanum zirconium oxide is easily decomposed on the surfaceLithium carbonate precipitates, reducing its ionic conductivity, especially when the particle size reaches the nanometer scale. The practical process of lithium lanthanum zirconium oxide is greatly hindered by the problems.
In the prior art, the modification research of the lithium lanthanum zirconium oxygen solid electrolyte focuses on stabilizing the cubic phase structure of the electrolyte through element doping so as to improve the ionic conductivity of the electrolyte. CN110247107A discloses a solid electrolyte, a preparation method and application thereof, In the invention, trivalent invariant elements such as In, Er, Ho and the like are introduced into a lithium lanthanum zirconium oxygen solid electrolyte, so as to realize doping at La ion position and improve the cubic structure stability of the material; the doping of La ion site elements increases the volume of tetrahedral vacancy, thereby improving the ionic conductivity of the electrolyte. However, the improvement range of the ionic conductivity of the invention is limited, and in addition, the invention does not relate to the problem of improving the residual lithium carbonate on the surface of the lithium lanthanum zirconium oxide, and the promotion effect on the practical application of the lithium lanthanum zirconium oxide cannot be achieved.
Disclosure of Invention
The invention aims to overcome the defects that the ionic conductivity of a lithium lanthanum zirconium oxygen solid electrolyte is not ideal in improvement effect and the problem that the conductivity of lithium carbonate precipitated on the surface of the lithium lanthanum zirconium oxygen solid electrolyte is reduced in the prior art is not effectively solved, and provides an oxide solid electrolyte, a preparation method thereof, a lithium battery and a battery pack.
In order to achieve the above object, a first aspect of the present invention provides a lithium lanthanum zirconium oxygen solid electrolyte, comprising: the device comprises a substrate and a surface coating layer for coating the substrate;
the chemical composition of the matrix satisfies the chemical formula Li 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein M is 1 Is at least one element of Ba, Fe, B, Zn, Al, Ga and Ge; m 2 At least one element of Rb, Sr, Ba, Ca, Y, Bi, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu and Ac; m is a group of 3 Is Mg, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ge, Se, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I,Hf. At least one element selected from Ir, Pt, Tl, Pb, Ce, Pu, Np, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, Br, I and S; x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.5, and u is more than or equal to 0 and less than or equal to 0.1;
the chemical composition of the surface coating layer satisfies the chemical formula Li v E w G h O l Wherein E is at least one element of Al, Ti and Zr; g is at least one element of Al, Ti, Zr and Mg; v is more than or equal to 0.5 and less than or equal to 10, w is more than or equal to 0.5 and less than or equal to 7, h is more than or equal to 0.5 and less than or equal to 7, and l is more than or equal to 1 and less than or equal to 15.
The second aspect of the present invention provides a method for preparing a lithium lanthanum zirconium oxygen solid electrolyte, comprising:
(1) mixing Li-containing compound and M 1 Compound, La-containing compound, and element-containing M 2 Compound, Zr-containing compound, element-containing M 3 Compounding and mixing the compound and the compound containing the element X to obtain a mixture;
(2) roasting the mixture to obtain a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding the lithium-containing lanthanum zirconium oxygen matrix, the solution or the nano-scale sol containing the elements E and G and the solvent, and then drying the obtained slurry to obtain an electrolyte precursor;
(3) and carrying out heat treatment on the electrolyte precursor in an oxygen-containing atmosphere to obtain the lithium lanthanum zirconium oxygen solid electrolyte.
The third aspect of the present invention provides the lithium lanthanum zirconium oxygen solid electrolyte prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides a lithium battery comprising the lithium lanthanum zirconium oxide solid electrolyte of the first or third aspect.
A fifth aspect of the invention provides a battery pack comprising the lithium battery of the fourth aspect.
Through the technical scheme, the invention has the following beneficial effects:
(1) the ion conductor provided by the invention coats the multi-site doped lithium lanthanum zirconium oxygen solid electrolyte, adopts multi-site element doping, and greatly improves the ion conductivity through multiple actions of forming lithium vacancy, increasing the lithium content in an octahedral position, increasing a lattice constant and the like on the premise of stabilizing a cubic phase structure.
(2) According to the lithium lanthanum zirconium oxygen doped solid electrolyte coated with the ionic conductor and provided by the invention, the coating capable of consuming lithium carbonate is introduced in the preparation process, so that the content of the residual lithium carbonate on the surface of the sample is effectively reduced, and the ionic conductivity of the sample is further improved.
(3) According to the multi-site lithium lanthanum zirconium oxygen doped solid electrolyte coated with the ionic conductor, the uniform ionic conductor coating layer is constructed on the surface of the primary particle, so that a barrier effect is realized on the surface of the solid electrolyte, the further reaction of the solid electrolyte and air is prevented, the secondary generation of lithium carbonate on the surface of a sample is prevented, the stability of the surface of the sample to the air is improved, and the high ionic conductivity is kept in the storage and use processes.
(4) The invention provides a preparation method of an ion conductor coated multi-site doped lithium lanthanum zirconium oxide solid electrolyte, which is characterized in that a cubic phase matrix with high ionic conductivity is prepared by a solid phase method, the uniform distribution of a coating element compound on the surface of the matrix is further realized by adopting a liquid phase coating and sand milling process, and the purpose of consuming residual lithium carbonate while constructing a uniform ion conductor coating layer on the surface of the matrix is achieved by combining a subsequent heat treatment process. The ionic conductivity, the structure and the surface stability of the lithium lanthanum zirconium oxygen solid electrolyte can be greatly improved.
