CN117594793A - Composite positive electrode material, preparation method and application thereof - Google Patents
Composite positive electrode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN117594793A CN117594793A CN202410070269.0A CN202410070269A CN117594793A CN 117594793 A CN117594793 A CN 117594793A CN 202410070269 A CN202410070269 A CN 202410070269A CN 117594793 A CN117594793 A CN 117594793A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- electrode material
- composite positive
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 105
- 239000011247 coating layer Substances 0.000 claims abstract description 46
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 24
- 238000005253 cladding Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims description 90
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001263 FEMA 3042 Substances 0.000 claims description 6
- 229930091371 Fructose Natural products 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- 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 6
- 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 6
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 235000010980 cellulose Nutrition 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 229920002258 tannic acid Polymers 0.000 claims description 6
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 6
- 229940033123 tannic acid Drugs 0.000 claims description 6
- 235000015523 tannic acid Nutrition 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 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 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920001690 polydopamine Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000011162 core material Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 239000010405 anode material Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229910021617 Indium monochloride Inorganic materials 0.000 description 8
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-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
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- LAYZVIPDEOEIDY-ZVGUSBNCSA-L (2R,3R)-2,3-dihydroxybutanedioate manganese(2+) Chemical compound [Mn++].O[C@H]([C@@H](O)C([O-])=O)C([O-])=O LAYZVIPDEOEIDY-ZVGUSBNCSA-L 0.000 description 1
- FQCHNZLQGCBANT-UHFFFAOYSA-L 2-hydroxyacetate;manganese(2+) Chemical compound [Mn+2].OCC([O-])=O.OCC([O-])=O FQCHNZLQGCBANT-UHFFFAOYSA-L 0.000 description 1
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910003001 Li-Ni-Co-Mn-O Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- IKQWZXRBSFSWTO-UHFFFAOYSA-K [O-]P([O-])([O-])=O.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical class [O-]P([O-])([O-])=O.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[N+](c1ccccc1)(c1ccccc1)c1ccccc1 IKQWZXRBSFSWTO-UHFFFAOYSA-K 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WMOSTDJFFWYKNF-UHFFFAOYSA-L hydrogen carbonate;manganese(2+) Chemical compound [Mn+2].OC([O-])=O.OC([O-])=O WMOSTDJFFWYKNF-UHFFFAOYSA-L 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 tetraalkylammonium phosphate compounds Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention relates to the technical field of batteries, in particular to a composite positive electrode material, a preparation method and application thereof. The composite positive electrode material comprises an inner core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the inner core, the second coating layer is coated on part of the surface of the first coating layer, and the second coating layer has an island-shaped structure; the inner core comprises a lithium manganese phosphate material, the first cladding layer comprises a carbon material, and the second cladding layer comprises a halide electrolyte. The composite positive electrode material has excellent electron conductivity and chemical stability under high voltage through the cooperation of each layer structure.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite positive electrode material, a preparation method and application thereof.
Background
The positive electrode material used in the lithium ion battery at present mainly comprises Li-Ni-Co-Mn-O ternary material and LiFePO 4 Lithium iron phosphate materials, and the like. Ternary materials have high energy density, but contain nickel, cobalt and other elements, so that the metal cost is higher. The lithium iron phosphate material has low cost, but has lower voltage corresponding to oxidation reduction, and the lithium ion battery taking the lithium iron phosphate material as the positive electrode has lower energy density. In contrast, lithium manganese phosphate materials (LiMnPO 4 ) The Mn element in the material has low cost, the discharge platform voltage of Mn is higher (more than 4.1V), and the energy density of the material is higher.
