CN113422033A - Yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material, preparation method and application - Google Patents
Yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material, preparation method and application Download PDFInfo
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- CN113422033A CN113422033A CN202110799580.5A CN202110799580A CN113422033A CN 113422033 A CN113422033 A CN 113422033A CN 202110799580 A CN202110799580 A CN 202110799580A CN 113422033 A CN113422033 A CN 113422033A
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- 239000011572 manganese Substances 0.000 title claims abstract description 65
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 Yttrium ion Chemical class 0.000 title claims abstract description 40
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000002641 lithium Chemical class 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000002243 precursor Substances 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 49
- 238000000975 co-precipitation Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 239000008139 complexing agent Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 22
- 239000012716 precipitator Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 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 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910014093 LiMn1/3Ni1/3Co1/3 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 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
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000009766 low-temperature sintering Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 2
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 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 abstract description 16
- 230000008569 process Effects 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Abstract
The invention relates to a yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material, a preparation method and application, and belongs to the field of preparation of lithium-rich manganese-based positive electrode materials. The preparation method comprises the steps of preparing a carbonate precursor containing three elements of nickel, cobalt and manganese through a coprecipitation reaction, uniformly mixing the carbonate precursor and a doping element-containing Y compound, dispersing the mixture in absolute ethyl alcohol, drying the mixture to obtain powder, then uniformly grinding and mixing the powder and a lithium compound, and calcining the mixture to obtain the lithium-rich manganese-based positive electrode material. According to the invention, yttrium ions are doped in the layered lithium-rich manganese, so that doping of yttrium ions in a transition metal layer is realized, strong Y-O bonds can effectively stabilize lattice oxygen, and a uniform yttrium oxide coating layer is coated on the surface of the yttrium-rich manganese, so that the stability of a crystal structure of the layered lithium-rich manganese oxide anode material in a circulation process can be effectively improved through synergistic modification, the loss of lattice oxygen is relieved, the surface of the material and the side reaction of electrolyte are effectively inhibited, and thus the capacity/voltage attenuation in the circulation process is effectively inhibited.
Description
Technical Field
The invention relates to the field of preparation of lithium-rich manganese-based cathode materials, in particular to a yttrium-doped yttrium oxide-coated lithium-rich manganese-based cathode material and a preparation method and application thereof.
Background
With the increasing demand for energy and the continuous and deep understanding of the importance of social and economic sustainable development, lithium ion batteries featuring high energy, high efficiency and environmental protection are receiving more and more attention. The rapid development of pure electric vehicles and plug-in hybrid electric vehicles puts higher requirements on the energy density, the cycle life and the like of lithium ion batteries, and the anode material is the most critical part for determining the performance of the lithium ion batteries. And the LiCoO is applied in the current market2、LiNi1/ 3Co1/3Mn1/3O2The specific capacity of the layered oxide anode material is always limited within 150 mAh/g. Spinel structure LiMn2O4Cathode material and polyanionic LiFePO4The theoretical specific capacity of the anode material is only 148mAh/g and 170mAh/g respectively, the actual capacity is lower, and the performance requirement of the high-specific energy density lithium ion battery on the anode material can not be met. Therefore, development of a positive electrode material having high specific energy and stable cyclability is a focus of research in the future.
