CN116553620A - High-entropy spinel oxide material and preparation method and application thereof - Google Patents
High-entropy spinel oxide material and preparation method and application thereof Download PDFInfo
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- CN116553620A CN116553620A CN202310424330.2A CN202310424330A CN116553620A CN 116553620 A CN116553620 A CN 116553620A CN 202310424330 A CN202310424330 A CN 202310424330A CN 116553620 A CN116553620 A CN 116553620A
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- salt
- oxide
- spinel
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- lithium
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 81
- 239000011029 spinel Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910018584 Mn 2-x O 4 Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- OMUZBRHGBVLFHZ-UHFFFAOYSA-L dilithium 2-hydroxy-2-oxoacetate hydroxide Chemical compound [OH-].[Li+].C(C(=O)O)(=O)[O-].[Li+] OMUZBRHGBVLFHZ-UHFFFAOYSA-L 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 150000003681 vanadium Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940090961 chromium dioxide Drugs 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 claims description 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- UPXYJUPSYMBDCO-UHFFFAOYSA-L magnesium;diacetate;hydrate Chemical compound O.[Mg+2].CC([O-])=O.CC([O-])=O UPXYJUPSYMBDCO-UHFFFAOYSA-L 0.000 claims description 2
- YISKQXFNIWWETM-UHFFFAOYSA-N magnesium;dinitrate;hydrate Chemical compound O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YISKQXFNIWWETM-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 8
- 229910015645 LiMn Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052566 spinel group Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/54—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]-, e.g. Li(CoxMn2-x)04, Li(MyCoxMn2-x-y)O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-entropy spinel oxide material, a preparation method and application thereof. The chemical formula of the material is LiA x Mn 2‑x O 4 The element A is a doping element and contains more than five of Li, mg, al, ti, V, cr, fe, co, ni, cu and Zn, wherein the value of x is 0.05-0.15; the single doping element accounts for 0.5-2% of the total atomic number of all doping elements and manganese elements in terms of atomic percentage. The material is used as the positive electrode of a lithium ion batteryThe active material still has excellent rate performance and cycle stability during rapid charge and discharge, compared with commercial LiMn 2 O 4 The high-entropy spinel has remarkable advantage in rate performance, can meet the requirements of the positive electrode material of the rapid charge-discharge battery under the rate of 10 ℃, realizes the construction of the rapid charge-discharge battery, and has important industrial application value.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials and electrochemistry, and particularly relates to a high-entropy spinel oxide material, a preparation method and application thereof.
Background
Increasing the charge and discharge rate is critical to the practical application of the battery. On the one hand, the specific energy of the current single battery is difficult to meet the endurance requirement, and the charging rate is improved, so that the disadvantage of insufficient endurance can be overcome, and the charging efficiency can be improved. On the other hand, the emerging fields such as smart grids, rail transit, ejection systems, aviation systems, high-orientation energy storage devices and the like require the energy storage battery to have the capability of discharging in a short time and high power, and super-capacitors or flywheels are commonly adopted in the fields to store energy at present, and compared with the battery, the super-capacitors have low energy density, the flywheels require larger space and have low energy conversion efficiency. Therefore, the development of the battery capable of being charged and discharged at a high speed has a wide application prospect.
The common lithium ion battery increases charge and discharge current, so that polarization is enhanced, heating is increased, and capacity is reduced. The lithium ion battery with the quick charge performance is required to have more than 80% of capacity at 0.1C rate under high rate, and in theory, the quick charge lithium ion battery can be fully charged with 80% of electric quantity only for 40 min. And the battery is required to run at a rate of 5C or more by the rapid charge and discharge, which means that the battery is charged or discharged once for less than 15 minutes. The extremely rapid charge and discharge will bring about a revolutionary shift in the application of power cells.