However, in conventional liquid lithium ion battery systems, liMnPO 4 The material has the phenomenon of Mn ion dissolution, so that the material has poor cycle performance. Unlike liquid lithium ion batteries, all-solid batteries use solid electrolytes instead of liquid electrolytes, and can fundamentally solve the problem that Mn ions are dissolved into the electrolytes. But LiMnPO 4 The Mn in the material has higher charging voltage, and the oxidation state of the material is higher in the full charge state, so that when the material is used for an all-solid-state battery, the all-solid-state electrolyte is easy to undergo oxidative decomposition reaction, and the cycle life of the battery is deteriorated. Furthermore, liMnPO 4 The material is a polyanion material, and has lower electronic conductivity, so that the battery has larger charge and discharge electrode and poor multiplying power performance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a composite anode material to solve the technical problems of low electronic conductivity and poor chemical stability of a lithium manganese phosphate material; the composite positive electrode material has excellent electron conductivity and chemical stability under high voltage.
The invention also aims to provide a preparation method of the composite positive electrode material, which is simple and feasible and can enable the composite positive electrode material to have excellent electrochemical performance.
Another object of the present invention is to provide a positive electrode sheet.
Another object of the present invention is to provide a solid-state battery.
It is another object of the present invention to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the composite positive electrode material comprises a core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the core, the second coating layer is coated on part of the surface of the first coating layer, and the second coating layer has an island-shaped structure;
the inner core comprises a lithium manganese phosphate material, the first cladding layer comprises a carbon material, and the second cladding layer comprises a halide electrolyte.
In one embodiment, the halide electrolyte has the formula Li x GQ y Wherein, the element G is selected from at least one of IIIB group and IIIA group, the element Q is selected from at least one of halogen group elements, x is more than 0 and less than or equal to 3, and y is more than 0 and less than or equal to 6.
In one embodiment, a plurality of the island structures are independent of each other or at least some of the island structures are connected.
In one embodiment, the island structure has a thickness of 10-500 nm.
In one embodiment, the lithium manganese phosphate material has the formula Li x MnPO 4 Wherein x is more than 0.8 and less than 1.2.
In one embodiment, the average particle size D50 of the inner core satisfies: 20nm < D50<2 μm.
In one embodiment, the thickness D of the first cladding layer satisfies: 1nm < D <100nm.
The preparation method of the composite positive electrode material comprises the following steps:
performing first sintering on a first mixed material of a manganese phosphate precursor, a first lithium source and a carbon source to obtain a first material; and performing second sintering on the second mixed material of the first material, the element G source and the second lithium source, wherein at least one of the element G source and the second lithium source contains halogen elements.
In one embodiment, the molar ratio of the first lithium source to the manganese phosphate precursor is (0.8-1.2): 1 in terms of lithium element and Mn element, respectively.
In one embodiment, the carbon source accounts for 0.01% -15% of the mass of the first mixed material.
In one embodiment, the carbon source comprises at least one of citric acid, polyvinyl alcohol, polypyrrole, vitamin C, polyethylene glycol, sucrose, glucose, fructose, cellulose, starch, polyvinylpyrrolidone, polydopamine, and tannic acid.
In one embodiment, the first lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate.
In one embodiment, the temperature of the first sintering is 400-1000 ℃, and the time of the first sintering is 6-20 hours.
In one embodiment, the first sintering is performed under protective gas conditions.
In one embodiment, the mass ratio of the first material to the second lithium source is (12-18): (0.05 to 0.3).
In one embodiment, the source of element G comprises at least one of a chloride of element G, a hydroxide of element G, and a carbonate of element G.
In one embodiment, the second lithium source comprises at least one of lithium chloride, lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate.
In one embodiment, the temperature of the second sintering is 200-500 ℃, and the time of the second sintering is 6-15 h.
In one embodiment, the second sintering is performed under protective gas conditions.
The positive plate comprises the composite positive material or the composite positive material prepared by the preparation method of the composite positive material.
A solid-state battery includes the positive electrode sheet.
A powered device includes the solid-state battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the composite positive electrode material, the first coating layer is coated on the surface of the inner core, so that the electronic conductivity of the positive electrode material can be improved, and the problem of non-ideal battery multiplying power performance caused by poor conductive performance of the inner core material is solved; the second coating layer is coated on the surface of the first coating layer in an island shape; by the cooperation of the layer structures, the positive electrode material has excellent electron conductivity and chemical stability under high voltage.
