CN115188941A - Multi-element anode material, preparation method thereof and lithium ion battery - Google Patents
Multi-element anode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115188941A CN115188941A CN202210749118.9A CN202210749118A CN115188941A CN 115188941 A CN115188941 A CN 115188941A CN 202210749118 A CN202210749118 A CN 202210749118A CN 115188941 A CN115188941 A CN 115188941A
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- 239000010405 anode material Substances 0.000 title claims abstract description 83
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 71
- 239000010416 ion conductor Substances 0.000 claims abstract description 70
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000013078 crystal Substances 0.000 claims description 42
- 239000007774 positive electrode material Substances 0.000 claims description 42
- 239000011572 manganese Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000012216 screening Methods 0.000 claims description 28
- 239000012266 salt solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims description 16
- 239000008139 complexing agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 239000002223 garnet Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- FYNXQOUDSWHQQD-UHFFFAOYSA-N tantalum(5+) pentanitrate Chemical compound [Ta+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYNXQOUDSWHQQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 108700041286 delta Proteins 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 55
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 description 23
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229960001078 lithium Drugs 0.000 description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000007600 charging Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 235000014872 manganese citrate Nutrition 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
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- H01—ELECTRIC ELEMENTS
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Abstract
The invention relates to the field of lithium ion batteries, and discloses a multi-element cathode material, a preparation method thereof and a lithium ion battery. The multi-element anode material comprises a matrix and a fast ion conductor coating layer coated on the surface of the matrix; component Li of fast ion conductor coating layer 7‑i A i La 3‑j A’ j Zr 2‑q A” q O 12+δ And Li u J v La 2‑w J’ w O 4+ω (ii) a Selection AAt least one of Mg, ca, al and Ga, A 'is selected from at least one of Sr, Y and Ce, A' is selected from at least one of Zn, cu, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb and Ta, i is more than or equal to 0 and less than or equal to 2,0 and less than or equal to 1,0 and less than or equal to 2,0 and less than or equal to 1, and i, j and k are not 0 at the same time; j is selected from at least one of Al, ni, co, mn, cu and Fe, J' is selected from at least one of Ca, ba, sr, la, Y, ce, rb and Ru, u is more than 0 and less than or equal to 1,0 and more than v and less than or equal to 1,0 and less than or equal to w and less than or equal to 1,0 and less than or equal to omega 1. The multi-component material provided by the invention can improve the discharge specific capacity, the rate capability, the cycle retention rate and the safety performance of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a multi-element cathode material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are widely applied to consumer electronics, and the rapid development of new energy automobile industry puts higher requirements on the performances of power batteries, such as energy density, safety, rapid charge and discharge, cycle life and the like. The nickel manganese lithium cobaltate anode material (referred to as a multi-element material for short) becomes a mainstream product of the high-performance lithium ion battery anode material. The specific capacity of the multi-component material is improved along with the increase of the nickel content, and great attention is paid to the multi-component material. However, the cycle life, rate capability and safety performance of the multi-component materials deteriorate with increasing nickel content.
The cathode material is modified by means of doping, cladding and the like so as to meet the application requirements of industrialization. The common coating means is to form an inert coating layer on the surface of a multi-component material matrix by a sol-gel or mechanical mixing method so as to relieve the problems of side reaction between a positive electrode material and electrolyte, transition metal dissolution and the like. In recent years, the coating of the fast ion conductor on the cathode material has led to extensive research, and in the prior art, the cathode material is usually coated by means of sol-gel or wet method to form a fast ion conductor layer (inter surface Engineering on cathode side for solid crystals, chemical Engineering Journal,2020,387 124089 cn 111755698), however, on the one hand, the optimal temperature for forming the fast ion conductor phase is greatly different from the optimal temperature for coating the cathode material, so the crystal form of the fast ion conductor generated in situ on the surface of the cathode material is poor, the lithium ion conduction rate is low, i.e. no active lithium ion conduction surface coating layer is formed; on the other hand, the solvent used in the preparation process often damages the crystal structure of the cathode material and reduces the cycle stability of the cathode material. In addition, a coating layer is formed on the multi-component material by adopting a dry coating method (Surface modification of nickel-rich cathode materials by ionic conductive materials, energy Technology,2021,2100422) without heat treatment or the like, wherein the chemical bonding force between the multi-component material and the fast ion conductor is weak and the effect is not obvious because of no heat treatment process.
Therefore, the research and development of the cathode material with the surface constructed with the fast ion conductor channel and the low interface impedance are of great significance.
Disclosure of Invention
The invention aims to overcome the problems that lithium ions cannot be effectively conducted due to poor crystal form of a fast ion conductor on the surface of a multi-component material and the bonding force between the fast ion conductor and the multi-component material is weak in the prior art, and provides a multi-component anode material, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a multi-element cathode material, wherein the multi-element cathode material comprises a substrate and a fast ion conductor coating layer coated on the surface of the substrate; the fast ion conductor coating layer comprises Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω ；
Wherein, in the Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ In the formula, A is selected from at least one of Mg, ca, al and Ga, A 'is selected from at least one of Sr, Y and Ce, A' is selected from at least one of Zn, cu, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb and Ta, i is more than or equal to 0 and less than or equal to 2,0 and less than or equal to 1,0 and less than or equal to q is more than or equal to 2,0 and less than or equal to 1, and i, j and k are not 0 at the same time;
wherein, in the Li u J v La 2-w J’ w O 4+ω Wherein J is selected from at least one of Al, ni, co, mn, cu and Fe, J' is selected from at least one of Ca, ba, sr, la, Y, ce, rb and Ru, u is more than 0 and less than or equal to 1,0 and v is less than or equal to 1,0 and less than or equal to w is less than or equal to 1,0 and less than or equal to omega 1.
The second aspect of the invention provides a preparation method of a multi-element cathode material, wherein the preparation method comprises the following steps:
(1) Preparing a mixed salt solution from cobalt salt, manganese salt and nickel salt according to the molar ratio of Ni to Co to Mn = (1-x-y) to x to y;
(2) Contacting the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution for coprecipitation reaction to obtain solid-liquid mixed slurry; filtering, washing, drying and screening the solid-liquid mixed slurry to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-component material precursor, the lithium source and the compound of the M' source to obtain a multi-component anode material matrix;
(4) A first process is adopted: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω Mixing the fast ionic conductor and the multi-element anode material matrix, and performing first sintering, crushing and screening to obtain a fast ionic conductor coated multi-element anode material;
alternatively, the first and second electrodes may be,
adopting a second process: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And mixing the lanthanum source, the J source compound, the J' source compound and the lithium salt with the multi-element positive electrode material matrix, and performing second sintering, crushing and screening to obtain the fast ion conductor coated multi-element positive electrode material.
The invention provides a multi-element anode material prepared by the preparation method.
The invention provides a lithium ion battery, wherein the lithium ion battery comprises the multi-element cathode material as a cathode material.