(5) The preparation method provided by the invention is easy to operate, the introduction mode of the doping element and the uniform ion conductor coating layer is simple, and the improvement effect on the material performance is obvious.
Drawings
Fig. 1 is a scanning electron microscope image of the lithium lanthanum zirconium oxide solid electrolyte prepared in example 1.
Fig. 2 is a scanning electron microscope image of the lithium lanthanum zirconium oxide solid electrolyte prepared in comparative example 1.
Fig. 3 is a high-resolution transmission electron microscope image of the lithium lanthanum zirconium oxide solid electrolyte prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a lithium lanthanum zirconium oxygen solid electrolyte, which comprises: the coating comprises a substrate and a surface coating layer for coating the substrate;
the chemical composition of the matrix satisfies the chemical formula Li 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein M is 1 Is at least one element of Ba, Fe, B, Zn, Al, Ga and Ge; m 2 At least one element of Rb, Sr, Ba, Ca, Y, Bi, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu and Ac; m 3 At least one element selected from Mg, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ge, Se, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Hf, Ir, Pt, Tl, Pb, Ce, Pu, Np, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, Br, I and S; x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.5, and u is more than or equal to 0 and less than or equal to 0.1;
the chemical composition of the surface coating layer satisfies the chemical formula Li v E w G h O l Wherein E is at least one element of Al, Ti and Zr; g is at least one element of Al, Ti, Zr and Mg; v is more than or equal to 0.5 and less than or equal to 10, w is more than or equal to 0.5 and less than or equal to 7, h is more than or equal to 0.5 and less than or equal to 7, and l is more than or equal to 1 and less than or equal to 15.
In some embodiments of the invention, the matrix has a chemical composition satisfying the formula Li 7-x M 1 x La 3- y M 2 y Zr 2-z M 3 z O 12-u X u Preferably, M is selected so that the lithium lanthanum zirconium oxygen solid electrolyte has higher ion conductivity 1 Is at least one of B, Al, Ga and GeAn element; m 2 Is at least one element of Sr, Ba, Y, Nd, Pm, Sm, Dy, Ho and Er; m is a group of 3 At least one element of Mg, Sc, Ti, Ge, Se, Tc, Ru, In, Hf, Ir, Pt, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, I and S; x is more than or equal to 0 and less than 0.07, y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.3, and u is more than or equal to 0 and less than or equal to 0.08.
In some embodiments of the invention, the chemical composition of the surface coating is such that Li is satisfied v E w G h O l Preferably, E is at least one element of Ti and Zr, so that the surface coating layer can more effectively play a role of a barrier and prevent secondary generation of lithium carbonate on the surface of the solid electrolyte, and further the lithium lanthanum zirconium oxygen solid electrolyte has higher ionic conductivity and stability; g is at least one element of Al, Ti and Zr; v is more than or equal to 1 and less than or equal to 8, w is more than or equal to 1 and less than or equal to 5, h is more than or equal to 1 and less than or equal to 5, and l is more than or equal to 2 and less than or equal to 12.
In some embodiments of the invention, the lithium lanthanum zirconium oxide solid electrolyte has an average particle size D 50 0.1-5 μm; further, the average grain size of the matrix is less than 4.5 μm, and the thickness of the surface coating layer is less than 0.5 μm; the matrix is as follows: the weight ratio of the surface coating layer is 100: (0.05-40). The relatively small matrix particle size and the thin surface coating layer can shorten the lithium ion diffusion path and also facilitate the preparation of a thinner solid electrolyte membrane.
In the present invention, in the garnet structure of the lithium lanthanum zirconium oxygen solid electrolyte, 8-fold coordinated LaO8 dodecahedron (24c) and 6-fold coordinated ZrO6 octahedron (16a) together constitute a structural framework. The lithium ion random portion occupies 48g or off-center 96h of two interstitial sites therein. The 24d tetrahedron is connected with four adjacent octahedrons in a coplanar manner to form a three-dimensional transmission network. By increasing the lithium content in the octahedron, the lithium ions are induced to tend to pass through the path with the lowest activation energy, namely the coplanar triangular bottleneck of the octahedron and the tetrahedron for transmission, so that the conductivity of the lithium ions can be effectively improved; the number of lithium atoms in the corresponding octahedral position can be observed to be between 5 and 7 by a high-resolution transmission electron microscope. By introducing element doping, on one hand, the charge balance relation around lithium ions is regulated and controlled to form lithium vacancies, and on the other hand, the introduced element atoms have larger sizes and can play a role of column support in the lithium ion migration process to increase the size of a migration path; larger heterogeneous atoms and point defects to a certain degree exist near the position of a lithium atom in a high-resolution transmission electron microscope, and the more remarkable increase of the lattice constant can be found by measuring the unit cell size of the lithium atom or calculating through an electron diffraction result.