(2) The preparation method of the composite positive electrode material is simple and easy to implement, and the composite positive electrode material has excellent electrochemical performance through the cooperation of all steps.
(3) The composite positive electrode material is further prepared into a positive electrode plate, and the battery prepared from the positive electrode plate has excellent multiplying power performance and cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a composite positive electrode material of the present invention.
Reference numerals:
1-inner core, 2-first coating layer, 3-second coating layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
According to one aspect of the invention, the invention relates to a composite positive electrode material, which comprises a core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the core, the second coating layer is coated on part of the surface of the first coating layer, and the second coating layer has an island-shaped structure;
the inner core comprises a lithium manganese phosphate material, the first cladding layer comprises a carbon material, and the second cladding layer comprises a halide electrolyte.
The inner core of the composite anode material is made of a lithium manganese phosphate material, and the material has higher charge-discharge voltage platform, so that the material has higher energy density; meanwhile, the Mn element in the material is low in cost, so that the material has good cost performance. The lithium manganese phosphate material has poor electronic conductivity, the first coating layer is coated on the surface of the inner core, and the first coating layer forms a compact coating form, so that the electronic conductivity of the positive electrode material can be improved, and the problem of non-ideal rate performance of the battery caused by poor electronic conductivity of the inner core material is solved. The lithium manganese phosphate material has a higher charge-discharge voltage platform, and when the material is used, the battery needs to be charged to a higher voltage. However, in the high voltage state, the lithium manganese phosphate material has strong oxidizing property, so that the sulfide, oxide, polymer and other solid electrolyte materials in contact with the lithium manganese phosphate material in the solid battery are easily oxidized and decomposed, thereby deteriorating the battery cycle performance. The invention ensures that the positive electrode material has excellent electron conductivity and chemical stability under high voltage through the cooperation of each layer structure.
In one embodiment, the halide electrolyte has the formula Li x GQ y Wherein element G is selected from at least one of group iiib and group iiia and element Q is selected from at least one of the halogen elements, such as at least one of F, cl, br, I; x is more than 0 and less than or equal to 3, and the value of x comprises 0.1, 0.5, 0.8, 1, 1.5, 1.8, 2, 2.5 or 3 and the like; y is more than 0 and less than or equal to 6, and the value of y comprises 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5 or 6 and the like. In one embodiment, the halide electrolyte has the formula Li x ACl y The element G is selected from at least one of Sc, Y and In, x is more than 0 and less than or equal to 3, and Y is more than 0 and less than or equal to 6.
In one embodiment, in the second cladding layer, a plurality of the island structures are independent from each other, or at least a part of the island structures are connected. In one embodiment, the thickness of the coating layer of each island structure is 10 to 500nm, for example, 10nm, 50nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500nm, or the like. The thickness of the cladding layer of each island structure refers to the peak thickness of the island structure. In one embodiment, the second coating layer has a coating ratio of 20% -60%, for example, 20%, 30%, 35%, 40%, 50%, 55% or 60%, and the coating ratio means: the coverage area of the second coating layer on the surface of the first coating layer accounts for the proportion of the area of the outer surface of the first coating layer. The second coating layer has proper thickness and coating rate, and is more beneficial to ensuring the electronic conductivity and the chemical stability of the composite positive electrode material under high voltage. The thickness detection of the island structure can be performed by adopting a scanning electron microscope.
In one embodiment, the lithium manganese phosphate material has the formula Li x MnPO 4 Wherein x is more than 0.8 and less than 1.2. In one embodiment, the average particle size D50 of the inner core satisfies: 20nm of<D50<2 μm, in one embodiment, the average particle size D50 of the inner core includes, but is not limited to, 50nm, 80nm, 100nm, 150nm, 200nm, 300nm, 500nm, 700nm, 800nm, 1 μm or 1.5 μm, etc. The lithium manganese phosphate material has proper average particle size, so that the electrochemical performance of the composite positive electrode material can be ensured.
