CN112919898A - Precursor for preparing ceramic material, ceramic material and preparation method - Google Patents
Precursor for preparing ceramic material, ceramic material and preparation method Download PDFInfo
- Publication number
- CN112919898A CN112919898A CN202110119546.9A CN202110119546A CN112919898A CN 112919898 A CN112919898 A CN 112919898A CN 202110119546 A CN202110119546 A CN 202110119546A CN 112919898 A CN112919898 A CN 112919898A
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- CN
- China
- Prior art keywords
- source
- source substance
- lithium
- acid
- ceramic material
- Prior art date
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- Pending
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 13
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 7
- 239000005715 Fructose Substances 0.000 claims description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 7
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 6
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 6
- 235000010980 cellulose Nutrition 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 6
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 6
- 229960003681 gluconolactone Drugs 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000008101 lactose Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 150000004677 hydrates Chemical class 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XAQAHRFIUNBQRU-UHFFFAOYSA-N OOO.[Li] Chemical compound OOO.[Li] XAQAHRFIUNBQRU-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- -1 lithium halide Chemical class 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005187 foaming Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000003746 solid phase reaction Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 239000002228 NASICON Substances 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000010855 food raising agent Nutrition 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention discloses a precursor for preparing a ceramic material, the ceramic material and a preparation method, and belongs to the technical field of ceramic materials. The method specifically comprises the following steps: adding a lithium source, an aluminum source, a germanium source, a titanium source, a phosphorus source and a sintering additive into a solvent in proportion to form a mixture; spray drying the mixture to obtain a precursor; putting the precursor into heating equipment for heat treatment, and carrying out heat treatment at 500-700 ℃ for 1-10 h to obtain pre-sintered powder; crushing the pre-sintered powder, and uniformly mixing after the treatment is finished; and (3) carrying out heat treatment on the uniformly mixed pre-sintered powder again at 800-1500 ℃ for 1-20 h to obtain the solid electrolyte powder material. According to the invention, the sintering additive is added into the mixture, so that no obvious foaming phenomenon exists in the solid-phase reaction, the wall sticking phenomenon of the sintered sample is effectively avoided, the subsequent crushing treatment is facilitated, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a precursor for preparing a ceramic material, the ceramic material and a preparation method.
Background
Lithium ion batteries have high energy density and power density, and with the progress of the times and the development of technologies, the requirements on lithium ion secondary batteries are higher and higher. Especially in the fields of electric automobiles and large-scale energy storage, the requirement on the safety of lithium ion batteries is more and more urgent. The inorganic solid electrolyte is a solid material with high ion conductivity, does not contain any liquid component, and is used as an electrolyte to prepare an all-solid-state lithium battery without worrying about the leakage problem of the electrolyte of the lithium battery, thereby ensuring the safety of the battery. Meanwhile, the inorganic solid electrolyte has higher mechanical and thermal stability than the polymer electrolyte, and ensures that the inorganic all-solid-state battery has wider application field.
NASICON (Na Super Ionic conductor) type structure is a solid electrolyte material which is widely researched, and the matrix of the solid electrolyte material is Na3Zr2Si2PO12. The sodium ions in the electrolyte are replaced by the lithium ions, so that the electrolyte can be applied to the lithium ion solid electrolyte, wherein the oxide system phosphate material has the characteristics of stable structural property, convenient synthesis and the like, and has good application potential when being used as the high-ionic-conductivity solid electrolyte.
Among the lithium ion solid electrolyte materials of NASICON structure type, LiM is the most preferable in combination2(PO4)3(M = Zr, Ti, Ge, Hf) material, it is common that Li is mainly used1+xAlxTi2−x(PO4)3(LATP for short) and Li1+xAlxGe2−x(PO4)3(LAGP for short), wherein x is more than 0 and less than 1.
When the LATP and LAGP electrolytes are prepared, phosphorus sources can be phosphorus-containing substances such as phosphorus pentoxide, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid and the like or hydrates thereof, wherein the ammonium dihydrogen phosphate and the diammonium hydrogen phosphate are low in price, wide in application and easy to obtain, can be used as food leavening agents, feeds, fertilizers, flame retardants, buffering agents, fire extinguishing agents and the like, can also be used as synthetic raw materials of lithium iron phosphate serving as a positive electrode material of a lithium ion battery, and is the best choice for industrially producing the phosphorus source materials by using the solid electrolytes.
