CN111732126A - Layered lithium-rich manganese oxide cathode material and preparation method and application thereof - Google Patents
Layered lithium-rich manganese oxide cathode material and preparation method and application thereof Download PDFInfo
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- CN111732126A CN111732126A CN202010707231.1A CN202010707231A CN111732126A CN 111732126 A CN111732126 A CN 111732126A CN 202010707231 A CN202010707231 A CN 202010707231A CN 111732126 A CN111732126 A CN 111732126A
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- positive electrode
- rich manganese
- manganese oxide
- lithium
- ion battery
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- 239000010405 anode material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
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- 238000000498 ball milling Methods 0.000 claims description 9
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- 229910052782 aluminium Inorganic materials 0.000 claims description 7
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- -1 Super P Chemical compound 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000009841 combustion method Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 6
- 229910052596 spinel Inorganic materials 0.000 abstract description 6
- 239000011029 spinel Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 11
- 230000001351 cycling effect Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910010158 Li2MO3 Inorganic materials 0.000 description 8
- 238000005118 spray pyrolysis Methods 0.000 description 8
- 229910018416 Mn0.33O2 Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910013191 LiMO2 Inorganic materials 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 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 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- WVOVLHZWOQJYOB-UHFFFAOYSA-M S(=O)(=O)(OF)[O-].[Li+] Chemical compound S(=O)(=O)(OF)[O-].[Li+] WVOVLHZWOQJYOB-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 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 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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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- 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
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention relates to the field of lithium ion batteries, and discloses a layered lithium-rich manganese oxide positive electrode material for effectively inhibiting voltage attenuation in a circulation process, and a preparation method and application thereof. The preparation method of the layered lithium-rich manganese oxide cathode material comprises the following steps: in the preparation process of the precursor of the layered lithium-rich manganese oxide positive electrode material of the lithium ion battery, the raw material precursor of the modified material is added, and then the layered lithium-rich manganese oxide composite positive electrode material is obtained through high-temperature heat treatment. According to the invention, the Ni element can effectively inhibit the migration of the transition metal element in the circulation process of the layered lithium-rich manganese anode material and inhibit the formation of a spinel phase, so that the capacity/voltage attenuation in the circulation process of the layered lithium-rich manganese anode material is effectively inhibited. The positive electrode and lithium ion battery using the material belong to the technical field of energy materials and energy conversion. The material as the anode material of the lithium ion battery has the advantages of high energy density, good cycle stability and rate capability and the like.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a layered lithium-rich manganese oxide anode material for effectively inhibiting voltage attenuation in a circulation process, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in the fields of portable electronic products, electric vehicles, energy storage power stations, and the like due to their high energy density and other characteristics. The new generation of electronic products put higher demands on the performance of the lithium ion battery, i.e., the lithium ion battery needs to have the characteristics of high power and long cycle life while improving the high energy density. The positive electrode material of a lithium ion battery is one of the key factors for achieving its high energy density. The commercially available and mature positive electrode materials include lithium cobaltate (LiCoO2), lithium nickel manganese cobalt (nimo 2, M ═ Ni, Co, Mn/Al), lithium manganese spinel (LiMn2O4), lithium iron phosphate (LiFePO4), and the like. But the specific capacity of the laminar anode material is always limited within 150 mAmp hour/gram. Spinel-structured LiMn2O4 positive electrode material and polymerThe theoretical specific capacity of the anionic LiFePO4 positive electrode material is only 148 mAmp hour/g and 170 mAmp hour/g respectively, the actual capacity is lower, and the performance requirement of the high-specific energy density lithium ion battery on the positive electrode material can not be met. Therefore, the positive electrode material becomes a bottleneck for further improving the performance of the lithium ion battery. The lithium-rich manganese-based anode material has ultrahigh specific capacity (more than 250 mAh.g)-1) Low cost and high safety, and is concerned by scientists and engineers in all countries of the world.
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, low first coulombic efficiency and the like. The formation of spinel structure caused by the Transition Metal (TM) ion migration and structural rearrangement during the cycling process of the layered lithium-rich manganese oxide cathode material is the root cause of capacity/voltage attenuation. Research reports that an ion doping/substitution method can be generally adopted to improve the structural stability of the layered lithium-rich manganese oxide cathode material and inhibit the phase change of the layered lithium-rich manganese oxide cathode material in the charge and discharge processes, so as to inhibit the capacity/voltage attenuation of the layered lithium-rich manganese oxide cathode material. At present, the common method is to use inactive elements such as Mg, Al, Fe, etc. to perform doping modification on the layered lithium-rich manganese oxide positive electrode material, however, the doping modification of these inactive elements can reduce the electrochemical capacity of the electrode material, and the modification effect is not very obvious.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a layered lithium-rich manganese oxide cathode material, and the modification method can effectively improve the energy density and the cycle life of the layered lithium-rich manganese oxide cathode material and further promote the industrialization of the layered lithium-rich manganese oxide cathode material. The second purpose of the invention is to provide a lithium ion battery anode using the anode material. It is a third object of the present invention to provide a lithium ion battery using the positive electrode.
In order to achieve the first object, the invention adopts the following technical scheme:
a preparation method of a layered lithium-rich manganese oxide cathode material comprises the following steps: in the preparation process of the precursor of the layered lithium-rich manganese oxide positive electrode material of the lithium ion battery, the raw material precursor of metallic nickel is added, and then the layered lithium-rich manganese oxide composite positive electrode material is obtained through high-temperature heat treatment.