In one embodiment, the thickness D of the first cladding layer satisfies: 1nm < D <100nm. The thickness of the first cladding layer includes, but is not limited to, 2nm, 3nm, 10nm, 20nm, 50nm, 60nm, 80nm, 90nm, or the like. The first coating layer adopted by the invention has proper thickness, and is more beneficial to improving the electronic conductivity of the anode material.
According to another aspect of the invention, the invention also relates to a preparation method of the composite positive electrode material, which comprises the following steps:
performing first sintering on a first mixed material of a manganese phosphate precursor, a first lithium source and a carbon source to obtain a first material; and performing second sintering on the second mixed material of the first material, the element G source and the second lithium source, wherein at least one of the element G source and the second lithium source contains halogen elements.
The method is simple and easy to operate through the matching of the steps, and the obtained composite positive electrode material has excellent electrochemical performance.
In one embodiment, the molar ratio of the first lithium source to the manganese phosphate precursor is (0.8-1.2): 1 in terms of lithium element and Mn element, respectively. The chemical formula of the manganese phosphate precursor is MnPO 4 . The manganese phosphate precursor can be prepared from a Mn source compound and a phosphorus source compound, wherein the Mn source compound is selected from one or more of manganese phosphate, manganese hydrogen phosphate, manganese dihydrogen phosphate, manganese carbonate, manganese hydrogen carbonate, manganese formate, manganese acetate, manganese oxide, manganese glycolate, manganese lactate, manganese citrate, manganese powder and manganese tartrate. The phosphorus source compound is selected from hydrogen phosphate and dihydrogen phosphateOne or more of phosphoric acid, tetraalkylammonium phosphate compounds, tetraphenylammonium phosphate compounds, ammonium phosphate, and monoammonium phosphate. In one embodiment, the first lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate.
In one embodiment, the carbon source accounts for 0.01% -15% of the mass of the first mixture, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12% or 15% of the mass of the first mixture. The invention adopts a proper amount of carbon source, and forms a first coating layer with proper thickness so as to ensure the physicochemical property of the first material, thereby laying a good foundation for obtaining the composite anode material with excellent electrochemical property subsequently.
In one embodiment, the carbon source comprises at least one of citric acid, polyvinyl alcohol, polypyrrole, vitamin C, polyethylene glycol, sucrose, glucose, fructose, cellulose, starch, polyvinylpyrrolidone, polydopamine, and tannic acid. The carbon source of the present invention may be selected from one or a combination of at least two of the above carbon sources, for example, a combination of polypyrrole and glucose, a combination of cellulose, starch and polyvinylpyrrolidone, and the like. In one embodiment, the carbon source is selected from the group consisting of citric acid, polypyrrole, and carbon source a is selected from at least one of vitamin C, sucrose, glucose, fructose, cellulose, starch, and tannic acid; the mass ratio of the citric acid to the polypyrrole to the carbon source A is 1: (0.2 to 0.4): (0.6 to 0.8).
In one embodiment, the temperature of the first sintering is 400-1000 ℃, and the time of the first sintering is 6-20 hours. In one embodiment, the temperature of the first sintering includes, but is not limited to, 400 ℃, 450 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, or the like. The time of the first sintering includes, but is not limited to, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 15h, 16h, 18h, 20h, etc. The first sintering is performed under a protective gas condition including at least one of an inert gas and nitrogen, and the inert gas may be argon, helium, or the like. According to the invention, through the proper first sintering temperature and time matching, the physicochemical property of the first material is further ensured, and the coating of the second coating layer is facilitated.
In one embodiment, the mass ratio of the first material to the second lithium source is (12-18): (0.05-0.3), such as 12:0.05, 13:0.06, 14:0.1, 15:0.2 or 18:0.3, etc.
In one embodiment, the temperature of the second sintering is 200-500 ℃, and the time of the second sintering is 6-15 h. In one embodiment, the temperature of the second sintering includes, but is not limited to, 200 ℃, 250 ℃, 280 ℃, 300 ℃, 350 ℃, 400 ℃, or 500 ℃, and the time of the second sintering includes, but is not limited to, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, or 15h. In one embodiment, the second sintering is performed under a protective gas including at least one of an inert gas and nitrogen, and the inert gas may be helium, argon, or the like. The electrochemical performance of the obtained composite anode material is further ensured by adopting the proper second sintering temperature and time coordination.