However, when the materials such as lag p and LATP are produced and prepared by using ammonium dihydrogen phosphate or diammonium hydrogen phosphate as raw materials, foaming problems occur in the solid-phase reaction process, so that the wall adhesion phenomenon is caused, manual intervention is forced during subsequent sample treatment, the production efficiency is low, crucible breakage is often caused, and the automatic and efficient production operation flow is not facilitated in industrial production.
Disclosure of Invention
In order to solve the technical problems in the background technology, the invention solves the problem of foaming in the solid phase reaction process when the NASICON structural ceramic material with high ionic conductivity is prepared by taking ammonium dihydrogen phosphate or diammonium hydrogen phosphate as a raw material.
The invention is realized by adopting the following technical scheme: the preparation method of the ceramic material specifically comprises the following steps:
adding a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive into a solvent in proportion to form a mixture;
secondly, spray drying the mixture to obtain a precursor;
thirdly, putting the precursor into heating equipment for heat treatment, and carrying out heat treatment at 500-700 ℃ for 1-10 h to obtain pre-sintered powder;
step four, crushing the pre-sintered powder, and uniformly mixing after the treatment is finished;
step five, carrying out heat treatment on the uniformly mixed pre-sintered powder again at 800-1500 ℃ for 1-20 h to obtain a solid electrolyte powder material; the solid electrolyte powder material does not stick to the wall during the preparation process.
In a further embodiment, the a source material is one of an aluminum source material, a gallium source material, an yttrium source material, a gadolinium source material and a lanthanum source material; the M source substance is one of a titanium source substance, a germanium source substance, a zirconium source substance and a hafnium source substance.
In a further embodiment, the lithium source is selected from at least one of lithium hydroxide, lithium oxyhydroxide, lithium oxide, lithium sulfide, lithium carbonate, lithium nitrate, lithium acetate, or lithium halide.
In further embodiments, the aluminum source is selected from at least one of aluminum acetate, aluminum nitrate, aluminum hydroxide, aluminum phosphate, aluminum sulfate, or hydrates thereof.
In a further embodiment, the germanium source is selected from at least one of germanium oxide, germanium powder germanium containing material;
the titanium source is selected from at least one of tetrabutyl titanate, titanium dioxide, metatitanic acid, titanium powder or hydrate thereof;
the phosphorus source is selected from at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
In a further embodiment, the sintering additive is selected from at least one of glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast, and ammonium carbonate;
the mass of the sintering additive is 0.5-15.0% of the mass of the mixture.
In a further embodiment, the solvent is at least one of ethanol, water, isopropanol, tetrahydrofuran, xylene, acetone, ethylene glycol.
The ceramic material is prepared by the preparation method, and the chemical general formula of the ceramic material is Li1+xAxM2−x(PO4)3，
Wherein A is at least one of Al, Ga, Y, Da, Gd and La;
m is at least one of Ti, Ge, Zr and Hf;
xthe value ranges are as follows: 0 < (R) >x≤0.8。
In further embodiments, the a is one of Al, Ga, Y, Gd, and La;
and M is one of Ti, Ge, Zr and Hf.
The ceramic material is used as a component of a lithium ion solid electrolyte or for preparing the lithium ion solid electrolyte.
A precursor for preparing a ceramic material is formed by drying a precursor mixture, wherein the precursor mixture comprises a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive.
In a further embodiment, the sintering additive is selected from at least one of glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast, and ammonium carbonate;
in a further embodiment, the mass of the sintering additive is 0.5-15.0% of the mass of the mixture, preferably 3.0-12.0%, more preferably 6.0-10.0%, and most preferably 8.0%.
The invention has the beneficial effects that: the sintering additive is added into the mixture, so that no obvious foaming phenomenon exists in the solid-phase reaction, the wall sticking phenomenon of the sintered sample is effectively avoided, the subsequent crushing treatment is facilitated, and the production efficiency is improved.
Drawings
FIG. 1 is a photograph of a sample in example 1.
Fig. 2 is an XRD spectrum of the electrolyte prepared using the sample prepared in example 1.
Fig. 3 is an ac impedance test chart of an electrolyte prepared using the sample prepared in example 1.
Fig. 4 is an XRD spectrum of the electrolyte prepared using the sample prepared in example 2.
Fig. 5 is an ac impedance test chart of an electrolyte prepared using the sample prepared in example 2.
