CN117594783B - Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof - Google Patents
Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN117594783B CN117594783B CN202410072980.XA CN202410072980A CN117594783B CN 117594783 B CN117594783 B CN 117594783B CN 202410072980 A CN202410072980 A CN 202410072980A CN 117594783 B CN117594783 B CN 117594783B
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- Prior art keywords
- lithium
- manganese
- positive electrode
- rich manganese
- electrode material
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 149
- 239000011572 manganese Substances 0.000 title claims abstract description 113
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 94
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010416 ion conductor Substances 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000002243 precursor Substances 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 238000005303 weighing Methods 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- -1 manganese salt compound Chemical class 0.000 claims description 21
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000975 co-precipitation Methods 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 13
- 229940044175 cobalt sulfate Drugs 0.000 claims description 13
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 229940099596 manganese sulfate Drugs 0.000 claims description 13
- 239000011702 manganese sulphate Substances 0.000 claims description 13
- 235000007079 manganese sulphate Nutrition 0.000 claims description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 13
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910016581 MnaCobNic Inorganic materials 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 229910017488 Cu K Inorganic materials 0.000 claims description 2
- 229910017541 Cu-K Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 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
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-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
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 44
- 238000005056 compaction Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 229940053662 nickel sulfate Drugs 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
- 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
-
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
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- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
-
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- C01G33/00—Compounds of niobium
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- 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
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C01P2006/10—Solid density
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Abstract
The invention relates to a lithium ion battery, in particular to a layered composite lithium-rich manganese-based positive electrode material, and a preparation method and application thereof. The positive electrode material comprises a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix. The invention can improve the compaction density and the circulation stability of the material, obviously improve the multiplying power performance and effectively inhibit the oxygen precipitation.
Description
Technical Field
The invention relates to a lithium ion battery, in particular to a layered composite lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
The lithium ion battery anode material with high energy density, high safety and low cost is a key for realizing the sustainable development of the novel lithium ion battery. The lithium-rich positive electrode material generally has higher specific capacity (> 250 mAh/g), higher voltage platform (> 3.6V), better thermal stability and safety, lower cost and no great pollution or harm to the environment, and becomes a next generation novel lithium ion battery positive electrode material with great development potential. However, the lithium-rich material still has the problems of fast capacity fade, low compaction density, oxygen release and the like, which hinders the commercialization application of the lithium-rich cathode material. The single crystal structure generally has higher crystallinity and lattice integrity and fewer grain boundaries and defects, and can inhibit particle breakage during pole piece mixing, improve energy density of the battery and inhibit generation of particle microcracks during circulation.
Currently, single crystal anodes mainly have two modes, namely high-temperature synthesis and molten salt synthesis, the high temperature can increase the grain growth speed, but can lead to increased volatilization of lithium salt, and additional lithium salt is required to be added to counteract the volatilization, and grinding and cleaning and annealing are required to reduce agglomeration. The molten salt synthesis is mainly based on a dissolution-recrystallization mechanism, the growth of micron-sized grains can be realized at a lower temperature, and chloride salt, chlorate, ferrous chloride and the like are added as auxiliary agents in the mixing process of a lithium-rich precursor and a lithium source, for example, peroxyacetic acid is adopted as the auxiliary agent in Chinese patent CN109537054A to obtain the monocrystal lithium-rich manganese-based anode material. Conventional methods using additives usually require a large amount of additives, and require complicated process flows, and have high production cost and high cost.
However, the monocrystalline lithium-rich manganese-based material still has the technical problems of larger grain size, poor multiplying power performance, lattice oxygen release and the like, and the monocrystalline lithium-rich manganese-based material needs to be subjected to surface modification to improve the performance. For example, the Chinese patent CN114094080A adopts Co 3O4 as an additive to prepare the single crystal lithium-rich layered-spinel composite cathode material, so that the single crystal rate performance is improved.
The manganese-based cathode material is still to be further improved.
Disclosure of Invention
The present invention aims to solve, at least to some extent, one of the technical problems in the prior art, or at least to provide a commercial choice.