The second aspect of the present invention provides a method for preparing a lithium lanthanum zirconium oxygen solid electrolyte, comprising:
(1) mixing Li-containing compound and M-containing element 1 Compound, La-containing compound, and element-containing M 2 Compound, Zr-containing compound, element-containing M 3 Compounding and mixing the compound and the compound containing the element X to obtain a mixture;
(2) roasting the mixture to obtain a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding the lithium lanthanum zirconium oxygen-containing matrix, the solution or the nano sol containing the elements E and G and the solvent, and then drying the obtained slurry to obtain an electrolyte precursor;
(3) and carrying out heat treatment on the electrolyte precursor in an oxygen-containing atmosphere to obtain the lithium lanthanum zirconium oxygen solid electrolyte.
In some embodiments of the invention, in step (1), M 1 May be at least one element selected from Ba, Fe, B, Zn, Al, Ga, and Ge; m 2 Can be at least one element selected from Rb, Sr, Ba, Ca, Y, Bi, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu and Ac; m 3 Can be at least one element of Mg, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ge, Se, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Hf, Ir, Pt, Tl, Pb, Ce, Pu, Np, Y, Ta, Nb, Mo, W; x can be at least one element of F, Cl, Br, I and S; preferably, M 1 Is at least one element of B, Al, Ga and Ge; m is a group of 2 Is at least one element of Sr, Ba, Y, Nd, Pm, Sm, Dy, Ho and Er; m 3 Is Mg, Sc, Ti, Ge, Se, Tc, Ru, In, Hf, Ir, Pt, Y, Ta,At least one element selected from Nb, Mo and W; x is at least one element of F, Cl, I and S.
In some embodiments of the invention, in step (1), the Li-containing compound, the element M-containing compound, and the element M are mixed together to form a mixture 1 Compound, La-containing compound, element-containing M 2 Compound, Zr-containing compound, element-containing M 3 The feeding amount of the compound and the compound containing the element X meet the chemical formula Li 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.5, and u is more than or equal to 0 and less than or equal to 0.1; preferably, the formula Li is satisfied 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein x is more than or equal to 0 and less than 0.07, y is more than or equal to 0 and less than or equal to 0.03, z is more than or equal to 0 and less than or equal to 0.3, and u is more than or equal to 0 and less than or equal to 0.08.
In some embodiments of the present invention, in the step (1), the Li-containing compound is added in an amount of 1% to 20% by weight in excess of the stoichiometric ratio satisfying the above chemical formula.
In some embodiments of the invention, in step (1), the Li-containing compound, the element-containing M 1 Compound, La-containing compound, element-containing M 2 Compound, Zr-containing compound, element-containing M 3 The compound and the compound containing the element X are respectively nano-scale oxide, hydroxide, nitrate, oxalate, organic alkoxide or carbonate.
In some embodiments of the present invention, in step (1), the mixing may employ methods, apparatuses and processes for material mixing, which are conventional in the art, and are not particularly limited herein. For example, a sand mill, a ball mill mixing tank, or a planetary mixing tank may be used.
In some embodiments of the present invention, in step (2), in order to better form a cubic phase after the mixture is calcined, and further obtain a lithium lanthanum zirconium oxygen-containing matrix with high ionic conductivity, the calcining conditions include: the roasting temperature can be 600-1400 ℃, and is preferably 800-1200 ℃; the calcination time may be from 2 to 22 hours, preferably from 6 to 12 hours.
In the present invention, the baking process may include pre-baking and secondary sintering; wherein the pre-sintering temperature can be 600-950 ℃, and the pre-sintering time can be 1-10 h; the secondary sintering temperature can be 950-.
In some embodiments of the invention, in step (2), the particle size of the lithium-containing lanthanum zirconium oxygen matrix is preferably up to D50 < 20 μm. To meet the particle size requirement, the sintered product is preferably subjected to a crushing treatment. The disruption treatment may be carried out by methods, equipment and processes conventional in the art, for example, a jet mill may be used.
In some embodiments of the present invention, in the step (3), E may be at least one element of Al, Ti, Zr; g can be at least one element of Al, Ti, Zr and Mg; preferably, E can be at least one element of Ti and Zr; g may be at least one element selected from Al, Ti and Zr.
In some embodiments of the present invention, in step (3), the dosage of the solution or nanosol containing elements E and G satisfies the formula Li v E w G h O l V is more than or equal to 0.5 and less than or equal to 10, w is more than or equal to 0.5 and less than or equal to 7, h is more than or equal to 0.5 and less than or equal to 7, and l is more than or equal to 1 and less than or equal to 15; preferably, the formula Li is satisfied v E w G h O l Wherein v is more than or equal to 1 and less than or equal to 8, w is more than or equal to 1 and less than or equal to 5, h is more than or equal to 1 and less than or equal to 5, and l is more than or equal to 2 and less than or equal to 12.
In some embodiments of the invention, in step (3), the solution or nanosol containing elements E and G is a solution or nanosol of an oxide, hydroxide, nitrate, oxalate, organic alkoxide or carbonate containing elements E and G in ethanol, isopropanol or NMP (N-methylpyrrolidone).
In some embodiments of the invention, in step (3), the lithium-containing lanthanum zirconium oxide matrix: solution or nanosol containing elements E and G: the weight ratio of the solvent can be (5-50): 0.05-2): 10-500.
In some embodiments of the present invention, in step (3), the solvent may be selected from ethanol, isopropanol, or NMP.