Fig. 6 is an XRD spectrum of the electrolyte prepared using the sample prepared in example 3.
Fig. 7 is an ac impedance test chart of an electrolyte prepared using the sample prepared in example 3.
FIG. 8 is a photograph of a sample used in comparative example 1.
Fig. 9 is an XRD spectrum of the electrolyte prepared using the sample prepared in comparative example 1.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The inventor finds that in the prior art, when the ammonium dihydrogen phosphate or the diammonium hydrogen phosphate is selected as a raw material to produce and prepare materials such as LAGP, LATP and the like, foaming can occur in a solid-phase reaction process to cause a wall sticking phenomenon, manual intervention is forced during subsequent sample treatment, the production efficiency is low, a crucible is often broken, and the automatic and efficient production operation flow is not facilitated in industrial production.
When the inventor utilizes ammonium dihydrogen phosphate or diammonium hydrogen phosphate as raw materials to prepare the NASICON structural ceramic material with high ionic conductivity, the foaming problem in the solid-phase reaction process can be solved by adding a proper sintering additive. The preparation method of the ceramic material specifically comprises the following steps:
adding a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive into a solvent in proportion to form a mixture;
secondly, spray drying the mixture to obtain a precursor;
thirdly, putting the precursor into heating equipment for heat treatment, and carrying out heat treatment at 500-700 ℃ for 1-10 h to obtain pre-sintered powder;
step four, crushing the pre-sintered powder, and uniformly mixing after the treatment is finished;
step five, carrying out heat treatment on the uniformly mixed pre-sintered powder again at 800-1500 ℃ for 1-20 h to obtain a solid electrolyte powder material; the solid electrolyte powder material does not stick to the wall during the preparation process.
In a further embodiment, the a source material is one of an aluminum source material, a gallium source material, an yttrium source material, a gadolinium source material and a lanthanum source material; the M source substance is one of a titanium source substance, a germanium source substance, a zirconium source substance and a hafnium source substance.
In a further embodiment, the lithium source is selected from at least one of lithium hydroxide, lithium oxyhydroxide, lithium oxide, lithium sulfide, lithium carbonate, lithium nitrate, lithium acetate, or lithium halide.
In further embodiments, the aluminum source is selected from at least one of aluminum acetate, aluminum nitrate, aluminum hydroxide, aluminum phosphate, aluminum sulfate, or hydrates thereof.
In a further embodiment, the germanium source is selected from at least one of germanium oxide, germanium powder germanium containing material;
the titanium source is selected from at least one of tetrabutyl titanate, titanium dioxide, metatitanic acid, titanium powder or hydrate thereof;
the phosphorus source is selected from at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
In a further embodiment, the sintering additive is selected from at least one of glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast, and ammonium carbonate;
the mass of the sintering additive is 0.5-15.0% of the mass of the mixture.
In a further embodiment, the solvent is at least one of ethanol, water, isopropanol, tetrahydrofuran, xylene, acetone, ethylene glycol.
The ceramic material is prepared by the preparation method, and the chemical general formula of the ceramic material is Li1+xAxM2−x(PO4)3，
Wherein A is at least one of Al, Ga, Y, Da, Gd and La;
m is at least one of Ti, Ge, Zr and Hf;
xthe value ranges are as follows: 0 < (R) >x≤0.8。
In further embodiments, the a is one of Al, Ga, Y, Gd, and La;
and M is one of Ti, Ge, Zr and Hf.
The ceramic material is used as a component of a lithium ion solid electrolyte or for preparing the lithium ion solid electrolyte.
A precursor for preparing a ceramic material is formed by drying a precursor mixture, wherein the precursor mixture comprises a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive.
In a further embodiment, the sintering additive is selected from at least one of glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast, and ammonium carbonate;
in a further embodiment, the mass of the sintering additive is 0.5-15.0% of the mass of the mixture, preferably 3.0-12.0%, more preferably 6.0-10.0%, and most preferably 8.0%.