The invention firstly provides a layered composite lithium-rich manganese-based positive electrode material, which comprises the following components: a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix;
The molecular formula of the lithium-rich manganese-based matrix is Li xMnaCobNicO2; x is more than 1 and less than or equal to 1.3,0.4 and less than or equal to a is less than or equal to 0.8, b is more than 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5;
The molecular formula of the oxygen ion conductor is A αBβOγ; alpha is more than or equal to 0.5 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 0.4, alpha+beta is more than or equal to 1 and gamma is more than or equal to 1 and less than or equal to 2, wherein element A is at least one of Ce, zr and Bi, and element B is at least one of Cs, mo, dy, Y, nb, ba, la, al, ca, rb, sr.
The molecular formula of the layered composite lithium-rich manganese-based positive electrode material can be expressed as Li xMnaCobNicO2@AαBβOγ.
In the layered composite lithium-rich manganese-based positive electrode material, the oxygen ion conductor has oxygen ion storage and migration characteristics, and the oxygen ion conductor is coated on the surface of the lithium-rich manganese-based material, so that the release of lithium-rich lattice oxygen can be effectively inhibited, and the multiplying power performance of the material is improved. The lithium-rich manganese-based material coated by the oxygen ion conductor is in a single crystal shape, the crystallinity of single crystal particles is higher, the surface is more stable, the specific surface area is smaller, the compaction density and the circulation stability of the material can be improved, and the oxygen precipitation can be effectively inhibited.
Further, x=1.18, a=0.52, b=0.15, c=0.15, α=0.9, β=0.1, γ=1.9.
Further, x=1.18, a=0.52, b=0.15, c=0.15, α=0.8, β=0.2, γ=1.9.
Further, in the oxygen ion conductor, the element A is one of Ce and Zr, and the element B is one of Cs, mo, dy, Y, nb.
Further, in the layered composite lithium-rich manganese-based positive electrode material, the oxygen ion conductor is coated on the surface of the lithium-rich manganese-based substrate.
Further, in the layered composite lithium-rich manganese-based positive electrode material, the molar ratio of the lithium-rich manganese-based matrix to the oxygen ion conductor is 1000:1-30, for example, 1000:1, 1000:5, 1000:10, 1000:15, 1000:20, 1000:25, 1000:30.
Further, the oxygen ion conductor has a specific structure, the space group is Fm-3m, and diffraction peaks are arranged at angles of 25 and 35 when the Cu-K alpha is adopted as an incident light source for carrying out X-ray powder diffraction test.
Further, the microstructure of the layered composite lithium-rich manganese-based positive electrode material is single crystal particles, and the median particle diameter (D50) is 0.1um-10um, for example 0.1um, 0.5um, 1um, 1.5um, 1.8um, 2um, 2.5um, 3um, 3.5um, 3.8um, 4um, 4.5um, 5um, 6um, 7um, 8um, 9um, 10um.
The invention also provides a preparation method of the layered composite lithium-rich manganese-based positive electrode material, which comprises the following steps:
Weighing a manganese salt compound, a cobalt salt compound and a nickel salt compound according to the stoichiometric ratio of the lithium-rich manganese-based matrix, and dissolving the manganese salt compound, the cobalt salt compound and the nickel salt compound in deionized water to obtain a metal salt solution; dissolving a precipitator in deionized water to obtain a precipitator solution; uniformly mixing the metal salt solution and the precipitant solution, reacting at 50-60 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
According to the stoichiometric ratio of the oxygen ion conductor, dissolving the compound of the element A and the compound of the element B into a solvent to obtain a first solution, wherein the solvent is one of deionized water, ethanol and acetone;
Uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, and evaporating to dryness to obtain a modified precursor;
And uniformly mixing the modified precursor with a lithium source according to the stoichiometric ratio of the layered composite lithium-rich manganese-based anode material, and calcining under an oxygen-containing atmosphere to obtain the layered composite lithium-rich manganese-based anode material.
Specifically, the manganese salt compound is selected from at least one of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate; the cobalt salt compound is at least one selected from cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate; the nickel salt compound is selected from at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
Specifically, the concentration of the metal salt solution is 0.5-2mol/L.
Specifically, the precipitant is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
Specifically, at least one of the compounds Ce(NO3)3、CeCl3、Ce(SO4)3、Zr(NO3)4、ZrCl4、Zr(SO4)4、Bi(NO3)3、BiCl3 of element a; the compound of the element B is at least one of a Y, cs, ba, la, dy, al, mo, nb, ca, rb, sr-containing soluble sulfate, nitrate or chloride salt.