In some embodiments of the present invention, in step (3), the sanding treatment may cause elements E and G to be more uniformly distributed on the surface of the lithium-containing lanthanum zirconium oxygen matrix. The sanding treatment may be carried out using equipment and processes conventional in the art, and is not particularly limited in this application so long as the sanded slurry is of a particle size such that D50 < 1 μm.
In some embodiments of the present invention, in step (3), the drying may be performed by a method conventional in the art, and is not particularly limited in the present application, as long as the water and the solvent in the slurry can be separated by drying.
In some embodiments of the present invention, in step (4), the heat treatment is preferably performed by sintering, and the conditions of the heat treatment include: the temperature can be 200-1000 ℃, and is preferably 400-800 ℃; the time can be 2 to 20 hours, preferably 6 to 12 hours.
In some embodiments of the present invention, in step (4), the product obtained after the heat treatment is preferably subjected to a crushing treatment so that the average particle diameter D50 of the prepared lithium lanthanum zirconium oxide solid electrolyte is 0.1 to 5 μm. The disruption treatment may employ methods, equipment and processes conventional in the art.
For the lithium lanthanum zirconium oxygen solid electrolyte prepared by the method provided by the invention, the ionic conductivity of the lithium lanthanum zirconium oxygen solid electrolyte in the initial state after preparation is compared with the ionic conductivity of the lithium lanthanum zirconium oxygen solid electrolyte after the lithium lanthanum zirconium oxygen solid electrolyte is stored for a plurality of times under the conditions of constant temperature and constant humidity, the reduction of the ionic conductivity is reduced, and the better maintenance can be achieved.
The third aspect of the present invention provides the lithium lanthanum zirconium oxygen solid electrolyte prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides a lithium battery comprising the lithium lanthanum zirconium oxide solid electrolyte of the first or third aspect.
A fifth aspect of the invention provides a battery pack comprising a lithium battery as claimed in the fourth aspect.
The present invention will be described in detail below by way of examples. In the following examples, common commercial products were used as materials unless otherwise specified.
Example 1
(1) Satisfies the formula Li in accordance with the chemical composition of the obtained matrix 6.98 Ga 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 Weighing lithium carbonate, gallium oxide, lanthanum oxide, strontium carbonate, zirconium oxide and magnesium oxide, and mixing the raw materials in a sand mill by a wet method, wherein a mixing medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 900 ℃ for 6h, then heating and secondary sintering at 1100 ℃ for 10 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 4 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding the ethanol sol containing the lithium lanthanum zirconium oxygen matrix, the titanium oxide and the zirconium oxide and ethanol in a sand mill to obtain D 50 A slurry of < 0.5 μm; drying the slurry in a vacuum oven at 100 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: ethanol sol of titanium oxide and zirconium oxide (the solid content of the sol is 10 wt%, and the ratio of the amount of Ti to Zr in the sol is 43: 7): the weight ratio of ethanol is 5: 0.05: 10;
(4) sintering the electrolyte precursor for 8 hours at 600 ℃ in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle diameter D50 is 1 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P1 (tested, the matrix is Li 1) 6.98 Ga 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 The surface coating layer is as follows: li 4 Ti 4.3 Zr 0.7 O 12 )。
Fig. 1 is a scanning electron micrograph of the lithium lanthanum zirconium oxide solid electrolyte prepared in example 1. As can be seen from fig. 1, after the surface coating, the lithium lanthanum zirconium oxygen solid electrolyte P1 has little lithium carbonate on the surface (as shown by the black part indicated by reference numeral 1 in the figure).
Fig. 3 is a high-resolution transmission electron microscope image of the lithium lanthanum zirconium oxide solid electrolyte prepared in example 1. As can be seen from FIG. 3, the cell of the element-doped lithium lanthanum zirconium oxygen solid electrolyte P1 has a large number of lattices with different shades under a high-resolution transmission electron microscope, which indicates that lithium ion vacancies exist in the cell.