The extremely rapid charge and discharge not only brings great challenges to the design of the battery module, but also brings higher requirements on the conductivity of the electrode material. The low ionic conductivity is a common cause of impeding the rapid charge and discharge performance of electrode materials. For common commercial cathode materials, olivine-type LiFePO 4 Only one-dimensional lithium ion channels but have poor characteristicsRate capability of layered LiCoO 2 And LiNi x Co y Mn 1-x-y O 2 The lithium ion battery has the potential of rapid charge and discharge due to the special two-dimensional lithium ion channel structure. However, if the positive electrode material is to have a higher ion mobility without changing the ion diffusion path length by nanocrystallization in order to realize a rapid charge and discharge, it is necessary to design a diffusion channel of a higher dimension. Although LiMn 2 O 4 Spinel has more excellent rate performance due to the three-dimensional ion diffusion channel, however, a large gap remains between realizing the rapid charge and discharge. Thus, how to modify LiMn 2 O 4 Spinel is a challenging task for meeting the requirements of the anode material for rapid charge and discharge, and has practical guiding significance for constructing the rapid charge and discharge battery.
Disclosure of Invention
The invention aims to provide a high-entropy spinel oxide material, a preparation method and application thereof, and a spinel oxide with doping sites having element high-entropy characteristics is constructed for the first time, and when the spinel oxide material is used as a lithium ion battery positive electrode active material, the spinel oxide material has excellent rate capability, and can meet the requirement of a 10C rate positive electrode material of a rapid charge and discharge battery.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
provides a spinel oxide material with high entropy, the chemical formula is LiA x Mn 2-x O 4 The element A is a doping element and contains more than five of Li, mg, al, ti, V, cr, fe, co, ni, cu and Zn, wherein the value of x is 0.05-0.15; the single doping element accounts for 0.5-2% of the total atomic number of all doping elements and manganese elements in terms of atomic percentage.
According to the scheme, the grain size of the high-entropy spinel oxide is 0.5-3 mu m, and the morphology is octahedral or truncated octahedral.
The invention also provides a preparation method of the high-entropy spinel oxide material, which comprises the following steps:
1) Mixing a lithium source, a manganese source and salt containing doping elements; wherein the salt containing doping elements is a combination of at least five salts containing different doping elements;
2) And (3) pre-sintering the mixture obtained in the step (1) at 400-600 ℃, then mixing the powder again, and then re-sintering the mixture at 850-950 ℃ to obtain the high-entropy spinel oxide material.
According to the above scheme, in the step 1), the lithium source is one of lithium carbonate, lithium hydroxide hydrate or lithium oxalate hydrate.
According to the above scheme, in the step 1), the manganese salt is one of manganese dioxide, manganous oxide and manganese carbonate.
According to the above scheme, in the step 1), the salt containing the doping element is selected from at least five of lithium salt, magnesium salt, aluminum salt, titanium salt, vanadium salt, chromium salt, ferric salt, cobalt salt, nickel salt, copper salt and zinc salt.
Preferably, the lithium salt is lithium carbonate, lithium hydroxide hydrate or lithium oxalate hydrate; the magnesium salt is magnesium oxide, magnesium acetate hydrate or magnesium nitrate hydrate; the aluminum salt is aluminum oxide or hydrated aluminum nitrate; the titanium salt is titanium dioxide; the vanadium salt is vanadium pentoxide; the chromium salt is chromium oxide, chromium dioxide or hydrated chromium nitrate; the ferric salt is ferric oxide, ferroferric oxide or hydrated ferric nitrate; cobalt salt is cobaltosic oxide, hydrated cobalt acetate or hydrated cobalt nitrate; the nickel salt is nickel oxide, hydrated nickel acetate or hydrated nickel nitrate; the copper salt is copper oxide, hydrated copper nitrate or hydrated copper acetate; the zinc salt is zinc oxide, zinc nitrate hydrate or zinc acetate hydrate.
According to the scheme, the molar ratio of the lithium source to the manganese source to the salt containing the doping element is (1.02-1.05): 2-x: x, wherein x ranges from 0.05 to 0.15.
According to the scheme, in the salt containing the doping elements, each doping element accounts for 0.5-2% of the total of all doping elements and manganese atoms in the manganese source in atom percent.
According to the scheme, in the step 2), the presintering time is 2-6h.
According to the scheme, in the step 2), the sintering time is 10-20h.
The invention also provides application of the high-entropy spinel oxide material as an anode active material of a lithium ion battery capable of being charged and discharged at a high speed.