The layered lithium-rich manganese-based oxide positive electrode has high capacity (more than 250mAh/g), low cost and good safety, and is taken as a main material of a next-generation power battery. However, the practical application of the layered lithium-rich manganese oxide positive electrode material is severely restricted by the problems of poor cycle stability and rate capability, severe voltage attenuation and the like. Irreversible lattice oxygen loss and side reactions at the electrode/electrolyte interface are the root causes of capacity/voltage fade during cycling of the layered lithium-rich manganese oxide positive electrode material. Oxyanion redox contains reversible redox (O) species in bulk2-→O2 n–) And irreversible lattice oxygen loss (O) from the surface2-→O2). Irreversible lattice oxygen loss induces irreversible transition metal loss during cyclingThe problems of capacity reduction, discharge voltage reduction and the like of the cathode material are caused by the migration and the lattice distortion. Ni4+Has higher activity in a high-voltage charging state, induces the side reaction of an electrode/electrolyte interface to occur, and leads the transition metal on the surface of the electrode to be dissolved, irreversibly transferred and structurally distorted. The synergistic effect of electrode/electrolyte interface side reactions and irreversible lattice oxygen loss can exacerbate the capacity fade, discharge voltage drop and reaction kinetics retardation of the positive electrode material. Therefore, the greatest challenge at present is not only to induce redox of oxygen anions, but also to stabilize irreversible lattice oxygen loss caused during redox and to suppress electrode/electrolyte interface side reactions. According to the invention, yttrium ions are doped in the layered lithium-rich manganese, so that doping of yttrium ions in a transition metal layer is realized, strong Y-O bonds can effectively stabilize lattice oxygen, and a uniform yttrium oxide coating layer is coated on the surface of the yttrium-rich manganese, so that the stability of a crystal structure of the layered lithium-rich manganese oxide anode material in a circulation process can be effectively improved through synergistic modification, the loss of lattice oxygen is relieved, and the side reaction of the surface of the material and an electrolyte is effectively inhibited, thereby effectively inhibiting the capacity/voltage attenuation in the circulation process.
Disclosure of Invention
The invention aims to provide a preparation method of a yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material, and the modification method can effectively improve the energy density and cycle life of the layered lithium-rich manganese-based positive electrode material and further promote the industrialization of the layered lithium-rich manganese-based positive electrode material.
In order to achieve the purpose, the invention discloses the following technical contents:
the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material has a chemical formula of xLi2MnO3·(1-x)LiMn1/3Ni1/3Co1/3O2-YyWherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.001 and less than or equal to 0.1 (preferably, y is more than or equal to 0.01 and less than or equal to 0.03); the mass fraction of the yttrium oxide coating layer in the lithium-rich manganese-based composite positive electrode material is 0.1-10 wt% (preferably 1-3 wt%).
A preparation method of a yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material comprises the steps of preparing a carbonate precursor containing three elements of nickel, cobalt and manganese through coprecipitation reaction, uniformly mixing the carbonate precursor and a compound containing a doping element Y with absolute ethyl alcohol, dispersing and drying, grinding and mixing the dried mixture and a lithium compound, grinding and calcining to obtain the lithium-rich manganese-based positive electrode material.
The method specifically comprises the following steps:
(1) preparing a carbonate precursor containing three elements of nickel, cobalt and manganese through coprecipitation reaction: firstly, adding a proper amount of reaction base solution with a certain concentration into a reaction kettle, mixing soluble manganese salt, nickel salt and cobalt salt according to the proportion of (4-8) to (1-4), and dissolving in deionized water to prepare a mixed salt solution; simultaneously pumping the mixed salt solution, the complexing agent and the precipitant into a reaction kettle containing reaction base liquid at a certain stirring speed, controlling the temperature of the reaction kettle to be 40-80 ℃ (preferably 40-60 ℃), controlling the pH value to be 7.0-11.5 (preferably 7.0-9.0), preparing a carbonate coprecipitation precursor through coprecipitation reaction, and washing, filtering and drying the carbonate coprecipitation precursor to obtain a carbonate precursor containing three elements of nickel, cobalt and manganese; the reaction base solution is a solution containing ammonium ions;
(2) and (2) uniformly mixing the carbonate precursor obtained in the step (1) and a compound containing the doping element Y, dispersing the mixture in absolute ethyl alcohol, continuously stirring to uniformly mix the mixture, then placing the mixture in a drying oven to be fully dried to obtain powder, and then grinding and uniformly mixing the powder and a lithium compound with a stoichiometric ratio to obtain a precursor mixture.
(3) And (3) calcining: and (3) placing the precursor mixture obtained in the step (2) into a tubular furnace, calcining, and then naturally cooling to room temperature to obtain the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based anode material, wherein the calcining temperature is 300-950 ℃.