Specifically, the solvent comprises one of deionized water, ethanol and acetone.
Specifically, the manganese cobalt nickel coprecipitation precursor is added to the first solution and then mixed (e.g., stirred).
Specifically, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride or lithium acetate.
Specifically, the calcination conditions are: heating to 200-600 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 4-24 h; then heating to 600-1000 ℃ at a heating rate of 0.5-10 ℃/min, and calcining for 6-40 h.
Specifically, the method further comprises the step of cooling (to room temperature) after calcination.
The invention also comprises the layered composite lithium-rich manganese-based positive electrode material prepared by the method.
The invention also comprises application of the layered composite lithium-rich manganese-based positive electrode material in a lithium ion battery.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the layered composite lithium-rich manganese-based positive electrode material.
According to the preparation method, the precursor is modified, the compound containing the elements A and B is introduced, and the monocrystalline lithium-rich manganese-based positive electrode material coated by the oxygen ion conductor can be directly obtained through sintering, so that the monocrystalline lithium-rich material coated by the oxygen ion conductor with the Fm-3m space group is formed in situ, meanwhile, the compaction density and the circulation stability of the material are improved, the multiplying power performance is obviously improved, and the oxygen precipitation is effectively inhibited. The compound containing the elements A and B adopted by the invention has extremely small dosage and no need of subsequent washing and purification, can directly form the oxygen ion conductor with oxygen ion storage and migration characteristics, has simple process and low equipment requirements, is efficient and is convenient for batch amplification and industrialized production. The synthesized monocrystal lithium-rich material prepared by the method has good particle dispersibility, uniform particles and controllable size.
Drawings
Fig. 1 is an SEM image of a layered composite lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention.
Fig. 3 is an SEM image of a conventional polycrystalline morphology lithium-rich material prepared according to comparative example 1 of the present invention.
Fig. 4 is an XRD pattern of a conventional polycrystalline morphology lithium-rich material prepared according to comparative example 1 of the present invention.
Fig. 5 is an SEM image of the modified polycrystalline lithium-rich material prepared in comparative example 2 according to the present invention.
Fig. 6 is an XRD pattern of the modified polycrystalline lithium-rich material prepared in comparative example 2 in the present invention.
Fig. 7 is an SEM image of the modified polycrystalline lithium-rich material prepared in comparative example 3 in the present invention.
Fig. 8 is an XRD pattern of the modified polycrystalline lithium-rich material prepared in comparative example 3 in the present invention.
Fig. 9 is an SEM image of the layered composite lithium-rich manganese-based positive electrode material prepared in example 2 of the present invention.
Fig. 10 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 2 of the present invention.
Fig. 11 is an SEM image of the layered composite lithium-rich manganese-based positive electrode material prepared in example 3 of the present invention.
Fig. 12 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 3 of the present invention.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce0.9Cs0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
(2) Dissolving Ce (NO 3)3 and CsNO 3 in deionized water to obtain a first solution, uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, evaporating to dryness, and drying to obtain a modified precursor, wherein the molar ratio of the manganese cobalt nickel coprecipitation precursor to Ce (NO 3)3 and CsNO 3 is 1000:9:1);
(3) And uniformly mixing the modified precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, heating to 550 ℃ at a heating rate of 3 ℃/min after mixing, continuously heating to 900 ℃ at the same heating rate after heat preservation for 5 hours, and carrying out heat preservation for 12 hours, wherein the sintering process is carried out in an air atmosphere, and cooling to room temperature to obtain the layered composite lithium-rich manganese-based positive electrode material.
Preparing a lithium ion battery: mixing the layered composite lithium-rich manganese-based positive electrode material prepared in the embodiment 1, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, uniformly coating the slurry on the surface of an aluminum foil sheet to obtain a positive electrode sheet, and assembling the positive electrode sheet in a glove box by taking a lithium sheet as a negative electrode sheet and taking 1mol/L of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1:1) as electrolyte.
Comparative example 1
A conventional polycrystalline morphology lithium-rich material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
(2) And weighing a manganese cobalt nickel coprecipitation precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the polycrystalline lithium-rich material Li 1.18Mn0.52Co0.15Ni0.15O2.