According to the scheme, the extremely rapid charge and discharge means that the capacity of the battery for charge and discharge at the rate of 10C reaches more than 80% of that of 0.1C, which means that the time for completing one charge or discharge of the battery is less than 6min.
The positive electrode of the lithium ion battery capable of being charged and discharged at a high speed comprises a positive electrode active material, wherein the positive electrode active material is the high-entropy spinel oxide material.
The positive electrode of the battery is the positive electrode of the lithium ion battery capable of being charged and discharged at a high speed.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention obtains the spinel oxide LiA with high entropy for the first time x Mn 2-x O 4 More than 5 elements exist in the Mn structure doping site, which is favorable for the shrinkage of cubic cells and improves the covalency of Mn-O, thereby having stable three-dimensional lithium ion diffusion channel in cell deformation caused by charge and discharge, and not only improving LiMn 2 O 4 The cycling stability of the anode material improves the charge-discharge capacity under high multiplying power more obviously; when used as a positive electrode active material of a lithium ion battery, the composite material still has excellent rate performance and cycle stability in rapid charge and discharge, compared with commercial LiMn 2 O 4 The high-entropy spinel has remarkable advantage in rate performance, can meet the requirements of the positive electrode material of the rapid charge-discharge battery under the rate of 10 ℃, realizes the construction of the rapid charge-discharge battery, and has important industrial application value.
2. The invention provides a preparation method of high-entropy spinel oxide, which adopts a solid phase method, has simple process and easy implementation, can obtain the high-entropy spinel oxide with regular morphology and uniform size, and is beneficial to industrial application.
Drawings
Fig. 1 is an XRD pattern of the high entropy spinel prepared in example 1.
Fig. 2 is an SEM image of the high entropy spinel prepared in example 1.
FIG. 3 is an EDS mapping graph of the high entropy spinel prepared in example 1.
FIG. 4 is a high entropy spinel (HE-LMO) prepared in example 1 and a commercial spinel LiMn 2 O 4 (LMO) comparison of first-turn charge-discharge curves.
FIG. 5 is a high entropy spinel and commercial spinel LiMn prepared in example 1 2 O 4 Comparison of rate capability.
FIG. 6 is a high entropy spinel and commercial spinel LiMn prepared in example 1 2 O 4 Comparison of cycle performance at 10C magnification.
FIG. 7 is a high entropy spinel (B) prepared in example 1 and a commercial spinel LiMn 2 O 4 (A) And a comparison graph (C) of the calculated lithium ion diffusion coefficient.
Fig. 8 is a plot of unit cell parameter changes (a) for the high entropy spinel, other single element doped spinels and commercial spinels prepared in example 1 and corresponding capacity performance at 10C magnification (B).
FIG. 9 is a commercial spinel LiMn 2 O 4 Low-power cross-section STEM and high-power HAADF STEM figures after 500 cycles at 10C magnification.
Fig. 10 is a low-power cross-sectional STEM plot and a high-power HAADF STEM plot of the high-entropy spinel prepared in example 1 after 500 cycles at 10C magnification.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
Providing a high entropy spinel oxide prepared by the steps of:
1) 1.922g Li is weighed 2 CO 3 ，10.92g MnCO 3 ，0.2g Cu(CH 3 COO) 2 ·H 2 O，0.214g Mg(CH 3 COO) 2 ·4H 2 O，0.22g Zn(CH 3 COO) 2 ·2H 2 O，0.404g Fe(NO 3 ) 3 ·9H 2 O,0.075g NiO, ball milling for 12h and mixing uniformly.
2) Presintering the mixture obtained in the last step at 500 ℃ for 5 hours, performing secondary ball milling on the presintered powder for 3 hours, and sintering at 900 ℃ for 16 hours to obtain the high-entropy spinel oxide material, wherein the chemical formula of the high-entropy spinel oxide is Li [ Cu ] 0.02 Mg 0.02 Fe 0.02 Zn 0.02 Ni 0.02 ]Mn 1.9 O 4 。
For the product of this example, the chemical formula is Li [ Cu ] 0.02 Mg 0.02 Fe 0.02 Zn 0.02 Ni 0.02 ]Mn 1.9 O 4 The test was performed with the high entropy spinel of (2) as follows:
FIG. 1 is an XRD pattern of the high entropy spinel prepared in this example, showing that the material is spinel crystal structure, belonging to Fd-3m space group, with some reduction in unit cell parameters due to multiple doping.