Example 2
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.95 Al 0.05 La 2.99 Y 0.01 Zr 1.99 Sc 0.01 O 12 Weighing lithium carbonate, aluminum oxide, lanthanum oxide, yttrium oxide, zirconium oxide and scandium oxide, and carrying out wet mixing on the raw materials in a sand mill, wherein a mixing medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 850 deg.C for 8h, heating, and secondary sintering at 1200 deg.C for 8 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 4.5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding isopropanol sol containing lithium lanthanum zirconium oxygen matrix, titanium oxide and zirconium oxide and isopropanol in a sand mill to obtain D 50 A slurry of < 0.4 μm; drying the slurry in a vacuum oven at 90 ℃ to obtain an electrolyte precursor; wherein, the lithium lanthanum zirconium oxygen containing matrix: isopropanol sol of titanium oxide and zirconium oxide (the solid content of the sol is 10 wt%, and the ratio of the amount of Ti to Zr in the sol is 4: 1): the weight ratio of the isopropanol is 10: 0.2: 30, of a nitrogen-containing gas;
(4) sintering the electrolyte precursor at 750 ℃ for 10 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle diameter D50 is 0.8 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P2 (tested, the matrix is Li 2) 6.95 Al 0.05 La 2.99 Y 0.01 Zr 1.99 Sc 0.01 O 12 The surface coating layer is as follows: li 2 Ti 0.8 Zr 0.2 O 3 )。
Example 3
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.99 Ge 0.01 La 2.98 Nd 0.02 Zr 1.95 Hf 0.05 O 12 Weighing lithium carbonate, germanium oxide, lanthanum oxide, neodymium oxide, zirconium oxide and hafnium oxide, and mixing the raw materials in a sand mill by a wet method, wherein a mixed medium is alcohol, and the mixing conditions comprise: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 900 ℃ for 6h, then heating and secondary sintering at 1100 ℃ for 10 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 3.5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding NMP sol containing lithium lanthanum zirconium oxygen matrix, alumina and zirconia and NMP in a sanding machine to obtain D 50 A slurry of < 0.05 μm; drying the slurry in a vacuum oven at 130 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: NMP sol of alumina and zirconia (the solid content of the sol is 10 wt%, and the mass ratio of Al to Zr in the sol is 1: 9): the weight ratio of NMP is 20: 0.5: 100, respectively;
(4) sintering the electrolyte precursor at 650 ℃ for 9 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to obtain the average particle diameter D50 of 0.1 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P3 (tested, the matrix is Li 3) 6.99 Ge 0.01 La 2.98 Nd 0.02 Zr 1.95 Hf 0.05 O 12 The surface coating layer is as follows: li 2 Zr 0.9 Al 0.1 O 3 )。
Example 4
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.92 Ba 0.08 La 3 Zr 1.5 V 0.5 O 12 Weighing lithium carbonate, barium carbonate, lanthanum oxide, zirconium oxide and vanadium oxide, mixing the raw materials in a sand mill by a wet method, and mixing a mediumIs alcohol, and the mixing conditions comprise: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 700 deg.C for 4h, heating, and secondary sintering at 1000 deg.C for 12 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 3.5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding ethanol sol containing a lithium lanthanum zirconium oxygen matrix, titanium oxide and zirconium oxide (the solid content of the sol is 10 wt%, and the quantity ratio of Ti to Zr in the sol is 2:3) and ethanol in a sand mill to obtain D 50 Slurry less than 0.4 μm; drying the slurry in a vacuum oven at 90 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: ethanolic sols of titanium oxide and zirconium oxide: the weight ratio of ethanol is 50: 2: 500;
(4) sintering the electrolyte precursor at 750 deg.C for 12 hr in dry air atmosphere, and crushing the sintered product in high-energy vibration mill to obtain average particle diameter D50 of 1 μm to obtain solid electrolyte P4 (matrix is Li 4) 6.92 Ba 0.08 La 3 Zr 1.5 V 0.5 O 12 The surface coating layer is as follows: li 4 Ti 2 Zr 3 O 12 )。
Example 5
(1) Satisfies the formula Li in accordance with the chemical composition of the obtained matrix 6.95 Fe 0.05 La 3 Zr 2 O 12 Weighing lithium carbonate, iron oxide, lanthanum oxide and zirconium oxide, and mixing the raw materials in a sand mill by a wet method, wherein a mixed medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 850 deg.C for 6h, heating, and secondary sintering at 1200 deg.C for 10 h. Crushing the secondary sintered product in a jet mill until the granularity of the secondary sintered product reaches D50 which is less than 4.5 mu m, thereby obtaining a matrix containing lithium, lanthanum, zirconium and oxygen;
(3) sanding the ethanol sol containing the lithium lanthanum zirconium oxygen matrix, the titanium oxide and the zirconium oxide and ethanol in a sand mill to obtain D 50 A slurry of < 0.5 μm; drying the slurry in a vacuum oven at 90 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: ethanol sol of titanium oxide and zirconium oxide (the solid content of the sol is 10 wt%, and the ratio of the Ti to Zr in the sol is 1: 1): the weight ratio of ethanol is 5: 0.1: 10;
(4) sintering the electrolyte precursor at 700 ℃ for 15 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle size D50 is 0.5 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P5 (tested, the matrix is Li 5) 6.95 Fe 0.05 La 3 Zr 2 O 12 The surface coating layer is as follows: li 2 Ti 0.5 Zr 0.5 O 3 )。
Example 6