Further, in the step (1), the reaction base solution is an ammonium sulfate solution or an ammonium bicarbonate solution; the soluble manganese salt is at least one of manganese sulfate, manganese nitrate and manganese acetate; the soluble nickel salt is at least one of nickel sulfate, nickel nitrate and nickel acetate; the soluble cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate; the complexing agent is ammonia water; the precipitant is sodium carbonate or sodium bicarbonate.
Further, in the step (1), the concentration of the reaction base solution is 0.01-1.0 mol/L (preferably 0.05-0.2 mol/L), the concentration of the complexing agent is 0.1-5.0 mol/L (preferably 0.5-3 mol/L), and the flow rate of the complexing agent is 0.1-5 mL/min; the concentration of the precipitant is 0.1-5.0 mol/L (preferably 1-3 mol/L); the flow rate of the precipitator is 0.2-6 mL/min; the concentration of the mixed salt solution is 0.1-5.0 mol/L (preferably 1-3 mol/L), and the flow rate of the mixed salt is 0.2-6 mL/min; the molar ratio of the precipitant to the mixed salt is 1:1.
Further, in the step (1), the stirring speed is 500-2000 r/min (preferably 1000-2000 r/min); the coprecipitation reaction time is 1-24 h. Controlling the flow rate of a precipitator and the flow rate of a mixed salt solution and a complexing agent by an online pH automatic control system to ensure that the pH value of a reaction system is 7.0-11.5; and drying the carbonate coprecipitation precursor, namely drying the carbonate coprecipitation precursor obtained by suction filtration in a vacuum drying oven at the temperature of 80-120 ℃ for 5-16 h.
Further, in the step (2), the stirring speed is 400-2000 rpm, the stirring time is 2-8 hours, and the mixture is placed in a drying oven for drying for 5-16 hours at the temperature of 50-120 ℃; the doping element Y compound is at least one of yttrium acetate, yttrium nitrate and yttrium oxide. The mol ratio of the compound containing the doping element Y accounts for 0.1-10% of the mol ratio of the carbonate precursor.
Further, in the step (2), the lithium compound is at least one of lithium hydroxide, lithium carbonate and lithium acetate. And uniformly mixing the dried powder and the lithium compound according to the molar ratio of 1: 1.02-1.5.
Further, in the step (3), the calcination is divided into low-temperature presintering and high-temperature sintering, wherein the low-temperature presintering temperature is 300-600 ℃, and the high-temperature sintering temperature is 700-950 ℃; the low-temperature sintering time is 2-6 h, the heating rate is 2-6 ℃/min, the high-temperature sintering time is 8-18 h, and the heating rate is 2-8 ℃/min. The calcination is completed in a tube furnace, and the atmosphere of the calcination is air or oxygen.
The yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material can be applied to the preparation of a positive electrode piece of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lithium-rich manganese-based anode material realizes doping of yttrium ions in the transition metal layer, and strong Y-O bonds can effectively stabilize lattice oxygen and relieve lattice oxygen loss, so that migration of transition metal ions to a lithium layer in the circulation process of the layered lithium-rich manganese oxide anode material is effectively inhibited, formation of a spinel phase is inhibited, and capacity/voltage attenuation in the circulation process of the layered lithium-rich manganese oxide anode material can be effectively inhibited.
(2) According to the lithium-rich manganese-based positive electrode material, the surface is coated with a uniform yttrium oxide coating layer, so that the side reaction of the material surface and an electrolyte is effectively inhibited, and the capacity/voltage attenuation in the circulation process is effectively inhibited.
(3) The yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material provided by the invention is simple in preparation process and easy to popularize, and is a method for effectively inhibiting capacity attenuation and voltage drop of the lithium-rich manganese-based positive electrode material in a circulation process.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a scanning electron micrograph of a coprecipitation precursor of carbonate according to example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a lithium-rich manganese-based positive electrode product according to example 1 of the present invention;
FIG. 3 is XRD diffraction patterns of the cathode materials prepared in examples 1 and 2 of the present invention and comparative example 1;
FIG. 4 is a TEM image of the Li-rich Mn-based positive electrode product of example 1 of the present invention; wherein (a) is at a scale of 200nm and (b) is at a scale of 20 nm.