FIG. 2 is a Scanning Electron Microscope (SEM) of the high entropy spinel prepared in this example, showing that the synthesized oxide particles range in size from 0.5 μm to 3 μm and are octahedral or truncated octahedral-like in morphology.
FIG. 3 is a mapping graph of the EDS elements of the high entropy spinel prepared in this example, showing a uniform distribution of Mn, cu, mg, fe, zn, ni, O, which also shows the above multi-cation doping into the crystal interior, forming the high entropy spinel.
The high-entropy spinel oxide prepared in the embodiment is used as a positive electrode active material of a lithium ion battery and assembled into a button cell, and the specific operation method comprises the following steps: mixing the above manganese-based layered oxide material with a vacancy-ordered superstructure with a carbon black conductive agent and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 9:0.5:0.5 mixing uniformly and dispersing in N-methylpyrrolidone (NMP) and stirring to form a slurry, uniformly coating the slurry on aluminum foil, drying and cutting into electrode sheets, and mixing with lithium sheets, a diaphragm and electrolyte (1 mol/L LiPF 6 The dissolution volume ratio is 1:1: 1) together to form a button cell, and performing constant current charge and discharge test on the button cell.
FIG. 4 shows the high entropy of the preparation of this exampleSpinel (HE-LMO) and commercial spinel LiMn 2 O 4 A first charge-discharge curve of (LMO). The first charge and discharge can be carried out, and the LMO can obtain 127.3mAhg -1 And a specific charge capacity of 117.4mAhg -1 The initial coulomb efficiency is 93.8%; the first-turn charge specific capacity of HE-LMO is 120.5mAhg -1 Specific discharge capacity of 117.5mAhg -1 The initial ring coulomb efficiency of HE-LMO is 97.5% higher than that of LMO, which indicates that HE-LMO has improved reversibility during charge and discharge. Both LMO and HE-LMO have similar dual platforms, which demonstrates that both have the same structure and are defined by Mn 3.5+/4+ Provides charge compensation. But the HE-LMO discharge plateau voltage is higher because there is less ion diffusion energy barrier in the HE-LMO and the polarization of the cell is reduced. The slopes of the two voltage platforms of 4V and 4.14V are slightly increased, and the transition between the platforms is smoother, which indicates that the high-entropy element inhibits Li in the charge and discharge process + And ordered rearrangements between Li vacancies.
FIG. 5 is a high entropy spinel (HE-LMO) and commercial spinel LiMn prepared in this example 2 O 4 Rate capability of (LMO). With the continuous increase of the multiplying power, the difference between the capacity of HE-LMO and the LMO is larger and larger. At a 10C rate, 94mAh g can be obtained by HE-LMO -1 While LMO has only 47.9mAh g -1 Only half of HE-LMO. When HE-LMO is used as a positive electrode active material of a lithium ion battery, the HE-LMO has 117.3mAh g respectively under the multiplying power of 0.1C and 10C -1 And 94mAh g -1 Is significantly higher than commercial LiMn at a capacity of 80.1% at a capacity of 0.1C at a rate of 10C 2 O 4 The spinel positive electrode material (39.3%) shows that the material can meet the requirements of the electrode material of the rapid charge and discharge battery.
FIG. 6 is a high entropy spinel (HE-LMO) and commercial spinel LiMn prepared in this example 2 O 4 (LMO) cycle performance at 1C and 10C rates, respectively. The circulation is carried out for 150 times under the 1C multiplying power, the capacity retention rate of the LMO is only 69.4 percent, and the capacity retention rate of the HE-LMO reaches 93 percent. Cycling 350 times at 10C rate, HE-LMO still provides 79.8mAh g -1 And LMO has a capacity of only 55.5mAh g -1 Is a function of the capacity of the battery. Thus, HE-LMO is superior to commercial LMO cathode materials, both in terms of lower cycle stability and in terms of rate capability up to 10C.