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the conventional polycrystalline morphology lithium-rich material prepared in comparative example 1, and a lithium ion battery was prepared in the same manner as in example 1.
Comparative example 2
A modified polycrystalline lithium-rich material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce1.0O1.9.
The preparation method comprises the following steps: (1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) And (3) respectively weighing the precursor and Ce (NO 3)3 into deionized water according to the molar ratio of 1000:10, uniformly stirring, evaporating to dryness, drying to obtain a modified precursor P1, (3) weighing the modified precursor and lithium carbonate (calculated by lithium) according to the molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the modified precursor.
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the modified polycrystalline lithium-rich material prepared in comparative example 2, and a lithium ion battery was prepared in the same manner as in example 1.
Comparative example 3
The modified polycrystalline lithium-rich material Li 1.18Mn0.52Co0.15Ni0.15O2@Cs1.0O1.9 comprises the following specific steps: (1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) according to a molar ratio of 1000: and (10) respectively weighing the precursor and Cs (NO 3)3, adding into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1, (3) weighing the modified precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, and cooling to room temperature in an air atmosphere in the sintering process to obtain the modified precursor.
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the modified polycrystalline lithium-rich material prepared in comparative example 3, and a lithium ion battery was prepared in the same manner as in example 1.
Example 2
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Zr0.9Mo0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The preparation method comprises the steps of (1) weighing and adding a precursor and Zr (NO 3)4 and Mo (NO 3)3) into ethanol according to a molar ratio of 1000:18:2, stirring uniformly, evaporating to dryness, drying to obtain a modified precursor P1, (3) weighing and adding the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, heating to 550 ℃ at a heating rate of 3 ℃/min after uniform mixing, heating to 900 ℃ after heat preservation for 5 hours, continuously heating to the same heating rate, and heating to heat preservation for 12 hours, wherein a sintering process is carried out in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with a matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and an oxygen ion conductor Zr 0.9Mo0.1O1.9 coated on the surface.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 2, a lithium ion battery was prepared in the same manner as in example 1.
Example 3
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce0.8Dy0.2O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The preparation method comprises the steps of (1) weighing and adding a precursor and Ce (NO 3)3 and Dy (NO 3)3) into acetone according to a molar ratio of 1000:8:2, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1, (3) weighing and uniformly mixing the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, heating to 550 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, continuously heating to 900 ℃ at the same heating rate, preserving heat for 12 hours, performing sintering in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with a matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and an oxygen ion conductor Ce 0.8Dy0.2O1.9 coated on the surface.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 3, a lithium ion battery was prepared in the same manner as in example 1.
Example 4
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Zr0.9Y0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The preparation method comprises the steps of (1) weighing and adding a precursor and Zr (NO 3)4 and Y (NO 3)3) into deionized water according to a molar ratio of 1000:9:1, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1, (3) weighing and adding the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing sintering in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with a matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and an oxygen ion conductor Zr 0.9Y0.1O1.9 coated on the surface.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 4, a lithium ion battery was prepared in the same manner as in example 1.
Example 5
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Zr0.9Nb0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The preparation method comprises the steps of (1) weighing and adding a precursor and Zr (NO 3)4 and Nb (NO 3)3) into deionized water according to a molar ratio of 1000:9:1, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1, (3) weighing and uniformly mixing the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, heating to 550 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, continuously heating to 900 ℃ at the same heating rate, preserving heat for 12 hours, performing sintering in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with a matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and an oxygen ion conductor Zr 0.9Nb0.1O1.9 coated on the surface.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 5, a lithium ion battery was prepared in the same manner as in example 1.
Example 6
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce0.9Nb0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The preparation method comprises the steps of (1) weighing and adding a precursor and Ce (NO 3)3 and Nb (NO 3)3) into deionized water according to a molar ratio of 1000:9:1, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1, (3) weighing and adding the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing sintering in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with a matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and an oxygen ion conductor Ce 0.9Nb0.1O1.9 coated on the surface.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 6, a lithium ion battery was prepared in the same manner as in example 1.
Example 7
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce0.9Cs0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The precursor is mixed with Ce 2（SO4)3 and Cs 2SO4 according to a molar ratio of 2000:9:1, weighing and adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) And (3) weighing the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with the matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and the surface coated with the oxygen ion conductor Ce 0.9Cs0.1O1.9.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 7, a lithium ion battery was prepared in the same manner as in example 1.