Through the technical scheme, the invention has the following advantages:
(1) According to the invention, a garnet-type fast ion conductor and a layered perovskite-type fast ion conductor coating layer are constructed on the multi-element cathode material through chemical bonds to form a lithium ion fast transmission channel, so that the electrochemical reaction rate at an interface is improved, the interface impedance is reduced, and the rate capability of the multi-element cathode material is improved; the stable crystal structure of the coating layer can inhibit side reaction between the multielement cathode material and the electrolyte, namely inhibit the increase of impedance in the circulating process.
(2) According to the invention, while the fast ion conductor coating layer is constructed on the surface of the multi-element anode material, the proportion of the components of lithium, nickel, cobalt and manganese in the surface layer of the multi-element anode material is changed, and a low-nickel shell layer is formed, which is beneficial to improving the structural stability and the thermal stability of the multi-element anode material.
(3) The invention adopts a dry coating process to simultaneously form the garnet fast ion conductor and the layered perovskite fast ion conductor coating layer on the surface of the multi-element anode material, has the advantages of easy production and processing, low cost and little pollution, and is beneficial to realizing mass production.
Drawings
FIG. 1 is an XRD pattern of the multi-component materials prepared in comparative example 1 and example 1;
FIG. 2 is a graph showing the first charge and discharge in a liquid lithium battery of the multi-component materials prepared in comparative example 1 and example 1;
fig. 3 is a graph showing cycle retention in liquid lithium batteries for the multi-component materials prepared in comparative example 1 and example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the present invention provides a multi-element cathode material, wherein the multi-element cathode material includes a substrate and a fast ion conductor coating layer coated on a surface of the substrate; the fast ion conductor coating comprises the following components of Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω ；
Wherein, in the Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ Wherein A is selected from at least one of Mg, ca, al and Ga, A 'is selected from at least one of Sr, Y and Ce, A' is selected from at least one of Zn, cu, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb and Ta, i is more than or equal to 0 and less than or equal to 2,0 and less than or equal to 1,0 and less than or equal to q and less than or equal to 2,0 and less than or equal to 1, and i, j and k are not 0 at the same time;
wherein, in the Li u J v La 2-w J’ w O 4+ω Wherein J is selected from at least one of Al, ni, co, mn, cu and Fe, J' is selected from at least one of Ca, ba, sr, la, Y, ce, rb and Ru, u is more than 0 and less than or equal to 1,0 and v is less than or equal to 1,0 and less than or equal to w is less than or equal to 1,0 and less than or equal to omega 1.
The inventors of the present invention found that: in the process of preparing the multi-element anode material, a dry coating process is adopted, a proper coating reaction driving force is provided by controlling the sintering temperature and the sintering rate and matching corresponding coating agents, a garnet type fast ion conductor and a layered perovskite type fast ion conductor coating layer are constructed on the surface of the multi-element anode material through chemical bonds, a lithium ion fast transmission channel is formed, the electrochemical reaction rate at an interface is improved, the interface impedance is reduced, and the multiplying power performance of the multi-element anode material is improved; the stable crystal structure of the coating layer can inhibit side reaction between the multi-element anode material and the electrolyte, namely inhibit the increase of impedance in the circulation process; in addition, when the fast ion conductor coating layer is constructed on the surface of the multi-element anode material, the proportion of the components of lithium, nickel, cobalt and manganese in the surface layer of the multi-element anode material is changed, and a low-nickel shell layer is formed, so that the structural stability and the thermal stability of the multi-element anode material are improved.
According to the invention, the composition of the matrix comprises Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (ii) a Wherein M and M' are each independently selected from at least one of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; z is more than or equal to 0.9 and less than or equal to 1.3,0.001 and less than or equal to 1,0 and less than or equal to 1,0 and more than alpha and less than or equal to 0.1,0 and more than beta and less than or equal to 0.1; preferably, M and M' are each independently selected from at least one of Al, ba, zr, ti, nb, Y, W, sr, cr, mo, la, ce, mg and B; z is more than or equal to 1.0 and less than or equal to 1.1,0.001 and less than or equal to 0.5,0 and less than or equal to y is more than or equal to 0.5,0 and more than alpha and less than or equal to 0.05,0 and more than beta and less than or equal to 0.05.
According to the invention, the X-ray diffraction pattern (XRD) of the multi-element cathode material also has Li besides characteristic peaks of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω At least one characteristic peak, the angle and the corresponding crystal surface are shown in the table 1, wherein the characteristic peak of the multielement positive electrode material only lists three strong peaks.
TABLE 1
According to the invention, li in XRD of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak intensity of crystal face I (103) The ratio of 0.2 < I (422 /I (103) < 1.5, preferably, 0.5 < I (422 /I (103) Less than 1.2; preferably, li in XRD (X ray diffraction) of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal face A (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak area of crystal plane A (103) The ratio of 1.0 < A (422 /A (103) < 5.0, preferably, 1.5 < A (422) /A (103) ＜3.0。
According to the invention, li in XRD of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak intensity of crystal face I (003) The ratio of 0.01% < I (422) /I (003) < 1.2%, preferably, 0.1% < I (422) /I (003) Less than 0.5 percent; preferably, li in XRD (X ray diffraction) of the multi-element cathode material 7- i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal plane A (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak area of crystal face A (003) The ratio of 0.01% < A (422) /A (003) < 1.2%, preferably, 0.1% < A (422) /A (003) ＜0.5％。
According to the invention, preferably, A is selected from at least one of medium Al and Ga, and A' is selected from medium Sr and/or Ce; a' is at least one selected from Co, ti, W, nb and Ta; i is more than or equal to 0 and less than or equal to 1,0 and less than or equal to 0.5,0 and less than or equal to q is more than or equal to 1,0 and less than or equal to delta is less than or equal to 0.5.
According to the present invention, it is preferable that J is selected from at least one of Al, ni, co, and Cu; j' is selected from at least one of Ba, sr, Y and Ce; u is more than 0 and less than or equal to 0.8,0 and more than or equal to v and less than or equal to 0.8,0 and less than or equal to w and less than or equal to 0.8,0 and less than or equal to omega and less than or equal to 0.8. According to the invention, the Li 7- i A i La 3-j A’ j Zr 2-q A” q O 12+δ Has a garnet structure; the Li u J v La 2-w J’ w O 4+ω Has a layered perovskite structure, and the two form an ion-electron conductive network, not onlyThe side reaction between the multi-element anode material and the electrolyte can be inhibited, the stability of the multi-element anode material in the battery cycle is improved, the lithium ion transmission at the interface of the anode and the electrolyte is improved, the multiplying power performance of the multi-element anode material is improved, and meanwhile, the increase of impedance in the cycle process can be inhibited by the stable crystal structure of the coating layer, so that the battery performance is improved.
According to the invention, the average particle diameter D of the multi-element cathode material 50 2-30 μm; preferably 3-20 μm.
According to the invention, the thickness of the fast ion conductor coating layer is 2-30nm; preferably 3-15nm.