FIG. 7 shows the high entropy spinel and commercial spinel LiMn prepared in this example 2 O 4 And the lithium ion diffusion coefficient is calculated based on constant current intermittent titration test. As the charging process proceeds, the commercial spinel LiMn 2 O 4 The lithium ion diffusion coefficient of (2) significantly decreases when delithiation exceeds 0.65. While the diffusion fluctuations in the high entropy spinel are smaller. Therefore, lithium diffusion at a stable high voltage is a fundamental cause for improving the rate capability of the material.
Fig. 8 shows the change in unit cell parameters and the corresponding capacity performance at 10C magnification for the high entropy spinel and the other doped spinels and commercial spinels prepared in this example. The original unit cell of the high entropy spinel is contracted to the greatest extent, and at the same time, the more excellent the performance at 10C magnification is. Only the high entropy spinel has a capacity of more than 80% at 10C rate compared to the commercial spinel and other mode doped spinels, which suggests that only the high entropy spinel prepared in this example can serve as a very fast charge positive electrode material in these materials.
FIG. 9 is a commercial spinel LiMn 2 O 4 Characterization of the structure after 500 cycles at 10C magnification. Commercial spinel LiMn 2 O 4 At this time, serious structural deterioration has occurred, and a large number of surface cracks and intra-crystal cracks occur due to the formation of a large number of crystal faults. This is because, when the degree of progress of delithiation is relatively large, collapse of the commercial spinel structure occurs, and the formation of these crystal face defects is caused by repeated severe cell deformation, which results in blockage of the original three-dimensional lithium ion diffusion channel inside the spinel, thereby affecting the intrinsic diffusion efficiency thereof.
Fig. 10 is a structural characterization of the high entropy spinel prepared in this example after 500 cycles at 10C magnification. The structure of the high-entropy spinel can still be kept complete under the working condition of 500 times of heavy current, so that the original three-dimensional lithium ion diffusion channel in the interior can be well preserved, and lithium ion diffusion can be stably carried out in the high-entropy spinel, and the high-entropy spinel is brought by larger original cell shrinkage caused by the introduction of a plurality of elements.
Example 2
A high entropy spinel oxide prepared by the steps of:
1) Weigh 3.844g Li 2 CO 3 ，16.5186g MnO 2 ，0.1591g CuO，0.0806g MgO，0.1628g ZnO，0.1597g Fe 2 O 3 ，0.1597g TiO 2 Ball milling is carried out for 12 hours and mixing is uniform.
2) Presintering the mixture obtained in the last step at 550 ℃ for 6 hours, performing secondary ball milling on the presintered powder for 2 hours, and sintering at 950 ℃ for 10 hours to obtain the material with the chemical formula of Li [ Cu ] 0.02 Mg 0.02 Fe 0.02 Zn 0.02 Ti 0.02 ]Mn 1.9 O 4 Is a high entropy spinel oxide material.
Example 3
A high entropy spinel oxide prepared by the steps of:
1) Weigh 3.844g Li 2 CO 3 ，16.5186g MnO 2 ，0.051g Al 2 O 3 ，0.2728g V 2 O 5 ，0.228g Cr 2 O 3 ，0.1605g Co 3 O 4 ，0.08g TiO 2 Ball milling is carried out for 12 hours and mixing is uniform.
2) Presintering the mixture obtained in the last step at 450 ℃ for 3 hours, performing secondary ball milling on the presintered powder for 4 hours, and then sintering at 920 ℃ for 20 hours to obtain the material with the chemical formula of Li [ Al ] 0.01 Ti 0.01 V 0.03 Cr 0.03 Co 0.02 ]Mn 1.9 O 4 Is a high entropy spinel oxide material.
Example 4
A high entropy spinel oxide prepared by the steps of:
1) Weigh 3.844g Li 2 CO 3 ，16.084g MnO 2 ，0.0796g CuO，0.0403g MgO，0.0814g ZnO，0.1065g Fe 2 O 3 ，0.1494g NiO，0.08g TiO 2 ，0.051g Al 2 O 3 ，0.182g V 2 O 5 ，0.152g Cr 2 O 3 ，0.1605g Co 3 O 4 Ball milling is carried out for 12 hours and mixing is uniform.