Example 8
A layered composite lithium-rich manganese-based positive electrode material has a molecular formula of Li 1.18Mn0.52Co0.15Ni0.15O2@Ce0.9Cs0.1O1.9.
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The precursor, ceCl 3 and CsCl are weighed according to the mol ratio of 1000:9:1 and added into deionized water, and the mixture is stirred uniformly, evaporated to dryness and dried to obtain a modified precursor P1; (3) And (3) weighing the modified precursor P1 and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the single crystal lithium-rich manganese-based positive electrode material with the matrix of Li 1.18Mn0.52Co0.15Ni0.15O2 and the surface coated with the oxygen ion conductor Ce 0.9Cs0.1O1.9.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 8, a lithium ion battery was prepared in the same manner as in example 1.
Experiment 1
The microcosmic morphology of the lithium-rich materials of examples 1 to 3 and comparative examples 1 to 2 was tested using a scanning electron microscope and X-ray powder diffraction was performed using Cu-kα as an incident light source. SEM and XRD patterns are shown in fig. 1-10, respectively.
As can be seen from the scanning electron microscope photograph of FIG. 1, the lithium-rich material obtained in example 1 has a single crystal morphology, uniform particle distribution, smooth surface and a particle size D50 of 3.8 um. As can be seen from the X-ray diffraction pattern of FIG. 2, the diffraction peaks of the material of example 1 can be marked as lamellar phases, and have characteristic peaks of lithium-rich materials and characteristic peaks of Fm-3m space groups of oxygen ion conductors.
As can be seen from the scanning electron microscope photograph of FIG. 3, the lithium-rich material of comparative example 1 has a polycrystalline morphology, and the phenomenon that particles are agglomerated into spheres is obvious. As can be seen from the X-ray diffraction pattern of fig. 4, the diffraction peaks of the lithium-rich material of comparative example 1 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material. As can be seen from comparative example 1, only a lithium-rich manganese-based material having a polycrystalline morphology can be obtained without any treatment.
As can be seen from the scanning electron microscope photograph of FIG. 5, the lithium-rich material of comparative example 2 has a polycrystalline morphology, the phenomenon that particles are agglomerated into spheres is obvious, and the size is in the nanometer scale. As can be seen from the X-ray diffraction pattern of fig. 6, the diffraction peaks of the lithium-rich material of comparative example 2 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material.
As can be seen from the scanning electron microscope photograph of FIG. 7, the lithium-rich material of comparative example 3 has a polycrystalline morphology, and the phenomenon that particles are agglomerated into spheres is obvious, and the size is in the nanometer scale. As can be seen from the X-ray diffraction pattern of fig. 8, the diffraction peaks of the lithium-rich material of comparative example 3 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material.
As is clear from comparative examples 2 and 3, no surface-coated lithium-rich single crystal positive electrode material could be obtained by adding only either element A or element B.
As can be seen from the scanning electron microscope photograph of FIG. 9, the lithium-rich material obtained in example 2 has a single crystal morphology, uniform particle distribution, smooth surface and a particle size D50 of 1.8 um. As can be seen from the X-ray diffraction pattern of fig. 10, the diffraction peaks of the lithium-rich material of example 2 can be marked as lamellar phases, having characteristic peaks of the lithium-rich material and characteristic peaks of Fm-3m space group.
As can be seen from the SEM photograph of FIG. 11, the lithium-rich material obtained in example 3 has a single crystal morphology, uniform particle distribution, smooth surface and a particle size D50 of 2.0 um. As can be seen from the X-ray diffraction chart of fig. 12, the diffraction peak of the lithium-rich material of example 3 can be marked as a lamellar phase, and has a characteristic peak of the lithium-rich material and a characteristic peak of Fm-3m space group.
Experiment 2
Electrochemical performance tests were performed on the lithium ion batteries of examples 1 to 8 and comparative examples 1 to 3 using an electrochemical tester. The test temperature was 25 ℃. The battery was tested for its initial charge and discharge performance at a current density of 0.1C (1c=200 mA/g) and a charge voltage range of 4.8 to 2V. The detailed results are shown in Table 1.