FIG. 5 is a graph of cycle performance and voltage drop at 0.5C rate for positive electrode materials prepared in examples 1 and 2 of the present invention and comparative example 1; wherein (a) is the cycle performance and (b) is the voltage drop.
Detailed Description
Example 1
(1) 200mL of 0.1mol/L NH was added to the reaction kettle4HCO3The solution is used as reaction base solution; MnSO (sodium sulfide) as soluble sulfate4·H2O、CoSO4·7H2O、NiSO4·6H2Dissolving O into 500mL of deionized water according to the mol ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.2mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing NH4HCO3In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 7.7, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 16h, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor. FIG. 1 is a scanning electron micrograph of the precursor prepared in example 1. As can be seen from the figure, the precursor synthesized in the reaction system is in a sphere-like shape, the average particle size is about 5 μm, and the size is relatively uniform.
(2) Y is the carbonate precursor with the mol ratio of 1 percent to the carbonate precursor2O3Uniformly mixing and dispersing in 50mL of absolute ethyl alcohol, continuously stirring for 6 hours to uniformly mix, then placing the mixture in a drying box at 80 ℃ to dry for 12 hours to fully dry to obtain powder, and then grinding and uniformly mixing the obtained precursor powder and lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under an air state, preserving heat for 5 hours at 500 ℃, then heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. FIG. 2 is a scanning electron micrograph of the cathode material prepared in example 1, from which it can be seen that the particle size of the baked cathode material is more uniform and the density is more compact than that of the precursorGood results are obtained. Fig. 3 is an XRD diffractogram of the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material prepared in example 1, and compared with a standard card, we can successfully synthesize a lithium-rich manganese-based positive electrode material with a layered structure, which belongs to a hexagonal system, and has a narrow half-peak width and a high peak intensity, indicating that the material has good crystallinity. FIG. 4 is a transmission electron micrograph of the yttrium ion doped yttrium oxide coated lithium-rich manganese-based anode material prepared in example 1, and it can be seen that the surface of the lithium-rich manganese-based anode material is coated with a uniform layer of Y with a thickness of about 4.5nm2O3And (4) coating.
And (2) respectively and uniformly mixing the obtained lithium-manganese-rich positive electrode material with a conductive agent super P and a binder PVDF (polyvinylidene fluoride) according to the mass ratio of 8:1:1, preparing the mixture into slurry by using NMP (1-methyl-2-pyrrolidone), uniformly coating the slurry on an aluminum foil, putting the aluminum foil into a drying oven, drying the aluminum foil for 24 hours at the temperature of 80-120 ℃, taking out the aluminum foil and punching the aluminum foil into a pole piece, thus obtaining the pole piece for the experimental battery. The material is used as an anode, a metal lithium sheet is used as a cathode to assemble a button cell, a charge-discharge test is carried out in a voltage window of 2.0-4.8V, the first discharge specific capacity is 251.4mAh/g under 0.1C multiplying power, and the first coulombic efficiency is 80.64%; FIG. 5 is a graph showing the cycle performance and voltage drop at 0.5C rate of the material prepared and purchased in example 1, and the specific discharge capacity is 156.2mAh/g and the capacity retention rate is 95.4% after 100 cycles at 0.5C rate. After the material is cycled for 200 times under the multiplying power of 0.5C, the voltage drop is 0.87, and the cycle performance and the voltage drop of the material are obviously improved by the double modification of yttrium ion doped yttrium oxide coating.