According to the invention, the mass ratio of the fast ion conductor coating layer to the matrix is (0.01-5): 100, preferably in a mass ratio of (0.05-1): 100.
the second aspect of the invention provides a preparation method of a multi-element cathode material, wherein the preparation method comprises the following steps:
(1) Preparing a mixed salt solution from cobalt salt, manganese salt and nickel salt according to the molar ratio of Ni to Co to Mn = (1-x-y) to x to y;
(2) Contacting the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution for coprecipitation reaction to obtain solid-liquid mixed slurry; filtering, washing, drying and screening the solid-liquid mixed slurry to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-component material precursor, the lithium source and the compound of the M' source to obtain a multi-component anode material matrix;
(4) A first process is adopted: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω Mixing the fast ionic conductor and the multi-element anode material matrix, and performing first sintering, crushing and screening to obtain a fast ionic conductor coated multi-element anode material;
alternatively, the first and second electrodes may be,
adopting a second process: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And mixing the lanthanum source, the J source compound, the J' source compound and the lithium salt with the multi-element positive electrode material matrix, and performing second sintering, crushing and screening to obtain the fast ion conductor coated multi-element positive electrode material.
According to the invention, the nickel salt, the cobalt salt and the manganese salt are each independently selected from at least one of the group consisting of sulfate, nitrate, chloride, oxalate, acetate and citrate.
Further, the nickel salt is selected from at least one of nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate, nickel acetate and nickel citrate; the cobalt salt is at least one selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate, cobalt acetate and cobalt citrate; the manganese salt is selected from at least one of manganese sulfate, manganese nitrate, manganese chloride, manganese oxalate, manganese acetate and manganese citrate.
According to the present invention, the precipitant solution may be a precipitant solution conventional in the art, for example, the precipitant solution is a sodium hydroxide solution.
According to the present invention, the complexing agent solution may be a complexing agent solution that is conventional in the art, for example, the complexing agent solution is an aqueous ammonia solution.
According to the invention, in the step (1), the concentration of the mixed salt solution is 1-3mol/L, the concentration of the precipitant solution is 1-15mol/L, the concentration of the complexing agent solution is 1-15mol/L, and the concentration of the M source salt solution is 0.01-1mol/L.
The dosage of the precipitant solution and the complexing agent solution is not particularly limited, and may be controlled according to the morphology and the particle size of the prepared multi-element cathode material precursor.
Further, the concentration of the mixed salt solution is 1.5-2.5mol/L, the concentration of the precipitant solution is 5-10mol/L, the concentration of the complexing agent solution is 5-10mol/L, and the concentration of the M source salt solution is 0.05-0.5mol/L.
According to the invention, the M source is used in an amount such that 0 < [ n (M) ]/[ n (Ni) + n (Co) + n (Mn) ] < 0.1.
In the invention, when the dosage of the M source meets the range, M element can effectively enter the precursor crystal lattice of the multi-element anode material, so that the doping of the precursor crystal lattice of the anode material at the molecular/ion scale is realized, and meanwhile, the crystal lattice distortion is not caused seriously to damage the structural stability and prevent the lithium ion transmission.
Further, the M source is used in an amount of 0.001. Ltoreq. N (M) ]/[ n (Ni) + n (Co) + n (Mn) ] < 0.05.
According to the invention, the compounds of the M source and of the M' source are selected from compounds of at least one element of the group consisting of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B.
In the present invention, the M source and the M' source may be the same or different.
Further, the salt solution of the M source is a water-soluble salt of the M source, and is preferably at least one selected from the group consisting of sodium metaaluminate, barium nitrate, zirconium chloride, titanium sulfate, niobium nitrate, tantalum nitrate, gallium nitrate, yttrium nitrate, ammonium tungstate, calcium chloride, lanthanum nitrate, cerium nitrate, magnesium nitrate, and sodium borate.
Further, the compound of the M 'source is selected from at least one of an oxide of the M' source, a hydroxide of the M 'source, and a carbonate of the M' source.
According to the invention, the particle diameter D of the multi-element anode material precursor 50 Is 1 to 30 μm, preferably 3 to 20 μm.
According to the invention, in step (2), the conditions of the coprecipitation reaction include: the pH value is 10-13, the reaction temperature is 40-70 ℃, and the reaction time is 5-20h.
Further, the conditions of the coprecipitation reaction include: the pH value is 11-12, the reaction temperature is 50-60 ℃, and the reaction time is 8-16h.
According to the invention, in step (3), the lithium source is used in a molar ratio of 0.90. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) + n (M)]Adding the mixture in an amount less than or equal to 1.30; further, the lithium source is equal to or less than [ n (Li) ] according to the molar ratio of 0.96]/[n(Ni)+n(Co)+n(Mn)+n(M)]Adding the mixture in an amount of less than or equal to 1.08; when the dosage of the lithium source meets the range, alpha-NaFeO with complete crystal form can be formed 2 The multi-element anode material has a structure thatHigh specific capacity.
According to the invention, the source of M 'is used in an amount equal to or less than 0.1 in a molar ratio of 0 < n (M')/[ n (Ni) + n (Co) + n (Mn) ]; further, the M 'source is added in a molar ratio of 0.001. Ltoreq. N (M')/[ n (Ni) + n (Co) + n (Mn) ]. Ltoreq.0.05. In the invention, when the dosage of the M 'source and the multi-element anode material precursor meets the range, the M' element enters the crystal lattice and/or the crystal boundary of the multi-element anode material precursor in the form of a nano group, so that doping is realized at a nano scale, and the stability of a crystal structure and the stability of a surface interface are improved.
According to the invention, in the step (3), the expression of the multi-element cathode material matrix is Li z [(Ni 1-x- y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (ii) a Z is more than or equal to 0.9 and less than or equal to 1.3,0.001 and less than or equal to 1,0 and less than or equal to 1,0 and more than alpha and less than or equal to 0.1,0 and more than beta and less than or equal to 0.1; preferably, 1.0. Ltoreq. Z.ltoreq. 1.1,0.001. Ltoreq. 0.5,0. Ltoreq. 0.5,0 < alpha. Ltoreq. 0.05,0 < beta. Ltoreq.0.05.
According to the invention, in step (4), if the first process is used, the Li is 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ The dosage relation of (A) satisfies the following mass ratio:
0.1％≤m(Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ )/m{Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 }≤5％。
the Li u J v La 2-w J’ w O 4+ω The dosage relation of (A) satisfies the following mass ratio:
0.1％≤m(Li u J v La 2-w J’ w O 4+ω )/m{Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 }≤5％。
according to the invention, in step (4), if the second step is usedThe lithium salt is n (Li)/[ n (J) + n (J')]Adding the mixture in an amount less than or equal to 2; the lanthanum source is added according to the molar ratio of n (La)/n (J) which is more than or equal to 2 and less than or equal to 6; when the lithium source and the lanthanum source are used in amounts satisfying the above ranges, li forming a layered perovskite structure may be additionally provided u J v La 2-w J’ w O 4+ω Fast ion conductor, avoiding Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ The crystal structure is destroyed in the sintering process, so that the prepared multi-element anode material has higher specific capacity. If more lithium carbonate and lithium hydroxide remain on the surface of the multi-element positive electrode material, especially the multi-element positive electrode material with the nickel content of more than 90 percent, the addition of lithium salt is not needed. Further, the lithium source is in a molar ratio of 0. Ltoreq. N (Li)/[ n (J) + n (J')]Adding the components in an amount less than or equal to 1.