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.99 Zn 0.01 La 3 Zr 1.9 Mn 0.1 O 12 Weighing lithium carbonate, zinc oxide, lanthanum oxide, zirconium oxide and manganese oxide, and carrying out wet mixing on the raw materials in a sand mill, wherein a mixed medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 750 deg.C for 5h, heating, and secondary sintering at 1250 deg.C for 9 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding isopropanol sol containing lithium lanthanum zirconium oxygen matrix, alumina and zirconia and isopropanol in a sand mill to obtain D 50 A slurry of < 0.8 μm; drying the slurry in a vacuum oven at 100 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: isopropanol sol of alumina and zirconia (the solid content of the sol is 10 wt%, and the mass ratio of Al to Zr in the sol is 1: 9): the weight ratio of the isopropyl alcohol is10：0.5：40；
(4) Sintering the electrolyte precursor at 680 ℃ for 10 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle diameter D50 is 4 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P6 (tested, the matrix is Li 6) 6.99 Zn 0.01 La 3 Zr 1.9 Mn 0.1 O 12 The surface coating layer is: li 2 Zr 0.9 Al 0.1 O 3 )。
Example 7
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.95 Ge 0.05 La 2.99 Ac 0.01 Zr 1.98 Co 0.02 O 12 Weighing lithium carbonate, germanium oxide, lanthanum oxide, actinium oxide, zirconium oxide and cobalt oxide, and carrying out wet mixing on the raw materials in a sand mill, wherein a mixed medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 rpm, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process can be divided into: presintering at 950 ℃ for 1h, then heating and secondary sintering at 950 ℃ for 12 h. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding NMP sol containing lithium lanthanum zirconium oxygen matrix, titanium oxide and zirconium oxide and NMP in a sanding machine to obtain D 50 A slurry of < 0.6 μm; drying the slurry in a 135 ℃ vacuum oven to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: an NMP sol of titanium oxide and zirconium oxide (the sol has a solid content of 10 wt%, and the ratio of the amount of Ti to Zr in the sol is 4: 1): the weight ratio of NMP is 20: 1: 100, respectively;
(4) sintering the electrolyte precursor at 1000 ℃ for 2 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle diameter D50 is 5 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P7 (tested, the matrix is Li 7) 6.95 Ge 0.05 La 2.99 Ac 0.01 Zr 1.98 Co 0.02 O 12 The surface coating layer is: li 4 Ti 4 ZrO 12 )。
Example 8
(1) Satisfies the formula Li according to the chemical composition of the obtained matrix 6.95 Ga 0.05 La 2.99 Rb 0.01 Zr 1.98 Tl 0.02 O 12 Weighing lithium carbonate, gallium oxide, lanthanum oxide, rubidium oxide, zirconium oxide and thallium oxide, and mixing the raw materials in a sand mill by a wet method, wherein a mixed medium is alcohol, and the mixing conditions comprise that: the rotation speed of the sand mill is 1000 revolutions per minute, and the mixing time is 2 hours, so that a mixture is obtained;
(2) roasting the mixture in a muffle furnace, wherein the process comprises the following steps: presintering at 600 ℃ for 10h, then heating and sintering at 1400 ℃ for 1h for the second time. Crushing the secondary sintered product in a jet mill to ensure that the granularity of the secondary sintered product reaches D50 less than 4.5 mu m, thus obtaining a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding the ethanol sol containing the lithium lanthanum zirconium oxygen matrix, the titanium oxide and the zirconium oxide and ethanol in a sand mill to obtain D 50 A slurry of < 0.3 μm; drying the slurry in a vacuum oven at 90 ℃ to obtain an electrolyte precursor; wherein, the lithium-containing lanthanum zirconium oxygen matrix: ethanol sol of titanium oxide and zirconium oxide (the solid content of the sol is 10 wt%, and the ratio of the Ti to Zr in the sol is 1: 1): the weight ratio of ethanol is 50: 1: 500, a step of;
(4) sintering the electrolyte precursor at 200 ℃ for 20 hours in a dry air atmosphere, and crushing the sintered product in a high-energy vibration mill to ensure that the average particle diameter D50 is 3 mu m to obtain the lithium lanthanum zirconium oxygen solid electrolyte, which is marked as P8 (tested, the matrix is Li 8) 6.95 Ga 0.05 La 2.99 Rb 0.01 Zr 1.98 Tl 0.02 O 12 The surface coating layer is as follows: li 2 Ti 0.5 Zr 0.5 O 3 )。
Comparative example 1
The method according to example 1, except that in step (3) only the lithium-containing lanthanum zirconium oxygen matrix and ethanol are sanded in a sand mill (weight of lithium-containing lanthanum zirconium oxygen matrix: ethanol)Ratio of 5:10), other conditions were the same as in example 1. A solid electrolyte was prepared and was designated DP1 (tested, formula Li) 6.98 Ga 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 No surface coating).
Fig. 2 is a scanning electron microscope image of the lithium lanthanum zirconium oxide solid electrolyte prepared in comparative example 1. As can be seen from fig. 2, a large amount of black lithium carbonate (as shown by reference numeral 1 in the figure) remained on the surface of the lithium lanthanum zirconium oxide solid electrolyte DP1 without the surface coating layer. The presence of a large inert layer of lithium carbonate can seriously impede the transport of lithium ions and reduce the ionic conductivity of the solid electrolyte.
Comparative example 2
The procedure of example 1 was followed except that the lithium lanthanum zirconium oxygen-containing matrix, the ethanol sol of silica and the ethanol in step (3) were subjected to sand milling in a sand mill (weight ratio of lithium lanthanum zirconium oxygen-containing matrix: ethanol sol of silica: ethanol: 5: 0.05: 10), and the other conditions were the same as in example 1. A solid electrolyte was prepared and was designated DP2 (test, matrix: Li) 6.98 Ga 0.0 2 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 The surface coating layer is as follows: li 4 SiO 4 )。
Comparative example 3
The process of example 1 is followed except that in step (3) the lithium lanthanum zirconium oxygen containing matrix: ethanolic sols of titanium oxide and zirconium oxide: the mass ratio of ethanol is 9: 8: 100, and the other conditions were the same as in example 1. A solid electrolyte was prepared, designated DP 3.