Example 2
(1) 200mL of 0.1mol/L NH was added to the reaction kettle4HCO3The solution is used as reaction base solution; soluble nitrate salt Mn (NO)3)2·4H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2Dissolving O into 500mL of deionized water according to the molar ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.3mol/L ammonia water is taken as a complexing agent, sodium bicarbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium bicarbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing NH4HCO3In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 7.7, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 16h, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) Y is the carbonate precursor with the mol ratio of 3 percent2O3Uniformly mixing and dispersing in 50mL of absolute ethyl alcohol, continuously stirring for 6 hours to uniformly mix, then placing the mixture in a drying box at 80 ℃ to dry for 12 hours to fully dry to obtain powder, and then grinding and uniformly mixing the obtained precursor powder and lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under an air state, preserving heat for 5 hours at 500 ℃, then heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. Fig. 3 is an XRD diffractogram of the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material prepared in example 2, and compared with a standard card, we can successfully synthesize a lithium-rich manganese-based positive electrode material with a layered structure, which belongs to a hexagonal system, and has a narrow half-peak width and a high peak strength, indicating that the material has good crystallinity.
The obtained lithium-rich cathode material is assembled into a button cell in the same way as in the embodiment 1, the first discharge specific capacity is 245.4mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 81.54 percent. FIG. 5 is a graph showing the cycle performance and voltage drop at 0.5C rate of the material prepared in example 2, wherein after the material is cycled at 0.5C rate for 100 times, the specific discharge capacity is 143.3mAh/g, and the capacity retention rate is 88.4%. After the material is cycled for 200 times under the multiplying power of 0.5C, the voltage drop is 0.68, and the cycle performance and the voltage drop of the material are obviously improved by the double modification of yttrium ion doped yttrium oxide coating.
Example 3
(1) 200mL of 0.3mol/L (NH) solution was added to the reaction vessel4)2SO4The solution is used as reaction base solution; MnSO (sodium sulfide) as soluble sulfate4·H2O、CoSO4·7H2O、NiSO4·6H2Dissolving O into 500mL of deionized water according to the mol ratio of 4:1:1 to prepare a mixed salt solution of 1 mol/L; 0.5mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 1mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing (NH)4)2SO4In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1000rpm, the temperature of the reaction kettle is controlled to be 60 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 8, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is controlled to be 0.5mL/min, the reaction time is 18h, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) Y (NO) in a molar ratio of the obtained carbonate precursor to the carbonate precursor of 1%3)3·6H2And uniformly dispersing the O mixture in 50mL of absolute ethyl alcohol, continuously stirring for 6 hours to uniformly mix the O mixture, then placing the mixture in a drying box at 80 ℃ to dry for 12 hours to fully dry the mixture to obtain powder, and then grinding and uniformly mixing the obtained precursor powder and lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 500 ℃ at the heating rate of 5 ℃/min under the air state, preserving the heat at 500 ℃ for 6 hours, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. The obtained lithium-rich cathode material is assembled into a button cell in the same way as in example 1, the first discharge specific capacity is 255.4mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 82.54%. After the material is cycled for 100 times under the multiplying power of 0.5C, the specific discharge capacity is 157.3mAh/g, and the capacity retention rate is 90.4%. After cycling 200 times at 0.5C rate, the voltage drop was 0.71.
Example 4
(1) 200mL of 0.1mol/L (NH) solution was added to the reaction vessel4)2SO4The solution is used as reaction base solution; dissolving soluble acetate Mn (CH)3COO)2·4H2O、Co(CH3COO)2·4H2O、Ni(CH3COO)2·4H2Dissolving O into 500mL of deionized water according to the molar ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.2mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing (NH)4)2SO4In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 8.5, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 24 hours, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) Y (NO) in a molar ratio of the obtained carbonate precursor to the carbonate precursor of 3%3)3·6H2And uniformly dispersing the O mixture in 50mL of absolute ethyl alcohol, continuously stirring for 6 hours to uniformly mix the O mixture, then placing the mixture in a drying box at 80 ℃ to dry for 12 hours to fully dry the mixture to obtain powder, and then grinding and uniformly mixing the obtained precursor powder and lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 500 ℃ at the heating rate of 5 ℃/min under the air state, preserving the heat at 500 ℃ for 6 hours, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. The obtained lithium-rich cathode material is assembled into a button cell in the same way as in the embodiment 1, the first discharge specific capacity is 248.4mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 81.54 percent. After the material is cycled for 100 times under the multiplying power of 0.5C, the specific discharge capacity is 155.3mAh/g, and the capacity retention rate is 91%. After cycling 200 times at 0.5C rate, the voltage drop was 0.73.