The dosage relation of the J source meets the following mass ratio:
m (J source)/m { Li is more than or equal to 0.1% z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 }≤5％。
The dosage relation of the J' source meets the following mass ratio:
m (J' source)/m { Li is more than or equal to 0.1% z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 The amount of which is less than or equal to 5 percent.
In the present invention, when Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω When the amounts of the lanthanum source, the J source and the J' source are in the above ranges, li having a garnet structure is formed on the surface of the multicomponent material while consuming lithium carbonate and lithium hydroxide remaining on the surface of the multicomponent material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li of layered perovskite structure u J v La 2-w J’ w O 4+ω Fast ion conductor claddingThe layer is convenient for the transmission of lithium ions in the coating layer, can inhibit the side reaction between the multi-element anode material and the electrolyte, and improves the specific capacity, the multiplying power and the cycle life of the multi-element anode material.
According to the invention, the compound of the lanthanum source is selected from at least one of lanthanum oxide, lanthanum hydroxide, lanthanum oxalate and lanthanum carbonate; the compound of the J source is selected from at least one of an oxide of the J source, a hydroxide of the J source and a carbonate of the J source; the J source is selected from at least one element compound of Al, ni, co, cu and Fe.
According to the present invention, the compound of the J 'source is selected from at least one of an oxide of the J' source, a hydroxide of the J 'source, and a carbonate of the J' source; the J' source is at least one element compound selected from Ca, ba, sr, Y, ce, rb and Ru.
According to the invention, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide and lithium nitrate.
According to the invention, in step (4), the conditions of the first sintering and the second sintering are the same or different, each comprising: the sintering temperature is 650-1000 ℃, preferably 800-950 ℃; the sintering time is 4-20h, preferably 6-15h; in addition, in the first process, the sintering rate in the first sintering is 3-10 ℃/min, and preferably 4-6 ℃/min; in the second process, the sintering rate in the second sintering is 0.5-2 ℃/min, preferably 0.8-1.5 ℃/min, so as to fully form the layered perovskite type fast ion conductor.
According to the invention, the M' source, li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω D of J Source, J' Source 50 Less than 200nm, and specific surface area greater than 20m 2 /g。
In the present invention, D is selected 50 Less than 200nm, and specific surface area greater than 20m 2 Source of M' in/g, li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω The J source and the J ' source can uniformly mix the M ' source and the multi-element positive electrode material precursor, and preferably, the M ' source and the Li source 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω J source, J' source Compound D 50 10-150nm, and specific surface area of 50-500m 2 /g。
According to the present invention, the specific operations of filtering, washing, drying, mixing (mixing), grinding, crushing, screening, and iron removal are not particularly limited as long as the requirements are satisfied. In the invention, the filtration can be realized by suction filtration, filter pressing, centrifugation and the like; drying can be realized by hot air, infrared rays, microwaves and the like; the mixing can be realized by adopting a high-speed mixer, a V-shaped mixer, a double-cone mixer or a coulter mixer; the grinding can be realized by adopting a stirring ball mill, a planetary ball mill or a sand mill; the crushing can be realized by adopting a double-roller crushing mode, a ball mill mode, an air flow mill mode or a mechanical milling mode; the screening can adopt an ultrasonic vibration screen; the iron removal can be realized by an electromagnetic iron remover.
The invention provides a multi-element cathode material prepared by the preparation method.
The invention provides a lithium ion battery, wherein the lithium ion battery comprises the multi-element cathode material as a cathode material.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the granularity of the precursor of the multi-element anode material is measured by a Mastersizer 2000 laser particle sizer;
the coating layer component in the anode material can be measured by a Rigaku X-ray diffractometer;
the thickness of the cladding layer in the anode material can be measured by a Hitachi HF5000 transmission electron microscope;
the raw materials such as nickel sulfate, cobalt sulfate, manganese sulfate and lithium hydroxide are commercially available products of battery grade unless otherwise specified.
Example 1
This example is to illustrate a positive electrode material prepared by the method of the present invention.
Step one, preparing a 2mol/L mixed salt solution according to the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 90. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 And (4) O complexing agent solution.
Step two, mixing the mixed salt solution, zirconium nitrate solution (M source), naOH solution and NH 3 ·H 2 The O complexing agent solution is continuously added into the stirred reactor in a cocurrent mode for reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃, and waiting for slurry D 50 The reaction was stopped when 10 μm was reached. And washing, filtering and drying the product to obtain a zirconium-doped multi-element anode material precursor, wherein zirconium nitrate is added according to the molar ratio of Zr/(Ni + Co + Mn) = 0.001.
Step three, uniformly mixing the zirconium-doped multi-element anode material precursor, the lanthanum hydroxide and the lithium hydroxide in the step two, wherein the lanthanum hydroxide D 50 =30nm, specific surface area 100m 2 Lanthanum hydroxide (M' source) was mixed in a molar ratio La/(Ni + Co + Mn) =0.001, and lithium hydroxide was mixed in a molar ratio Li/(Ni + Co + Mn + Zr + La) = 1.05. And sintering the mixture at 850 ℃ for 10 hours, crushing and screening to obtain the zirconium-lanthanum-doped multi-element cathode material matrix.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 Mixing uniformly, wherein, li 6.4 Al 0.2 La 3 Zr 2 O 12 D of (A) 50 =50nm, specific surface area 120m 2 /g，Li 0.5 La 2 Al 0.5 O 4 D of (1) 50 =50nm, specific surface area 100m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 The mass ratio is 1000:3.5:3.5. heating the mixture to 600 ℃ at the speed of 5 ℃/min, sintering for 10 hours, crushing and screening to obtain a fast ion conductor coated multi-element cathode material A1, wherein the composition of the fast ion conductor coated multi-element cathode material A1 is shown in table 2; in addition to the characteristic peaks of the multi-component material, li also exists in the XRD pattern of A1 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 Characteristic peaks, as shown in fig. 1.
Example 2
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 1.875 Sr 0.125 Co 0.5 O 4 Mixing uniformly, wherein, li 6.4 Al 0.2 La 3 Zr 2 O 12 D of (A) 50 =50nm, specific surface area 120m 2 /g，Li 0.5 La 1.875 Sr 0.125 Co 0.5 O 4 D of (A) 50 =50nm, specific surface area 150m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 1.875 Sr 0.125 Co 0.5 O 4 The mass ratio is 1000:3.5:3.5. and then heating the mixture to 600 ℃ at the speed of 5 ℃/min, sintering for 10 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A2, wherein the composition of the fast ion conductor coated multi-element cathode material A2 is shown in Table 2.
Example 3
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、La 2 O 3 、Co(OH) 2 And LiOH, wherein Li is 6.4 Al 0.2 La 3 Zr 2 O 12 D of (A) 50 =50nm, specific surface area 120m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 /g，Co(OH) 2 D of (A) 50 =30nm, specific surface area 100m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、La 2 O 3 、Co(OH) 2 The LiOH mass ratio is 1000:3.5:3.04:0.43:0.1. and heating the mixture to 720 ℃ at a speed of 1.5 ℃/min, sintering for 8 hours, crushing, and screening to obtain the fast ion conductor coated multi-element cathode material A3, wherein the composition of the fast ion conductor coated multi-element cathode material A3 is shown in Table 2.