The substrate for DP3 was tested as: li 6.98 Ga 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 The surface coating layer is as follows: li 11 Ti 9 Zr 8 O 35 。
Comparative example 4
The process as in example 1, with the difference that in step (1) the chemical composition of the matrix obtained satisfies the formula Li 6.98 Zr 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 Lithium carbonate, zirconium oxide, lanthanum oxide, strontium carbonate, zirconium oxide, and magnesium oxide were weighed and the other conditions were the same as in example 1. A solid electrolyte was prepared and was designated DP4 (test, matrix: Li) 6.98 Zr 0.02 La 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 The surface coating layer is as follows: li 4 Ti 4.3 Zr 0.7 O 12 )。
Comparative example 5
The process as in example 1, with the difference that in step (1) the chemical composition of the matrix obtained satisfies the formula Li 6 GaLa 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 Lithium carbonate, gallium oxide, lanthanum oxide, strontium carbonate, zirconium oxide, and magnesium oxide were weighed under the same conditions as in example 1. A solid electrolyte was prepared and was designated DP5 (test, matrix: Li) 6 GaLa 2.99 Sr 0.01 Zr 1.98 Mg 0.02 O 12 The surface coating layer is as follows: li 4 Ti 4.3 Zr 0.7 O 12 )。
Test example
The solid electrolytes P1-P8 and DP1-DP4 prepared in examples 1 to 8 of the present invention and comparative examples 1 to 5 were subjected to conductivity tests, and the ion conductivities of the above solid electrolytes were respectively tested in the initial state after the preparation and after being stored under constant temperature and humidity conditions for 10 days. The specific test process is as follows:
1. conductivity test at initial State
1) Taking 10g of each of P1-P8 and DP1-DP4, placing 2g of sample powder in a mold with the diameter of 11mm, tabletting under the condition of 100MPa, and preparing a compact disc from the sample;
2) placing the pressed compact wafer in an alumina crucible with a cover, uniformly covering the wafer with the residual 8g of sample powder, closing the crucible cover, sintering at 1150 ℃ for 8 hours, taking out the wafer, and polishing to obtain a solid electrolyte ceramic wafer;
3) and (3) placing the solid electrolyte ceramic wafer in an electrochemical workstation to test the alternating current impedance (the test frequency is set to be 0.01-10MPa) at room temperature, and calculating according to a formula (I) to obtain the corresponding ionic conductivity.
σ＝L/RS (Ⅰ)
Wherein σ is ionic conductivity (S/cm); r is an alternating current impedance value (omega); l is the thickness (cm) of the solid electrolyte ceramic wafer; s is the area (cm) of the solid electrolyte ceramic sheet 2 )。
The test results are shown in table 1.
2. Ion conductivity test after 10 days of storage under constant temperature and humidity conditions
1) 10g of each of the samples P1-P8 and DP1-DP4 was stored in a constant temperature and humidity chamber at a relative humidity of 60% and a temperature of 45 ℃ for 10 days.
2) The sample after 10 days of storage was tested for ionic conductivity according to the conductivity test method and parameters described above for initial conditions.
The test results are shown in table 1.
TABLE 1
As can be seen from the results in Table 1, P1-P8 had higher ionic conductivity than DP1-DP5 regardless of 10 days of storage in the initial state or under constant temperature and humidity conditions. The conductivity of each sample in the initial state is higher than that of each sample stored under the conditions of constant temperature and constant humidity for 10 days, but the ionic conductivity of P1-P8 is reduced in a low way, and the ionic single conductivity of DP1-DP5 is reduced exponentially and greatly. Wherein, the surface coating layers in DP2 and DP3 and the basal bodies in DP4 and DP5 do not meet the conditions of the invention, and the ion conductivity value can not reach the level of P1-P8; and DP1 contained no surface coating, and the decrease in ionic conductivity was the highest in all samples after 10 days of storage under constant temperature and humidity conditions.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A lithium lanthanum zirconium oxygen solid electrolyte, characterized in that the electrolyte comprises: the device comprises a substrate and a surface coating layer for coating the substrate;
the chemical composition of the matrix satisfies the chemical formula Li 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein M is 1 Is at least one element of Ba, Fe, B, Zn, Al, Ga and Ge; m 2 At least one element of Rb, Sr, Ba, Ca, Y, Bi, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu and Ac; m 3 At least one element selected from Mg, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ge, Se, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Hf, Ir, Pt, Tl, Pb, Ce, Pu, Np, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, Br, I and S; x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.5, and u is more than or equal to 0 and less than or equal to 0.1;
the chemical composition of the surface coating layer satisfies the chemical formula Li v E w G h O l Wherein E is at least one element of Al, Ti and Zr; g is at least one element of Al, Ti, Zr and Mg; v is more than or equal to 0.5 and less than or equal to 10, w is more than or equal to 0.5 and less than or equal to 7, h is more than or equal to 0.5 and less than or equal to 7, and l is more than or equal to 1 and less than or equal to 15.
2. The electrolyte of claim 1, wherein M 1 At least one element of B, Al, Ga and Ge; m 2 At least one element of Sr, Ba, Y, Nd, Pm, Sm, Dy, Ho and Er; m 3 At least one element of Mg, Sc, Ti, Ge, Se, Tc, Ru, In, Hf, Ir, Pt, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, I and S；0≤x＜0.07，0≤y≤0.03，0≤z≤0.3，0≤u≤0.08。
3. The electrolyte according to claim 1 or 2, wherein E is at least one element of Ti, Zr; g is at least one element of Al, Ti and Zr; v is more than or equal to 1 and less than or equal to 8, w is more than or equal to 1 and less than or equal to 5, h is more than or equal to 1 and less than or equal to 5, and l is more than or equal to 2 and less than or equal to 12.