Example 1
Using lithium hydroxide monohydrate, alumina, titanium oxide and ammonium dihydrogen phosphate as raw materials, according to the stoichiometric Li1.3Al0.3Ti1.7(PO4)3Proportionally mixing, and adding glucose accounting for 2% of the mass of the mixture. And (3) placing the mixed material in an ethanol solvent for ball milling for 24h, and removing the solvent by spray drying to obtain an LATP precursor. And pre-sintering the precursor of the LATP sample at a low temperature of 500 ℃. And (3) pre-burning at low temperature to obtain a sample, ball-milling for 24h again, spray-drying to remove the solvent, and sintering at 1000 ℃ for 10 h. The photograph of the sample is shown in fig. 1, and no foaming and wall sticking phenomenon are obvious. The XRD test was performed on the electrolyte, as shown in fig. 2, and the test result was consistent with that of comparative example 1. The electrolyte was subjected to an AC impedance test, as shown in FIG. 3, and the sample conductivity was calculated to be 5.63X 10 from the test results-4S/cm, consistent with the test results of comparative example 1. Shows that the sintering additive of the sample is completely removed in the high-temperature sintering processBesides, the phase structure and the performance of the sample are not influenced.
Example 2
Using lithium hydroxide monohydrate, gallium oxide, germanium oxide and ammonium dihydrogen phosphate as raw materials according to the stoichiometric Li1.5Ga0.5Ge1.5(PO4)3Proportionally mixing, and adding maltose accounting for 5% of the mass of the mixture. And (3) placing the mixed material in an ethanol solvent for ball milling for 24h, and removing the solvent by spray drying to obtain a precursor. And pre-sintering the precursor of the sample at a low temperature of 500 ℃. And (3) performing low-temperature presintering on the obtained sample, performing ball milling for 24 hours again, performing spray drying to remove a solvent, and sintering at 1000 ℃ for 10 hours to obtain the electrolyte material. XRD test was performed on the electrolyte, as shown in fig. 4, and the test result was consistent with that of comparative example 1. The electrolyte was subjected to an AC impedance test, and as shown in FIG. 5, the sample conductivity was calculated to be 5.71X 10 from the test results-4S/cm, consistent with the test results of comparative example 1. The sintering additive of the sample is completely removed in the high-temperature sintering process, and the phase structure and the performance of the sample are not influenced.
Example 3
Using lithium hydroxide monohydrate, alumina, titanium oxide and ammonium dihydrogen phosphate as raw materials, according to the stoichiometric Li1.4Al0.4Ti1.6(PO4)3Proportionally mixing, and adding 1% of cellulose and 2% of fructose by mass of the mixture. And (3) placing the mixed material in an ethanol solvent for ball milling for 24h, and removing the solvent by spray drying to obtain an LATP precursor. And pre-sintering the precursor of the LATP sample at a low temperature of 500 ℃. And (3) pre-burning at low temperature to obtain a sample, ball-milling for 24h again, spray-drying to remove the solvent, and sintering at 1000 ℃ for 10 h. XRD test was performed on the electrolyte, as shown in fig. 6, and the test result was consistent with that of comparative example 1. The electrolyte was subjected to an AC impedance test, as shown in FIG. 7, and the sample conductivity was calculated to be 5.65X 10 from the test results-4S/cm, consistent with the test results of comparative example 1. The sintering additive of the sample is completely removed in the high-temperature sintering process, and the phase structure and the performance of the sample are not influenced.
Comparative example 1
Using lithium hydroxide monohydrate, alumina, titanium oxide and ammonium dihydrogen phosphate as raw materials, according to the stoichiometric Li1.4Al0.4Ti1.6(PO4)3And (4) proportioning and mixing. And (3) placing the mixed material in an ethanol solvent for ball milling for 24h, and removing the solvent by spray drying to obtain an LATP precursor. And pre-sintering the precursor of the LATP sample at a low temperature of 500 ℃. And (3) pre-burning at low temperature to obtain a sample, ball-milling for 24h again, spray-drying to remove the solvent, and sintering at 1000 ℃ for 10 h. The photograph of the sample is shown in FIG. 8, and the foaming phenomenon is obvious. XRD testing was performed on the electrolyte as shown in fig. 9. Performing AC impedance test on the electrolyte, and calculating the conductivity of the sample to be 5.60 × 10 according to the test result-4S/cm。
The sintering additive is added into the mixture, so that no obvious foaming phenomenon exists in the solid-phase reaction, the wall sticking phenomenon of the sintered sample is effectively avoided, the subsequent crushing treatment is facilitated, and the production efficiency is improved.