Example 5
(1) 200mL of 0.4mol/L NH was added to the reaction kettle4HCO3The solution is used as reaction base solution; soluble nitrate salt Mn (NO)3)2·4H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2Dissolving O into 500mL of deionized water according to the molar ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.4mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing NH4HCO3In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 7.5, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 24 hours, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) Y (CH) in a molar ratio of the obtained carbonate precursor to the carbonate precursor of 1%3COO)3·4H2And O is uniformly mixed and dispersed in 50mL of absolute ethyl alcohol, stirring is continuously carried out for 6 hours to uniformly mix the O, then the O is placed in a drying box at the temperature of 80 ℃ to be dried for 12 hours to fully dry the O to obtain powder, and then the obtained precursor powder and lithium hydroxide are ground and uniformly mixed according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 550 ℃ at the heating rate of 5 ℃/min under the air state, preserving the heat at 550 ℃ for 6 hours, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. The obtained lithium-rich cathode material is assembled into a button cell in the same way as in the embodiment 1, the first discharge specific capacity is 250.5mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 80.2%. After the lithium ion battery is cycled for 100 times under the multiplying power of 0.5C, the specific discharge capacity is 159.4mAh/g, and the capacity retention rate is 93%. After cycling 200 times at 0.5C rate, the voltage drop was 0.68.
Example 6
(1) 200mL of 0.2mol/L NH was added to the reaction kettle4HCO3The solution is used as reaction base solution; dissolving soluble acetate Mn (CH)3COO)2·4H2O、Co(CH3COO)2·4H2O、Ni(CH3COO)2·4H2Dissolving O into 500mL of deionized water according to the molar ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.2mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing NH4HCO3In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 7.5, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 20 hours, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) Mixing the obtained carbonate precursor with 3 mol% of Y (CH) in the carbonate precursor3COO)3·4H2Mixing O, dispersing in 50mL anhydrous ethanol, stirring for 6 hr, drying at 80 deg.CDrying in a box for 12 hours to obtain powder after full drying, and then grinding and uniformly mixing the precursor powder and the lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 550 ℃ at the heating rate of 5 ℃/min under the air state, preserving the heat at 550 ℃ for 6 hours, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the yttrium ion doped yttrium oxide coated lithium-rich manganese-based positive electrode material. The obtained lithium-rich cathode material is assembled into a button cell in the same way as in the embodiment 1, the first discharge specific capacity is 248.3mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 79.2%. After the material is cycled for 100 times under the multiplying power of 0.5C, the specific discharge capacity is 154.4mAh/g, and the capacity retention rate is 90.5%. After cycling 200 times at 0.5C rate, the voltage drop was 0.65.
Comparative example 1
(1) 200mL of 0.1mol/L NH was added to the reaction kettle4HCO3The solution is used as reaction base solution; MnSO (sodium sulfide) as soluble sulfate4·H2O、CoSO4·7H2O、NiSO4·6H2Dissolving O into 500mL of deionized water according to the mol ratio of 4:1:1 to prepare a mixed salt solution of 2 mol/L; 0.2mol/L ammonia water is taken as a complexing agent, sodium carbonate is dissolved in 500mL deionized water to prepare 2mol/L sodium carbonate solution which is taken as a precipitator, and the three are simultaneously pumped into a solution containing NH4HCO3In a reaction kettle for reacting the base solution, the stirring speed is controlled to be 1200rpm, the temperature of the reaction kettle is controlled to be 55 ℃, the flow rate of a precipitator is controlled to be 0.5mL/min by an online pH automatic control system, the pH value of a reaction system is controlled to be 7.7, the flow rate of a mixed salt solution is controlled to be 0.5mL/min, the flow rate of a complexing agent is 0.5mL/min, the reaction time is 16h, and a carbonate coprecipitation precursor is prepared through coprecipitation reaction. And washing and filtering the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel-cobalt-manganese-containing ternary carbonate coprecipitation precursor.