2) Presintering the mixture obtained in the last step at 550 ℃ for 5 hours, performing secondary ball milling on the presintered powder for 3.5 hours, and sintering at 850 ℃ for 18 hours to obtain the powder with the chemical formula of Li [ Cu ] 0.01 Mg 0.01 Fe 0.02 Ni 0.02 Zn 0.01 Al 0.01 Ti 0.01 V 0.02 Cr 0.0 2 Co 0.02 ]Mn 1.9 O 4 Is a high entropy spinel oxide material.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (10)
1. A spinel oxide material with high entropy is characterized by having a chemical formula of LiA x Mn 2-x O 4 The element A is a doping element and contains more than five of Li, mg, al, ti, V, cr, fe, co, ni, cu and Zn, wherein the value of x is 0.05-0.15; the single doping element accounts for 0.5-2% of the total atomic number of all doping elements and manganese elements in terms of atomic percentage.
2. The high entropy spinel oxide material according to claim 1, wherein the particle size of the high entropy spinel oxide material is 0.5-3 μm and the morphology is octahedral or truncated octahedral-like.
3. A method of preparing the high entropy spinel oxide material of claim 1, comprising the steps of:
1) Mixing a lithium source, a manganese source and salt containing doping elements; wherein the salt containing doping elements is a combination of at least five salts containing different doping elements;
2) And (3) pre-sintering the mixture obtained in the step (1) at 400-600 ℃, then mixing the powder again, and then re-sintering the mixture at 850-950 ℃ to obtain the high-entropy spinel oxide material.
4. The method according to claim 3, wherein in the step 1),
the lithium source is one of lithium carbonate, lithium hydroxide hydrate or lithium oxalate hydrate;
the manganese salt is one of manganese dioxide, manganous oxide, manganese oxide and manganese carbonate;
the salt containing doping element is selected from at least five of lithium salt, magnesium salt, aluminum salt, titanium salt, vanadium salt, chromium salt, ferric salt, cobalt salt, nickel salt, copper salt and zinc salt.
5. The method according to claim 4, wherein the lithium salt is lithium carbonate, lithium hydroxide hydrate or lithium oxalate hydrate; the magnesium salt is magnesium oxide, magnesium acetate hydrate or magnesium nitrate hydrate; the aluminum salt is aluminum oxide or hydrated aluminum nitrate; the titanium salt is titanium dioxide; the vanadium salt is vanadium pentoxide; the chromium salt is chromium oxide, chromium dioxide or hydrated chromium nitrate; the ferric salt is ferric oxide, ferroferric oxide or hydrated ferric nitrate; cobalt salt is cobaltosic oxide, hydrated cobalt acetate or hydrated cobalt nitrate; the nickel salt is nickel oxide, hydrated nickel acetate or hydrated nickel nitrate; the copper salt is copper oxide, hydrated copper nitrate or hydrated copper acetate; the zinc salt is zinc oxide, zinc nitrate hydrate or zinc acetate hydrate.
6. A method according to claim 3, wherein the molar ratio of the lithium source, the manganese source and the salt containing the doping element is (1.02-1.05): 2-x: x, wherein x ranges from 0.05 to 0.15; in the salt containing doping elements, each doping element accounts for 0.5-2% of the total of all doping elements and manganese atoms in the manganese source in atom percent.
7. The method according to claim 3, wherein in the step 2), the pre-sintering time is 2 to 6 hours; the sintering time is 10-20h.
8. Use of the high entropy spinel oxide material according to claim 1 as a positive active material for lithium ion batteries with rapid charge and discharge.
9. A positive electrode of a lithium ion battery capable of being charged and discharged at a high speed, comprising a positive electrode active material, wherein the positive electrode active material is the high-entropy spinel oxide material according to claim 1.
10. A lithium ion battery capable of being charged and discharged at a high speed, comprising the positive electrode according to claim 9.
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