Example 4
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、La 2 O 3 、Al 2 O 3 And LiOH, wherein Li is 6.4 Al 0.2 La 3 Zr 2 O 12 D of (1) 50 =50nm, specific surface area 120m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 /g，Al 2 O 3 D of (A) 50 =20nm, specific surface area 230m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 、La 2 O 3 、Al 2 O 3 The LiOH mass ratio is 1000:3.5:3.18:0.25:0.1. and then heating the mixture to 750 ℃ at the speed of 1 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A4, wherein the composition of the fast ion conductor coated multi-element cathode material is shown in Table 2.
Example 5
This example is intended to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 Mixing uniformly, wherein, li 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 D of (1) 50 =25nm, specific surface area 140m 2 /g，Li 0.5 La 2 Al 0.5 O 4 D of (A) 50 =50nm, specific surface area 100m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 The mass ratio is 1000:3.5:3.5. and then heating the mixture to 450 ℃ at the speed of 5 ℃/min, sintering for 10 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A5, wherein the composition of the fast ion conductor coated multi-element cathode material is shown in Table 2.
Example 6
This example is to illustrate a positive electrode material prepared by the method of the present invention.
Step one, preparing a 2mol/L mixed salt solution according to the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate being 60. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 And (4) O complexing agent solution.
Step two, mixing the mixed salt solution, zirconium nitrate solution (M source), naOH solution and NH 3 ·H 2 The O complexing agent solution is continuously added into the stirred reactor in a cocurrent mode for reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃, and waiting for slurry D 50 The reaction was stopped when 5 μm was reached. And washing, filtering and drying the product to obtain a zirconium-doped multi-element anode material precursor, wherein zirconium nitrate is added according to the molar ratio of Zr/(Ni + Co + Mn) = 0.001.
Step three, the step ofUniformly mixing the zirconium-doped multi-element anode material precursor, lanthanum hydroxide and lithium hydroxide in the second step, wherein the lanthanum hydroxide D 50 =30nm, specific surface area 100m 2 Lanthanum hydroxide (M' source) was mixed in a molar ratio La/(Ni + Co + Mn) =0.001, and lithium hydroxide was mixed in a molar ratio Li/(Ni + Co + Mn + Zr + La) = 1.05. And sintering the mixture at 880 ℃ for 10 hours, and crushing and screening to obtain the zirconium-lanthanum-doped multi-element positive material matrix.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.5 Al 0.1 La 3 Zr 1.8 Nb 0.2 O 12 、La 2 O 3 、Co(OH) 2 And LiOH, wherein Li is 6.5 Al 0.1 La 3 Zr 1.8 Nb 0.2 O 12 D of (A) 50 =45nm, specific surface area 130m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 /g，Co(OH) 2 D of (A) 50 =30nm, specific surface area 100m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.5 Al 0.1 La 3 Zr 1.8 Nb 0.2 O 12 、La 2 O 3 、Co(OH) 2 The LiOH mass ratio is 1000:3.5:3.04:0.43:0.15. and heating the mixture to 720 ℃ at the speed of 1 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A6, wherein the composition of the fast ion conductor coated multi-element cathode material A6 is shown in table 2.
Example 7
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in example 5.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 、La 2 O 3 、Al 2 O 3 And LiOH, wherein Li is 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 D of (1) 50 =25nm, specific surface areaIs 140m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 /g，Al 2 O 3 D of (A) 50 =20nm, specific surface area 230m 2 Perg, zirconium lanthanum doped multi-element anode material matrix and Li 6.7 Ga 0.1 La 2.7 Sr 0.3 Zr 2 O 12 、La 2 O 3 、Al 2 O 3 The LiOH mass ratio is 1000:3.5:3.18:0.25:0.15. and then heating the mixture to 695 ℃ at 1 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A7, wherein the composition of the fast ion conductor coated multi-element cathode material A7 is shown in Table 2.
Example 8
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in example 5.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Ga 0.2 La 3 Zr 1.8 Co 0.2 O 12 、La 2 O 3 CuO and LiOH, wherein Li 6.4 Ga 0.2 La 3 Zr 1.8 Co 0.2 O 12 D of (A) 50 =30nm, specific surface area 130m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 D of/g, cuO 50 =20nm, specific surface area 200m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Ga 0.2 La 3 Zr 1.8 Co 0.2 O 12 、La 2 O 3 The mass ratio of CuO to LiOH is 1000:3.5:3.02:0.37:0.11. and then heating the mixture to 720 ℃ at the speed of 1 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material A8, wherein the composition of the fast ion conductor coated multi-element cathode material is shown in Table 2.
Example 9
This example is to illustrate a positive electrode material prepared by the method of the present invention.
The first step, the second step and the third step are the same as those in example 5.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Ga 0.2 La 3 Zr 1.8 Ti 0.2 O 12 、La 2 O 3 、Fe 2 O 3 And LiOH, wherein Li is 6.4 Ga 0.2 La 3 Zr 1.8 Ti 0.2 O 12 D of (A) 50 =30nm, specific surface area 130m 2 /g，La 2 O 3 D of (A) 50 =20nm, specific surface area 160m 2 /g，Fe 2 O 3 D of (1) 50 =20nm, specific surface area 230m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Ga 0.2 La 3 Zr 1.8 Ti 0.2 O 12 、La 2 O 3 、Fe 2 O 3 The LiOH mass ratio is 1000:3.5:3.02:0.43:0.11. and then heating the mixture to 715 ℃ at the speed of 1 ℃/min, sintering for 8 hours, and crushing and screening to obtain the fast ion conductor coated multi-element cathode material A9, wherein the composition of the fast ion conductor coated multi-element cathode material is shown in Table 2.
Comparative example 1
Step one, preparing a 2mol/L mixed salt solution according to the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 90. Preparing 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 And (4) O complexing agent solution.
Step two, mixing the salt solution, naOH solution and NH 3 ·H 2 The O complexing agent solution is continuously added into the stirred reactor in a cocurrent mode for reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃, and waiting for slurry D 50 The reaction was stopped when 10 μm was reached. And washing, filtering and drying the product to obtain the precursor of the multi-element cathode material.
And step three, uniformly mixing the multi-element anode material precursor in the step two with lithium hydroxide, wherein the lithium hydroxide is mixed according to the molar ratio of Li/(Ni + Co + Mn) = 1.05. And sintering the mixture at 850 ℃ for 10 hours, and crushing and screening to obtain the multi-element positive electrode material D1. The composition of the multi-element cathode material D1 is shown in table 2; only characteristic peaks of the multielement material exist in the XRD pattern of D1, as shown in figure 1.