TABLE 1
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A layered composite lithium-rich manganese-based positive electrode material, characterized by comprising: a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix;
The molecular formula of the lithium-rich manganese-based matrix is Li xMnaCobNicO2; x is more than 1 and less than or equal to 1.3,0.4 and less than or equal to a is less than or equal to 0.8, b is more than 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5;
The molecular formula of the oxygen ion conductor is A αBβOγ; alpha is more than or equal to 0.5 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 0.4, alpha+beta is more than or equal to 1 and gamma is more than or equal to 1 and less than or equal to 2, wherein element A is at least one of Ce, zr and Bi, and element B is at least one of Cs, mo, dy, Y, nb, ba, la, al, ca, rb, sr;
the space group of the oxygen ion conductor is Fm-3m; when the Cu-K alpha is adopted as an incident light source for X-ray powder diffraction test, diffraction peaks are arranged at angles 25 and 35; the layered composite lithium-rich manganese-based positive electrode material has a microstructure of single crystal particles, and the median particle diameter is 0.1um-10um.
2. The layered composite lithium-rich manganese-based positive electrode material according to claim 1, wherein x=1.18, a=0.52, b=0.15, c=0.15, α=0.9, β=0.1, γ=1.9;
or x=1.18, a=0.52, b=0.15, c=0.15, α=0.8, β=0.2, γ=1.9.
3. The layered composite lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein in the layered composite lithium-rich manganese-based positive electrode material, the molar ratio of the lithium-rich manganese-based matrix to the oxygen ion conductor is 1000:1-30.
4. The layered composite lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein in the oxygen ion conductor, element a is one of Ce and Zr, and element B is one of Cs, mo, dy, Y, nb.
5. The method for preparing the layered composite lithium-rich manganese-based positive electrode material according to any one of claims 1 to 4, comprising the steps of:
Weighing a manganese salt compound, a cobalt salt compound and a nickel salt compound according to the stoichiometric ratio of the lithium-rich manganese-based matrix, and dissolving the manganese salt compound, the cobalt salt compound and the nickel salt compound in deionized water to obtain a metal salt solution; dissolving a precipitator in deionized water to obtain a precipitator solution; uniformly mixing the metal salt solution and the precipitant solution, reacting at 50-60 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
According to the stoichiometric ratio of the oxygen ion conductor, dissolving the compound of the element A and the compound of the element B into a solvent to obtain a first solution, wherein the solvent is one of deionized water, ethanol and acetone;
Uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, and evaporating to dryness to obtain a modified precursor;
And uniformly mixing the modified precursor with a lithium source according to the stoichiometric ratio of the layered composite lithium-rich manganese-based anode material, and calcining under an oxygen-containing atmosphere to obtain the layered composite lithium-rich manganese-based anode material.
6. The method for preparing a layered composite lithium-rich manganese-based positive electrode material according to claim 5, wherein the manganese salt compound is at least one selected from manganese sulfate, manganese chloride, manganese acetate and manganese nitrate; the cobalt salt compound is at least one selected from cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate; the nickel salt compound is at least one selected from nickel sulfate, nickel chloride, nickel acetate or nickel nitrate; and/or the number of the groups of groups,
The precipitant is at least one of sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide; and/or the number of the groups of groups,
At least one of the compounds Ce(NO3)3、CeCl3、Ce(SO4)3、Zr(NO3)4、ZrCl4、Zr(SO4)4、Bi(NO3)3、BiCl3 of element a; the compound of the element B is at least one of a Y, cs, ba, la, dy, al, mo, nb, ca, rb, sr-containing soluble sulfate, nitrate or chloride salt.
7. The method for preparing a layered composite lithium-rich manganese-based positive electrode material according to claim 5 or 6, wherein the calcination conditions are: heating to 200-600 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 4-24 h; then heating to 600-1000 ℃ at a heating rate of 0.5-10 ℃/min, and calcining for 6-40 h.
8. A layered composite lithium-rich manganese-based positive electrode material, characterized by being prepared by the method of any one of claims 5 to 7.
9. Use of the layered composite lithium-rich manganese-based positive electrode material according to any one of claims 1-4 and 8 in lithium ion batteries.
10. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the layered composite lithium-rich manganese-based positive electrode material of any one of claims 1-4, 8.
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