In a preferred embodiment, the preparation method of the composite positive electrode material comprises the following steps:
(a) Uniformly mixing a manganese phosphate precursor, a first lithium source and a carbon source in a ball mill to form a precursor mixture, and performing first sintering under the condition of protective gas, wherein the first sintering temperature is 400-1000 ℃, and the first sintering time is 6-20 hours to obtain a first material;
wherein the first lithium source is selected from at least one of lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate and lithium phosphate; the carbon source is at least one selected from citric acid, polyvinyl alcohol, polypyrrole, vitamin C, polyethylene glycol, sucrose, glucose, fructose, cellulose, starch, polyvinylpyrrolidone, polydopamine and tannic acid;
the first material is provided with a manganese phosphate core and a carbon coating layer coated on the core, wherein the chemical formula of the manganese phosphate core is Li x MnPO 4 Wherein x is more than 0.8 and less than 1.2; the average grain diameter D50 of the core lithium manganese phosphate material is 30 nm-1.5 mu m; carbon-coated layerThe thickness is 2 nm-95 nm;
(b) Uniformly mixing the first material obtained in the step (a), an element G source and a second lithium source in a ball mill to obtain a mixed material, wherein at least one of the element G source and the second lithium source contains halogen elements;
wherein the source of element G comprises at least one of a chloride of element G, a hydroxide of element G, and a carbonate of element G; the second lithium source comprises at least one of lithium chloride, lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate;
and (3) placing the mixed material in protective gas for second sintering, wherein the temperature of the second sintering is 200-500 ℃, the time of the second sintering is 6-15 h, and a second coating layer is formed to obtain the composite positive electrode material, wherein the second coating layer has an island structure, the thickness of the island structure is 10-500 nm, and the coating rate is 20% -60%.
According to another aspect of the invention, the invention also relates to a positive electrode sheet, which comprises the composite positive electrode material or the composite positive electrode material prepared by the preparation method of the composite positive electrode material.
In one embodiment, the positive electrode sheet includes a positive electrode current collector and a positive electrode material layer disposed on at least one side surface of the positive electrode current collector. The positive electrode material layer comprises the composite positive electrode material.
According to another aspect of the present invention, the present invention also relates to a solid-state battery including the positive electrode sheet. The solid-state battery includes a positive electrode sheet, a negative electrode sheet, and a solid-state electrolyte sheet. The solid-state battery of the present invention has excellent rate performance and cycle performance.
According to another aspect, the invention also relates to a powered device comprising said solid-state battery. The solid-state battery can provide power for electric equipment. The electric equipment comprises a bicycle, an electric motorcycle, an electric automobile or an electric tool and the like.
The following is a further explanation in connection with specific examples, comparative examples.
Example 1
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 700 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.21g of InCl 3 And 0.12g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 350 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
The structural schematic diagram of the composite material obtained in this embodiment is shown in fig. 1, and the composite material comprises a core 1, a first cladding layer 2 and a second cladding layer 3, wherein the first cladding layer 2 is coated on the surface of the core 1, the second cladding layer 3 is coated on part of the surface of the first cladding layer 2, and the second cladding layer 3 has an island-shaped structure; the inner core 1 is made of lithium manganese phosphate material, the first coating layer 2 is made of carbon material, and the second coating layer 3 is made of halide electrolyte obtained by the method.
Example 2
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 670 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.21g of InCl 3 And 0.12g LiCl, uniformly mixed in a ball mill, and then placed in an atmosphere sintering furnace, and subjected to secondary sintering in a nitrogen atmosphere at a secondary sintering temperatureThe temperature is 350 ℃ and the time is 8 hours, and then the composite anode material is obtained after natural cooling.