Comparative example 2
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 0.5 La 2 Al 0.5 O 4 Mixing uniformly, wherein, li 0.5 La 2 Al 0.5 O 4 D of (A) 50 =50nm, specific surface area 100m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 0.5 La 2 Al 0.5 O 4 The mass ratio is 1000:7. and heating the mixture to 720 ℃ at the speed of 5 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material D2, wherein the composition of the fast ion conductor coated multi-element cathode material D2 is shown in the table 2.
Comparative example 3
The first step, the second step and the third step are the same as those in the embodiment 1.
Step four, doping zirconium lanthanum into a multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 Mixing uniformly, wherein, li 6.4 Al 0.2 La 3 Zr 2 O 12 D of (A) 50 =50nm, specific surface area 120m 2 G, zirconium lanthanum doped multi-element anode material matrix and Li 6.4 Al 0.2 La 3 Zr 2 O 12 The mass ratio is 1000:7. and then heating the mixture to 720 ℃ at the speed of 1 ℃/min, sintering for 8 hours, crushing and screening to obtain the fast ion conductor coated multi-element cathode material D3, wherein the composition of the fast ion conductor coated multi-element cathode material is shown in Table 2.
Comparative example 4
A multicomponent material D4 was prepared as in example 1 except that in step four, the sintering temperature was 350 ℃, the sintering time was 8 hours, the temperature rise rate was 5 ℃/min and the composition is shown in table 2; the XRD pattern of D4 has characteristic peaks of multi-component materials, and Li is also present 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 Characteristic peaks, as shown in FIG. 1, but the peak intensity ratio and peak area ratio are outside the scope of the present invention.
Comparative example 5
A multi-component material D4 was prepared as in example 1, except that in step four, the lanthanum zirconium was doped into the multi-component positive electrode material matrix, li 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 The mass ratio is 1000:0.5:0.5, the composition of which is shown in Table 2.
TABLE 2
Test example 1
The positive electrode material prepared in the embodiment and the comparative example is used for assembling the liquid lithium ion battery, and the specific steps are as follows: the method comprises the following steps of mixing a positive electrode material, acetylene black and polyvinylidene fluoride according to a mass ratio of 95:2.5:2.5 dispersing in a proper amount of NMP, coating on aluminum foil, drying, cutting into a positive pole piece with the diameter of 12mm, and vacuum drying the positive pole piece at 120 ℃ for 12h, and then vacuum sealing and storing. The negative electrode uses a lithium metal sheet with the diameter of 16mm and the thickness of 1 mm; the diaphragm is a Celgard porous membrane with the thickness of 25 mu m; the electrolyte is LiPF 6 Using equal volume of ethylene carbonate, dimethyl carbonate and diethyl carbonate as solvent, liPF 6 The concentration of (2) is 1mol/L.
And assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into the 2025 type button cell in an argon-filled glove box with the water content and the oxygen content of less than 5 ppm. The electrochemical performance of the liquid lithium ion battery is tested, and the specific test comprises the following steps: the test temperature was maintained at 25 ℃. Charging to 4.3V with 0.1C charging current, charging to charging current less than or equal to 0.01C with constant voltage, discharging to 3V with 0.1 discharging current to form 2 periods, and repeating 1C charging and discharging. And (4) observing the charge-discharge capacity and the cycle performance of the cathode material in the liquid lithium ion battery. The test results are shown in table 3.
TABLE 3
As can be seen from tables 2 to 3:
the multi-component positive electrode materials prepared by the invention from the example 1 to the example 10 have Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω Characteristic peak, and Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak intensity of crystal face I (422) The ratio of 0.01% < I (422) /I (003) ＜1.2％；Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal face A (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak area of crystal face A (003) The ratio of 0.01% < A (422) /A (003) ＜1.2％；Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak intensity of crystal face I (103) The ratio of 0.2 < I (422 /I (103) ＜1.5；Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal face A (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak area of crystal face A (103) The ratio of 1.0 < A (422 /A (103) Is less than 5.0. Is less introduced with Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω Comparative example 1 of coating layer; introduction of only Li u J v La 2-w J’ w O 4+ω Comparative example 2 of clad layer and introduction of only Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ The multi-element anode material of the coating layer in the comparative example 3 has higher specific discharge capacity, rate capability and cycle retention rate. The fast ion transmission channel constructed on the surface of the multi-element anode material can improve the interface reaction rate of the anode and the electrolyte, reduce the interface impedance and improve the multiplying power performance of the multi-element anode material, and meanwhile, the stable crystal structure of the coating layer can also inhibit the impedance increase in the circulation process; thereby improving battery performance.
Specifically, by Li, as compared with comparative examples 2 and 3 6.4 Al 0.2 La 3 Zr 2 O 12 、Li 0.5 La 2 Al 0.5 O 4 Or cobalt hydroxide, lanthanum oxide and lithium hydroxide form the materials of the invention with the characteristic structure of the embodiment 1, the embodiment 2, the embodiment 3, the embodiment 4 and the embodiment 5, which have higher specific discharge capacity, rate capability and cycle retention rate.
Specifically, in comparison with comparative example 4, the sintering temperature range is defined by Li using the present invention 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 The embodiment 1 with the characteristic structure of the invention has higher specific discharge capacity, rate capability and cycle retention rate.
Further, example 1 using the preferred heat treatment process of the present invention has a higher specific discharge capacity than example 5 not using the preferred heat treatment process.
Further, example 1 using the preferred composition ratio of the present invention has higher specific discharge capacity, rate capability and cycle performance than comparative example 5, which is not the composition ratio of the present invention.
In particular, with Li 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 The charge and discharge curves of the liquid lithium ion battery obtained by assembling the multi-element cathode material A1 coated with the fast ion conductor and the non-coated multi-element cathode material D1 are shown in figure 2 at 0.1C. As can be seen from FIG. 2, the specific discharge capacities of the two lithium ion batteries in the liquid state are 225.3mAh/g and 210.4mAh/g respectively, and the charge-discharge polarization of the two lithium ion batteries is lower than that of the two lithium ion batteries in the liquid state.
With Li 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 Fig. 3 shows the cycle retention rate curves of the liquid lithium ion battery obtained by assembling the multiple positive electrode material A1 coated with the fast ion conductor and the multiple positive electrode material D1 not coated with the fast ion conductor at 1C. As can be seen from fig. 3, the cycle retention rate of the liquid lithium ion battery using A1 as the positive electrode is higher than that of the liquid lithium ion battery using D1 as the positive electrode, which indicates that the coating layer can effectively avoid side reactions between the positive electrode and the electrolyte, thereby improving the battery performance; and the specific discharge capacity 202.1mAh/g of A1 under 1C is higher than the specific discharge capacity 188.6mAh/g of D1, which indicates that the coating layer has better lithium ion conduction characteristic.
With Li in Table 4 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 The capacity of the multi-element anode material A1 of the fast ion conductor coating layer in the liquid lithium ion battery system is higher than that of the multi-element anode material A1 only made of Li 0.5 La 2 Al 0.5 O 4 A coated multi-element cathode material D2 and Li only 6.4 Al 0.2 La 3 Zr 2 O 12 The coated multi-element anode material D3 shows that an active coating layer which has higher ionic/electronic conductivity and is stable to electrolyte can be obtained through reasonable fast ion conductor coating, and the capacity and the structural stability of the multi-element anode material are improved.