In the embodiment of the invention, the raw materials required by the high ionic conductivity ceramic material are easy to react with other raw materials due to the fact that the phosphorus source compound is generally in a molten state below 400 ℃ in the sintering process, and gases such as carbon dioxide are released, so that the raw materials are porous, loose and expanded in volume during heat treatment, and thus the wall sticking phenomenon is shown. Sintering additives such as glucose can take on a viscous state during sintering, which can strongly restrict the flowability of the raw materials at high temperatures, thereby greatly reducing the sticky state.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (12)
1. The preparation method of the ceramic material is characterized by comprising the following steps:
adding a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive into a solvent in proportion to form a mixture;
secondly, spray drying the mixture to obtain a precursor;
thirdly, putting the precursor into heating equipment for heat treatment, and carrying out heat treatment at 500-700 ℃ for 1-10 h to obtain pre-sintered powder;
step four, crushing the pre-sintered powder, and uniformly mixing after the treatment is finished;
step five, carrying out heat treatment on the uniformly mixed pre-sintered powder again at 800-1500 ℃ for 1-20 h to obtain a solid electrolyte powder material; the solid electrolyte powder material does not stick to the wall during the preparation process.
2. The method for preparing a ceramic material according to claim 1,
the A source substance is one of an aluminum source substance, a gallium source substance, an yttrium source substance, a gadolinium source substance and a lanthanum source substance; the M source substance is one of a titanium source substance, a germanium source substance, a zirconium source substance and a hafnium source substance.
3. The method for preparing a ceramic material according to claim 1,
the lithium source is at least one selected from lithium hydroxide, lithium oxyhydroxide, lithium oxide, lithium sulfide, lithium carbonate, lithium nitrate, lithium acetate or lithium halide.
4. The method of claim 1, wherein the aluminum source is at least one selected from the group consisting of aluminum acetate, aluminum nitrate, aluminum hydroxide, aluminum phosphate, aluminum sulfate, and hydrates thereof.
5. The method for preparing a ceramic material according to claim 1, wherein the germanium source is at least one selected from germanium oxide and germanium-containing substance of germanium powder;
the titanium source is selected from at least one of tetrabutyl titanate, titanium dioxide, metatitanic acid, titanium powder or hydrate thereof;
the phosphorus source is selected from at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
6. The method of claim 1, wherein the sintering additive is at least one selected from glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast, and ammonium carbonate.
7. The method of claim 1, wherein the solvent is at least one of ethanol, water, isopropanol, tetrahydrofuran, xylene, acetone, and ethylene glycol.
8. A ceramic material prepared by the method of claim 1, wherein the ceramic material has a chemical formula of Li1+xAxM2−x(PO4)3，
Wherein A is at least one of Al, Ga, Y, Da, Gd and La;
m is at least one of Ti, Ge, Zr and Hf;
xthe value ranges are as follows: 0 < (R) >x≤0.8。
9. A ceramic material according to claim 8,
the A is one of Al, Ga, Y, Gd and La;
and M is one of Ti, Ge, Zr and Hf.
10. The precursor for preparing the ceramic material is characterized by being prepared by drying a precursor mixture, wherein the precursor mixture comprises a lithium source substance, an A source substance, an M source substance, a phosphorus source substance and a sintering additive.
11. The precursor according to claim 10, wherein the sintering additive is at least one selected from glucose, glucono-delta-lactone, fructose, sucrose, lactose, maltose, cellobiose, cellulose, starch, citric acid, tartaric acid, glycine, salicylic acid, oxalic acid, malic acid, adipic acid, ethylenediaminetetraacetic acid, polyacrylic acid, hexamethylenetetramine, polyethylene glycol, yeast and ammonium carbonate.
12. A precursor according to claim 10, wherein the mass of the sintering additive is 0.5-15.0%, preferably 3.0-12.0%, more preferably 6.0-10.0%, and most preferably 8.0% of the mass of the mixture.
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| CN117059919A (en) * | 2023-08-04 | 2023-11-14 | 江苏大学 | LATP solid electrolyte and preparation method thereof |
| WO2024021822A1 (en) * | 2022-07-27 | 2024-02-01 | 宜宾南木纳米科技有限公司 | Magnesium-based solid electrolyte, preparation method therefor, and battery |
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| CN117059919A (en) * | 2023-08-04 | 2023-11-14 | 江苏大学 | LATP solid electrolyte and preparation method thereof |
| CN117059919B (en) * | 2023-08-04 | 2024-07-12 | 江苏大学 | LATP solid electrolyte and preparation method thereof |
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