(2) And grinding and uniformly mixing the obtained carbonate precursor and lithium hydroxide according to the molar ratio of 1: 1.5.
(3) And (3) transferring the material obtained in the step (2) into a tubular furnace, heating to 500 ℃ at the heating rate of 5 ℃/min under the air state, preserving the heat at 500 ℃ for 5 hours, then heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 12 hours, naturally cooling to room temperature, grinding, and sieving to obtain the lithium-rich manganese-based cathode material in the comparative example 1. Fig. 3 is an XRD diffractogram of the lithium-rich manganese-based positive electrode material prepared in comparative example 1, which belongs to a lithium-rich manganese-based positive electrode material with a hexagonal system and a layered structure, and it can be known from comparison of example 1 that the Y element in the synthesis method of our invention is uniformly doped into the lattice of the material, thereby ensuring the homogeneity of the material.
The obtained lithium-rich cathode material is assembled into a button cell in the same way as in the embodiment 1, the first discharge specific capacity is 235.4mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency is 70.54%. FIG. 5 is a graph showing the cycle performance and voltage drop at 0.5C rate of the material prepared in comparative example 1, and the specific discharge capacity is 99.8mAh/g and the capacity retention rate is only 58.7% after the material is cycled at 0.5C rate for 100 times. After cycling 200 times at 0.5C rate, the voltage drop was 0.99.
Table 1 is a table of electrochemical performance test data of lithium-rich materials prepared according to different embodiments of the present invention
As can be seen from table 1, the electrochemical performance of the lithium-rich manganese-based positive electrode material after the double modification is obviously improved, because the strong Y-O bond can effectively stabilize lattice oxygen and alleviate lattice oxygen loss, the migration of transition metal ions to a lithium layer in the circulation process of the layered lithium-rich manganese oxide positive electrode material is effectively inhibited, the formation of a spinel phase is inhibited, and the capacity/voltage attenuation in the circulation process of the layered lithium-rich manganese oxide positive electrode material can be effectively inhibited. And the yttrium oxide coating layer with uniform surface can effectively inhibit the side reaction of the material surface and the electrolyte, thereby effectively inhibiting the capacity/voltage attenuation in the circulating process.
Claims (10)
1. The yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material is characterized in that the chemical formula of the lithium-rich manganese-based positive electrode material is xLi2MnO3·(1-x)LiMn1/3Ni1/3Co1/3O2-YyWherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.001 and less than or equal to 0.1; the mass fraction of the yttrium oxide coating layer in the lithium-rich manganese-based composite positive electrode material is 0.1-10 wt%.
2. The preparation method of the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material of claim 1, wherein a carbonate precursor containing three elements of nickel, cobalt and manganese is prepared through a coprecipitation reaction, the carbonate precursor and a compound containing a doping element Y are uniformly mixed and dispersed with absolute ethyl alcohol and dried, the dried mixture is ground and mixed with a lithium compound, and the ground mixture is calcined to prepare the lithium-rich manganese-based positive electrode material.