Example 3
A method of preparing a composite material comprising the steps of:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 730 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.21g of InCl 3 And 0.12g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 350 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
Example 4
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 700 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.21g of InCl 3 And 0.12g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 380 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
Example 5
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 ，2.4g LiOH,2g of citric acid, and uniformly mixing in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 700 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.21g of InCl 3 And 0.12g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 410 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
Example 6
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 700 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.105g of InCl 3 And 0.06g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 350 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
Example 7
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,2g citric acid, were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 700 ℃, the time is 12 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.315g of InCl 3 And 0.18g of LiCl, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering under nitrogen atmosphere, wherein the second sintering temperature is 350 ℃, the time is 8 hours, and naturally cooling to obtain the composite anode material.
Example 8
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g of LiOH,1g of citric acid, 0.4g of polypyrrole and 0.6g of fructose are uniformly mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 710 ℃, the time is 10 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.315g of InCl 3 And 0.18g of lithium hydroxide, uniformly mixing in a ball mill, placing in an atmosphere sintering furnace, performing second sintering in a nitrogen atmosphere at 385 ℃ for 7 hours, and naturally cooling to obtain the composite anode material.
Example 9
The preparation method of the composite positive electrode material comprises the following steps:
(a) 15g MnPO is weighed 4 2.4g LiOH,1g citric acid, 0.2g tannic acid, 0.8g polypyrrole were homogeneously mixed in a ball mill to form a precursor mixture;
(b) And placing the precursor mixture in an atmosphere sintering furnace, and performing first sintering under the protection of nitrogen, wherein the temperature of the first sintering is 710 ℃, the time is 10 hours, and taking out the material from the atmosphere furnace after natural cooling to obtain the carbon-coated lithium manganese phosphate material, namely the first material.
(c) 15g of the first material was weighed and mixed with 0.315g of ScCl 3 And 0.18g of lithium hydroxide, and uniformly mixed in a ball millAnd then placing the mixture in an atmosphere sintering furnace, performing second sintering under the nitrogen atmosphere, wherein the temperature of the second sintering is 390 ℃, the time is 7 hours, and then naturally cooling to obtain the composite anode material.
Comparative example 1
The preparation method of the positive electrode material comprises the following steps:
15g of MnPO is weighed 4 2.4g LiOH was homogeneously mixed in a ball mill to form a precursor mixture. The precursor mixture was placed in an atmosphere sintering furnace and sintered at 700 ℃ for 12 hours under an atmosphere of 5% hydrogen and 95% nitrogen. And (5) taking the material out of the atmosphere furnace after natural cooling to obtain the lithium manganese phosphate material.
Comparative example 2
The preparation method of the positive electrode material comprises the following steps:
the preparation was carried out in the same manner as in step (a) and step (b) of example 1 to obtain a positive electrode material.
Comparative example 3
A preparation method of a positive electrode material was the same as in example 1 except that citric acid was not added in the step (a).
Examples
The preparation and performance test of the battery comprise the following steps:
in an argon glove box, 100mg of Li was weighed 6 PS 5 The Cl sulfide solid electrolyte powder is placed in an insulating outer cylinder, the powder is pressed and molded under the pressure of 300MPa, meanwhile, the positive plate is manufactured by the composite positive electrode material, and the preparation method of the positive plate comprises the following steps: mixing the positive electrode material with Li 6 PS 5 The Cl sulfide solid electrolyte and the activated carbon are prepared from the following components in percentage by mass: 29:1, mixing the mixture to obtain a mixed material, and homogenizing the mixed material, slurry prepared by hydrogenated styrene-butadiene block copolymer (SEBS) and dimethylbenzene to obtain positive electrode slurry, wherein the mass ratio of the mixed material to the SEBS to the dimethylbenzene is 95:5:100; uniformly coating the anode slurry on an aluminum foil current collector and drying to obtain an anode plate; an all-solid-state mold battery was assembled with a Li/In alloy counter electrode.
Respectively carrying out charge and discharge tests at 0.1C and 0.5C multiplying power, wherein the ratio of the 0.5C discharge specific capacity to the 0.1C discharge specific capacity is the capacity retention rate under the multiplying power test; and (3) performing charge-discharge cycle performance test on the 1C multiplying power, wherein the ratio of the capacity to the first capacity after 100 cycles is the capacity retention rate after cycles.