4. The electrolyte of any of claims 1-3, wherein the electrolyte has an average particle size D 50 0.1-5 μm; the average grain diameter of the matrix is less than 4.5 mu m, and the thickness of the surface coating layer is less than 0.5 mu m; the matrix is as follows: the weight ratio of the surface coating layer is 100: (0.05-40).
5. A preparation method of a lithium lanthanum zirconium oxygen solid electrolyte comprises the following steps:
(1) mixing Li-containing compound and M-containing element 1 Compound, La-containing compound, and element-containing M 2 Compound, Zr-containing compound, element-containing M 3 Compounding and mixing the compound and the compound containing the element X to obtain a mixture;
(2) roasting the mixture to obtain a lithium-containing lanthanum zirconium oxygen matrix;
(3) sanding the lithium lanthanum zirconium oxygen-containing matrix, the solution or the nano sol containing the elements E and G and the solvent, and then drying the obtained slurry to obtain an electrolyte precursor;
(3) and carrying out heat treatment on the electrolyte precursor in an oxygen-containing atmosphere to obtain the lithium lanthanum zirconium oxygen solid electrolyte.
6. The method according to claim 5, wherein M is 1 Is at least one element of Ba, Fe, B, Zn, Al, Ga and Ge; m 2 At least one element of Rb, Sr, Ba, Ca, Y, Bi, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu and Ac; m 3 Is selected from Mg, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ge, Se, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Hf, Ir, Pt, Tl, Pb, Ce, Pu, Np, Y, Ta, Nb, Mo, WAt least one element; x is at least one element of F, Cl, Br, I and S;
and/or E is at least one element of Al, Ti and Zr; g is at least one element of Al, Ti, Zr and Mg.
7. The method according to claim 6, wherein M is 1 Is at least one element of B, Al, Ga and Ge; m 2 At least one element of Sr, Ba, Y, Nd, Pm, Sm, Dy, Ho and Er; m 3 At least one element of Mg, Sc, Ti, Ge, Se, Tc, Ru, In, Hf, Ir, Pt, Y, Ta, Nb, Mo and W; x is at least one element of F, Cl, I and S;
and/or E is at least one element of Ti and Zr; g is at least one element of Al, Ti and Zr.
8. The production method according to any one of claims 5 to 7, wherein the Li-containing compound and the element M are contained 1 Compound, La-containing compound, and element-containing M 2 Compound, Zr-containing compound, element-containing M 3 The feeding amount of the compound and the compound containing the element X meets the chemical formula Li 7-x M 1 x La 3-y M 2 y Zr 2-z M 3 z O 12-u X u Wherein x is more than or equal to 0 and less than 0.1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.5, and u is more than or equal to 0 and less than or equal to 0.1;
and/or the dosage of the solution or the nano-scale sol containing the elements E and G meets the chemical formula Li v E w G h O l V is more than or equal to 0.5 and less than or equal to 10, w is more than or equal to 0.5 and less than or equal to 7, h is more than or equal to 0.5 and less than or equal to 7, and l is more than or equal to 1 and less than or equal to 15;
and/or, the lithium lanthanum zirconium oxygen containing matrix: solution or nanosol containing elements E and G: the weight ratio of the solvent is (5-50): (0.05-2): 10-500).
9. The production method according to any one of claims 5 to 8, wherein the Li-containing compound and the element M are contained 1 Compound, La-containing compound, and element-containing M 2 Compound, Zr-containing compound, element-containing M 3 Compound, element containingThe X compounds are respectively nano-scale oxides, hydroxides, nitrates, oxalates, organic alkoxides or carbonates.
10. The production method according to any one of claims 5 to 9, wherein the solution or nano-sized sol containing the elements E and G is a solution or nano-sized sol of an oxide, hydroxide, nitrate, oxalate, organic alkoxide or carbonate containing the elements E and G in ethanol, isopropanol or NMP.
11. The production method according to any one of claims 5 to 10, wherein the solvent is selected from ethanol, isopropanol or NMP.
12. The method according to any one of claims 5-11, wherein the calcination temperature is 600-; the roasting time is 2-22h, preferably 6-12 h;
and/or the heat treatment temperature is 200-1000 ℃, preferably 400-800 ℃; the heat treatment time is 2-20h, preferably 6-12 h.
13. The production method according to any one of claims 5 to 12, wherein the firing process includes pre-firing and secondary sintering; wherein the presintering temperature is 600-950 ℃, and the presintering time is 1-10 h; the secondary sintering temperature is 950 ℃ and 1400 ℃, and the secondary sintering time is 1-12 h.
14. A lithium lanthanum zirconium oxide solid electrolyte prepared by the preparation method of any one of claims 5 to 13.
15. A lithium battery comprising the lithium lanthanum zirconium oxide solid state electrolyte of any of claims 1 to 4 and 14.
16. A battery pack comprising the lithium battery of claim 15.
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