3. The preparation method of the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material according to claim 2, characterized by comprising the following steps:
(1) preparing a carbonate precursor containing three elements of nickel, cobalt and manganese through coprecipitation reaction: firstly, adding a proper amount of reaction base solution with a certain concentration into a reaction kettle, mixing soluble manganese salt, nickel salt and cobalt salt according to the proportion of (4-8) to (1-4), and dissolving in deionized water to prepare a mixed salt solution; simultaneously pumping the mixed salt solution, the complexing agent and the precipitant into a reaction kettle containing reaction base liquid at a certain stirring speed, controlling the temperature of the reaction kettle to be 40-80 ℃ and the pH value to be 7.0-11.5, preparing a carbonate coprecipitation precursor through coprecipitation reaction, and washing, filtering and drying the carbonate coprecipitation precursor to obtain a carbonate precursor containing three elements of nickel, cobalt and manganese; the reaction base solution is a solution containing ammonium ions;
(2) uniformly mixing the carbonate precursor obtained in the step (1) and a compound containing a doping element Y, dispersing the mixture in absolute ethyl alcohol, continuously stirring to uniformly mix the mixture, then placing the mixture in a drying oven to be fully dried to obtain powder, and then grinding and uniformly mixing the powder and a lithium compound with a stoichiometric ratio to obtain a precursor mixture;
(3) and (3) calcining: and (3) placing the precursor mixture obtained in the step (2) into a tubular furnace, calcining, and naturally cooling to room temperature to obtain the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based anode material, wherein the calcining temperature is 300-950 ℃.
4. The preparation method of the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (1), the reaction base solution is ammonium sulfate solution or ammonium bicarbonate solution; the soluble manganese salt is at least one of manganese sulfate, manganese nitrate and manganese acetate; the soluble nickel salt is at least one of nickel sulfate, nickel nitrate and nickel acetate; the soluble cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate; the complexing agent is ammonia water; the precipitant is sodium carbonate or sodium bicarbonate.
5. The preparation method of the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (1), the concentration of the reaction base solution is 0.01-1.0 mol/L, the concentration of the complexing agent is 0.1-5.0 mol/L, and the flow rate of the complexing agent is 0.1-5 mL/min; the concentration of the precipitator is 0.1-5.0 mol/L; the flow rate of the precipitator is 0.2-6 mL/min; the concentration of the mixed salt solution is 0.1-5.0 mol/L, and the flow rate of the mixed salt is 0.2-6 mL/min; the molar ratio of the precipitant to the mixed salt is 1:1.
6. The preparation method of the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (1), the stirring speed is 500-2000 rpm; the coprecipitation reaction time is 1-24 h; controlling the flow rate of a precipitator and the flow rate of a mixed salt solution and a complexing agent by an online pH automatic control system to ensure that the pH value of a reaction system is 7.0-11.5; and drying the carbonate coprecipitation precursor, namely drying the carbonate coprecipitation precursor obtained by suction filtration in a vacuum drying oven at the temperature of 80-120 ℃ for 5-16 h.
7. The preparation method of the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (2), the stirring speed is 400-2000 rpm, the stirring time is 2-8 h, and the material is dried in a drying oven at 50-120 ℃ for 5-16 h; the doping element Y compound is at least one of yttrium acetate, yttrium nitrate and yttrium oxide; the mol ratio of the compound containing the doping element Y accounts for 0.1-10% of the mol ratio of the carbonate precursor.
8. The method for preparing the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (2), the lithium compound is at least one of lithium hydroxide, lithium carbonate and lithium acetate; and uniformly mixing the dried powder and the lithium compound according to the molar ratio of 1: 1.02-1.5.
9. The preparation method of the yttrium ion doped yttrium oxide coated and modified lithium-rich manganese-based positive electrode material according to claim 2, wherein in the step (3), the calcination is performed by low-temperature pre-sintering and high-temperature sintering, wherein the low-temperature pre-sintering temperature is 300-600 ℃, and the high-temperature sintering temperature is 700-950 ℃; the low-temperature sintering time is 2-6 h, the heating rate is 2-6 ℃/min, the high-temperature sintering time is 8-18 h, and the heating rate is 2-8 ℃/min; the calcination is completed in a tube furnace, and the atmosphere of the calcination is air or oxygen.
10. The application of the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material prepared by the preparation method of claims 2-9, and the yttrium ion doped yttrium oxide coated modified lithium-rich manganese-based positive electrode material is applied to the preparation of a positive electrode plate of a lithium ion battery.
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