The test results are shown in Table 1.
Table 1 battery performance test results
As can be seen from table 1, the battery obtained from the composite cathode material of the present invention has excellent rate performance and cycle performance. The positive electrode materials of comparative examples 1 to 3 gave batteries having relatively poor rate performance and cycle performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (15)
1. The composite positive electrode material is characterized by comprising a core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the core, the second coating layer is coated on part of the surface of the first coating layer, and the second coating layer has an island-shaped structure;
the inner core comprises a lithium manganese phosphate material, the first cladding layer comprises a carbon material, and the second cladding layer comprises a halide electrolyte.
2. The composite positive electrode material according to claim 1, wherein the halide electrolyte has a chemical formula of Li x GQ y Wherein the element G is selected from one of IIIB group or IIIA groupThe element Q is at least one of halogen elements, x is more than 0 and less than or equal to 3, and y is more than 0 and less than or equal to 6.
3. The composite positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) A plurality of the island structures are independent from each other, or at least part of the island structures are connected;
(2) The thickness of the island-shaped structures is 10-500 nm.
4. The composite positive electrode material according to claim 1, wherein the lithium manganese phosphate material has a chemical formula of Li x MnPO 4 Wherein x is more than 0.8 and less than 1.2;
and/or, the average particle diameter D50 of the inner core satisfies: 20nm < D50<2 μm.
5. The composite positive electrode material according to claim 1, wherein the thickness D of the first coating layer satisfies: 1nm < D <100nm.
6. The method for preparing a composite positive electrode material according to any one of claims 1 to 5, comprising the steps of:
performing first sintering on a first mixed material of a manganese phosphate precursor, a first lithium source and a carbon source to obtain a first material; and performing second sintering on the second mixed material of the first material, the element G source and the second lithium source, wherein at least one of the element G source and the second lithium source contains halogen elements.
7. The method for preparing a composite positive electrode material according to claim 6, wherein the molar ratio of the first lithium source to the manganese phosphate precursor is (0.8-1.2) 1 in terms of lithium element and Mn element, respectively;
and/or the mass of the carbon source accounts for 0.01% -15% of the mass of the first mixed material.
8. The method of producing a composite positive electrode material according to claim 6 or 7, characterized by comprising at least one of the following features (1) to (2):
(1) The carbon source comprises at least one of citric acid, polyvinyl alcohol, polypyrrole, vitamin C, polyethylene glycol, sucrose, glucose, fructose, cellulose, starch, polyvinylpyrrolidone, polydopamine and tannic acid;
(2) The first lithium source includes at least one of lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate.
9. The method of producing a composite positive electrode material according to claim 6, characterized by comprising at least one of the following features (1) to (2):
(1) The temperature of the first sintering is 400-1000 ℃, and the time of the first sintering is 6-20 h;
(2) The first sintering is performed under protective gas conditions.
10. The method for preparing a composite positive electrode material according to claim 6, wherein the mass ratio of the first material to the second lithium source is (12-18): (0.05 to 0.3).
11. The method of producing a composite positive electrode material according to claim 6 or 10, characterized by comprising at least one of the following features (1) to (2):
(1) The element G source includes at least one of a chloride of element G, a hydroxide of element G, and a carbonate of element G;
(2) The second lithium source includes at least one of lithium chloride, lithium hydroxide, lithium oxide, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate, and lithium phosphate.
12. The method of producing a composite positive electrode material according to claim 6, characterized by comprising at least one of the following features (1) to (2):
(1) The temperature of the second sintering is 200-500 ℃, and the time of the second sintering is 6-15 h;
(2) The second sintering is performed under protective gas conditions.
13. A positive electrode sheet, characterized by comprising the composite positive electrode material according to any one of claims 1 to 5 or the composite positive electrode material prepared by the preparation method of the composite positive electrode material according to any one of claims 6 to 12.
14. A solid-state battery comprising the positive electrode sheet according to claim 13.
15. A powered device comprising the solid state battery of claim 14.
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