Further, li can be formed in situ on the surface of the high-nickel ternary material in example 4 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Ni 0.5 O 4 Coating layer indicating high nickel ternary material and Li 6.4 Al 0.2 La 3 Zr 2 O 12 Reaction takes place, i.e. a higher nickel content can promote the formation of Li 0.5 La 2 Ni 0.5 O 4 。
Test example 2
The positive electrode materials prepared in the embodiment and the comparative proportion are used for assembling the solid lithium ion battery, and the specific steps are as follows:
the PEO and the LiTFSI are subjected to banburying according to the mass ratio of 3:1, then hot-pressed to form a thin film with the thickness of 30 mu m, and then the electrolyte film cut into the diameter of 19mm is placed at 60 ℃ for vacuum drying for 10h and then is stored in a vacuum sealing way.
Mixing a positive electrode material, acetylene black, PVDF and LiTFSI according to a mass ratio of 90:2:2:6, dispersing in a proper amount of NMP, coating on aluminum foil, drying, cutting into a positive pole piece with the diameter of 12mm, and vacuum-drying the positive pole piece at 120 ℃ for 12h, and then vacuum-sealing and storing.
And (3) taking metal lithium as a negative electrode, and assembling the positive electrode piece and the PEO electrolyte membrane into a 2025 type button cell in an argon-filled glove box with the water content and the oxygen content both less than 5 ppm. The electrochemical performance of the solid lithium ion battery is tested, and the specific test comprises the following steps: the test temperature was maintained at 60 ℃. Charging to 4.2V with 0.1C charging current, constant voltage charging to charging current less than or equal to 0.01C, discharging to 3V with 0.1 discharging current to form 2 periods, and repeating the charging and discharging with 0.2C current. And (4) observing the charge-discharge capacity and the cycle performance of the anode material in the solid lithium ion battery. The results are shown in Table 4.
TABLE 4
With Li 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 Multielement anode material A1 of fast ion conductor coating layer and non-coated layerAnd assembling the multi-element positive electrode material D1 to obtain the liquid lithium ion battery. From table 4, it can be seen that the discharge specific capacities of the two solid-state lithium batteries are 237.3mAh/g and 220.4mAh/g respectively, and the charge-discharge polarization of the solid-state lithium ion battery using A1 as the anode is smaller than that of the solid-state lithium ion battery using D1 as the anode, which indicates that the fast ion conductor coating layer can reduce the impedance between the anode and the electrolyte, improve the electrochemical reaction rate at the interface between the anode and the electrolyte, improve the rate capability of the multi-element anode material, and simultaneously, the stable crystal structure of the coating layer can also inhibit the increase of the impedance in the cycle process, thereby improving the battery performance.
With Li 6.4 Al 0.2 La 3 Zr 2 O 12 And Li 0.5 La 2 Al 0.5 O 4 The solid-state lithium ion battery is assembled by the multi-element cathode material A1 coated with the fast ion conductor and the non-coated multi-element cathode material D1, and the cycle retention rates of the two at 0.2C are respectively 78.3% and 47.7% as can be seen from Table 4. The cycle performance of the fast ionic conductor coated multi-element anode material is obviously superior to that of a matrix, and the coating layer can effectively avoid side reaction between an anode and electrolyte, so that the cycle retention rate of the battery is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. The multielement cathode material is characterized by comprising a matrix and a fast ion conductor coating layer coated on the surface of the matrix; the fast ion conductor coating comprises the following components of Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And Li u J v La 2-w J’ w O 4+ω ；
Wherein the content of the first and second substances,in the presence of Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ In the formula, A is selected from at least one of Mg, ca, al and Ga, A 'is selected from at least one of Sr, Y and Ce, A' is selected from at least one of Zn, cu, co, ge, hf, ir, mn, mo, ti, ru, se, te, W, sn, sb, nb and Ta, i is more than or equal to 0 and less than or equal to 2,0 and less than or equal to 1,0 and less than or equal to q and less than or equal to 2,0 and less than or equal to delta 1, and i, j and k are not 0 at the same time;
wherein, in the Li u J v La 2-w J’ w O 4+ω Wherein J is selected from at least one of Al, ni, co, mn, cu and Fe, J' is selected from at least one of Ca, ba, sr, la, Y, ce, rb and Ru, u is more than 0 and less than or equal to 1,0 and v is less than or equal to 1,0 and less than or equal to w is less than or equal to 1,0 and less than or equal to omega 1.
2. The multi-element positive electrode material of claim 1, wherein Li in XRD of the multi-element positive electrode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak intensity of crystal face I (103) The ratio of 0.2 < I (422 /I (103) < 1.5, preferably, 0.5 < I (422 /I (103) ＜1.2；
And/or Li in XRD (X-ray diffraction) of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal plane A (422) With Li u J v La 2-w J’ w O 4+ω (103) Peak area of crystal face A (103) The ratio of 1.0 < A (422) /A (103) < 5.0, preferably, 1.5 < A (422) /A (103) ＜3.0。
3. The multi-element positive electrode material according to claim 1, wherein a is selected from Al and/or Ga, a' is selected from medium Sr and/or Ce; a' is at least one selected from Co, ti, W, nb and Ta; i is more than or equal to 0 and less than or equal to 1,0 and less than or equal to 0.5,0 and less than or equal to q and less than or equal to 1,0 and less than or equal to delta and less than or equal to 0.5;
j is selected from at least one of Al, ni, co and Cu; j' is selected from at least one of Ba, sr, Y and Ce, u is more than 0 and less than or equal to 0.8,0 and more than or equal to v and less than or equal to 0.8,0 and less than or equal to w and less than or equal to 0.8,0 and less than or equal to omega and less than or equal to 0.8.
4. The multi-element positive electrode material according to claim 1 or 2, wherein the Li is 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ Has a garnet structure; the Li u J v La 2-w J’ w O 4+ω Has a layered perovskite structure.
5. The multi-element positive electrode material according to claim 1, wherein the component of the matrix comprises Li z [(Ni 1-x- y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 ；
Wherein M and M' are each independently selected from at least one of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; z is more than or equal to 0.9 and less than or equal to 1.3,0.001 and less than or equal to 1,0 and less than or equal to 1,0 and more than alpha and less than or equal to 0.1,0 and more than beta and less than or equal to 0.1;
preferably, M and M' are each independently selected from at least one of Al, ba, zr, ti, nb, Y, W, sr, cr, mo, la, ce, mg and B; z is more than or equal to 1.0 and less than or equal to 1.1,0.001 and less than or equal to 0.5,0 and less than or equal to y and less than or equal to 0.5,0, alpha is more than or equal to 0.05,0, beta is more than or equal to 0.05.
6. The multi-element cathode material according to claim 5, wherein Li in XRD of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak intensity of crystal face I (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak intensity of crystal face I (003) The ratio of 0.01% < I (422) /I (003) < 1.2%, preferably, 0.1% < I (422) /I (003) ＜0.5％；
And/or Li in XRD (X-ray diffraction) of the multi-element cathode material 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ (422) Peak area of crystal face A (422) With Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (003) Peak area of crystal plane A (003) The ratio of 0.01% < A (422) /A (003) < 1.2%, preferably, 0.1% < A (422 /A (003) ＜0.5％。
7. The multi-element positive electrode material according to any one of claims 1 to 4, wherein the multi-element positive electrode material has an average particle diameter D 50 2-30 μm; preferably 3 to 20 μm;
and/or the thickness of the fast ion conductor coating layer is 2-30nm; preferably 3-15nm;
and/or the mass ratio of the fast ion conductor coating layer to the matrix is (0.01-5): 100, preferably 0.05 to 1% by mass.
8. The preparation method of the multielement cathode material is characterized by comprising the following steps of:
(1) Preparing a mixed salt solution from cobalt salt, manganese salt and nickel salt according to the molar ratio of Ni to Co to Mn = (1-x-y) to x to y;
(2) Contacting the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution for coprecipitation reaction to obtain solid-liquid mixed slurry; filtering, washing, drying and screening the solid-liquid mixed slurry to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-component material precursor, the lithium source and the compound of the M' source to obtain a multi-component anode material matrix;
(4) A first process is adopted: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω Mixing the mixture with the multi-element anode material matrix, and performing first sintering, crushing and screening to obtain a fast ion conductor coated multi-element anode material;
alternatively, the first and second electrodes may be,
adopting a second process: mixing Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ And mixing the lanthanum source, the J source compound, the J' source compound and the lithium salt with the multi-element positive electrode material matrix, and performing second sintering, crushing and screening to obtain the fast ion conductor coated multi-element positive electrode material.
9. The preparation method according to claim 8, wherein the concentration of the mixed salt solution is 1 to 3mol/L, the concentration of the precipitant solution is 1 to 15mol/L, the concentration of the complexing agent solution is 1 to 15mol/L, and the concentration of the M-source salt solution is 0.01 to 1mol/L;
and/or the M source is used in an amount of 0 < [ n (M) ]/[ n (Ni) + n (Co) + n (Mn) ] < 0.1;
preferably, the M source is used in an amount such that 0.001 ≦ n (M) ]/[ n (Ni) + n (Co) + n (Mn) ] ≦ 0.05;
and/or, the compounds of said M source and said M' source are selected from compounds of at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B;
and/or the salt solution of the M source is a water-soluble salt of the M source, preferably at least one of sodium metaaluminate, barium nitrate, zirconium chloride, titanium sulfate, niobium nitrate, tantalum nitrate, gallium nitrate, yttrium nitrate, ammonium tungstate, calcium chloride, lanthanum nitrate, cerium nitrate, magnesium nitrate and sodium borate.
10. The production method according to claim 8, wherein the particle diameter D of the multi-component positive electrode material precursor 50 Is 1-30 μm, preferably 3-20 μm;
and/or, in step (2), the conditions of the coprecipitation reaction include: the pH value is 10-13, the reaction temperature is 40-70 ℃, and the reaction time is 5-20h.
11. The production method according to claim 8, wherein the lithium source is used in an amount of 0.90. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) + n (M) ]. Ltoreq.1.30 in a molar ratio;
and/or, the M 'source is added according to the molar ratio of 0 < n (M')/[ n (Ni) + n (Co) + n (Mn) ] < 0.1;
preferably, the M 'source is used in an amount such that 0.001. Ltoreq. N (M')/[ n (Ni) + n (Co) + n (Mn) ]. Ltoreq.0.05;
and/or, the compound of the M 'source is selected from at least one of an oxide of the M' source, a hydroxide of the M 'source, and a carbonate of the M' source.
12. The production method according to claim 8, wherein, in the step (3), the expression of the matrix of the multi-component positive electrode material is Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 (ii) a Z is more than or equal to 0.9 and less than or equal to 1.3,0.001 and less than or equal to 1,0 and less than or equal to y and less than or equal to 1,0, alpha is more than or equal to 0.1,0, beta is more than or equal to 0.1; preferably, 1.0 ≦ z ≦ 1.1,0.001 ≦ x ≦ 0.5,0 ≦ y ≦ 0.5,0 < α ≦ 0.05,0 < β ≦ 0.05;
and/or, the Li 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ The dosage of the lead-free acid is more than or equal to 0.1 percent and less than or equal to m (Li) according to the mass ratio 7-i A i La 3-j A’ j Zr 2-q A” q O 12+δ )/m{Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 Adding the component in an amount less than or equal to 5 percent;
and/or, the Li u J v La 2-w J’ w O 4+ω The dosage of the lead-free lithium ion battery is more than or equal to 0.1 percent and less than or equal to m (Li) according to the mass ratio u J v La 2-w J’ w O 4+ω )/m{Li z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 Adding the component in an amount less than or equal to 5 percent;
and/or, in the step (4), the lithium salt is added according to the molar ratio of 0 ≦ n (Li)/[ n (J) + n (J') ] ≦ 2;
and/or the lanthanum source is added according to the molar ratio of n (La)/n (J) which is more than or equal to 2 and less than or equal to 6;
and/or the dosage of the J source is more than or equal to 0.1 percent and m (J source)/m { Li [% ] according to the mass ratio z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 5% or less;
and/or the dosage of the J 'source is more than or equal to 0.1 percent and more than or equal to m (J' source)/m { Li% z [(Ni 1-x-y Co x Mn y ) 1-α M α ] 1-β M’ β O 2 Adding the component in an amount less than or equal to 5 percent;
and/or, the J source is at least one element compound selected from Al, ni, co, cu and Fe;
and/or, the J source compound is selected from at least one of an oxide of the J source, a hydroxide of the J source and a carbonate of the J source;
and/or, the J' source is at least one element compound selected from Ca, ba, sr, Y, ce, rb and Ru;
and/or, the compound of the J 'source is selected from at least one of an oxide of the J' source, a hydroxide of the J 'source and a carbonate of the J' source.
13. The production method according to claim 8, wherein in step (4), the conditions of the first sintering and the second sintering are the same or different, each including: the sintering temperature is 650-1000 ℃, preferably 800-950 ℃; the sintering time is 4-20h, preferably 6-15h;
and/or the sintering temperature rise rate in the first sintering is 3-10 ℃/min, preferably 4-6 ℃/min;
and/or the sintering temperature rise rate in the second sintering is 0.5-2 ℃/min, preferably 0.8-1.5 ℃/min.
14. The production method according to claim 8 or 11, wherein the compound of M' source, li 7-i A i La 3-j A’ j Zr 2- q A” q O 12+δ 、Li u J v La 2-w J’ w O 4+ω The compound of the J source, and D of the compound of the J' source 50 Less than 200nm, and specific surface area greater than 20m 2 /g；
Preferably, D 50 10-150nm, and 50-500m of specific surface area 2 /g。
15. A multi-element positive electrode material produced by the production method according to any one of claims 8 to 14.
16. A lithium ion battery, characterized in that it comprises as a positive electrode material the multielement positive electrode material according to any of claims 1-7 and 15.
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