The invention also discloses the layered lithium-rich manganese oxide cathode material prepared by the preparation method.
In order to achieve the second object, the invention adopts the following technical scheme:
a lithium ion battery anode is prepared by using the layered lithium-rich manganese oxide anode material as an anode material, mixing the anode material with a conductive agent, carrying out ball milling to obtain a mixture, mixing the mixture with a binder to form a slurry, coating the slurry on an aluminum foil, and drying to obtain the lithium ion battery anode.
In order to achieve the third object, the invention adopts the following technical scheme:
the lithium ion battery comprises a positive electrode, a negative electrode capable of releasing and inserting lithium ions and an electrolyte between the negative electrode and the positive electrode, wherein the positive electrode is the positive electrode of the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modification method has the advantages of simplicity, effectiveness, quickness, low cost, strong controllability, wide application range and the like;
(2) according to the invention, excessive Ni element is added into the layered lithium-rich manganese, and the doping of Ni at Li position is realized by utilizing the ion exchange characteristics of Ni and Li, so that 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, the capacity/voltage attenuation in the circulation process of the layered lithium-rich manganese oxide positive electrode material can be effectively inhibited, and the energy density of the original material is not reduced.
Drawings
FIG. 1 is a comparison of the XRD patterns of the product of example 1 of the present invention;
FIG. 2 is a graph of (a) cycle performance and (b) midpoint voltage decay for the product of example 1 of the present invention;
FIG. 3 is a plot of (a) rate performance versus (b) rate capacity retention for the product of example 1 of the present invention;
FIG. 4 is a graph of (a) cycle performance and (b) midpoint voltage decay for the product of example 2 of this invention;
FIG. 5 is a comparison of the XRD patterns of the product of example 3 of the present invention;
FIG. 6 is a graph of (a) cycle performance and (b) midpoint voltage decay for the product of example 3 of this invention;
FIG. 7 is a graph of the cycle performance of the product of example 4 of the present invention;
FIG. 8 is a midpoint voltage decay curve of the product of example 4 of the present invention;
FIG. 9 is a comparison of the midpoint voltage decay curves for the product of example 5 of the present invention;
FIG. 10 is a comparison of the midpoint voltage decay curves for the product of example 6 of the present invention;
FIG. 11 is a comparison of the midpoint voltage decay curves for the product of example 7 of the present invention;
FIG. 12 is a comparison of the midpoint voltage decay curves for the product of example 8 of the present invention;
FIG. 13 is a cycle performance curve for the product of example 9 of the present invention;
FIG. 14 is a plot of the mid-point discharge voltage cycling performance of the product of example 9 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a layered lithium-rich manganese oxide cathode material, which comprises the following steps: in the preparation process of the precursor of the layered lithium-rich manganese oxide positive electrode material of the lithium ion battery, the raw material precursor of the modified material is added, and then the layered lithium-rich manganese oxide composite positive electrode material is obtained through high-temperature heat treatment.
In the preparation process of the layered lithium-rich manganese oxide positive electrode material of the lithium ion battery, the excessive Ni element precursor is added to regulate and control the structure of the layered lithium-rich manganese oxide positive electrode material, and because the Ni element can effectively inhibit the migration of transition metal elements in the cyclic process of the layered lithium-rich manganese oxide positive electrode material and inhibit the formation of a spinel phase, the capacity/voltage attenuation in the cyclic process of the layered lithium-rich manganese oxide positive electrode material is effectively inhibited. The positive electrode and lithium ion battery using the material belong to the technical field of energy materials and energy conversion. The material as the anode material of the lithium ion battery has the advantages of high energy density, good cycle stability and rate capability and the like. The preparation method of the composite material is simple and suitable for large-scale production.
According to the invention, the layered lithium-rich manganese oxide cathode material is xLi2MnO3-(1-x)LiMO2Wherein M is at least one selected from Ni, Co, Mn, Cr and Fe; 0. ltoreq. x.ltoreq.1, preferably 0.1. ltoreq. x.ltoreq.0.8.
Preferably, x in the layered lithium-rich manganese oxide cathode material is more than or equal to 0.1 and less than or equal to 0.8, and if x is too small or too large, the comprehensive electrochemical performance of the lithium-rich material is reduced, so x is selected within a reasonable range.
Preferably, the modifying material is Ni element.
Preferably, the raw material precursor of the modifying material is added in an amount such that the molar ratio of the doping amount of the metal Ni to the layered lithium-rich manganese oxide positive electrode material is 0.01 to 0.1, preferably 0.01 to 0.06. If the doping amount is too small, the modification effect cannot be achieved; too much doping can affect the structure of the starting material and thus its electrochemical performance.
Preferably, the precursor is prepared by at least one method selected from the group consisting of a spraying method, a coprecipitation method, a sol-gel method, a combustion method, a solid phase method, and a molten salt method. The materials obtained by different preparation methods have different phase structures, component distributions, morphologies, particle sizes and the like, and have important influence on various performances of the electrode material.
Preferably, the raw materials used for the layered lithium-rich manganese oxide cathode material precursor and the raw material precursor of the modification material are each independently selected from at least one of acetate, nitrate, sulfate, carbonate, oxalate, and metal oxide. Different raw materials have different solubilities and melting points, which have important influence on the composition distribution and phase composition of the synthetic material.
Preferably, the temperature of the heat treatment is 600-1000 ℃; the atmosphere of the high-temperature heat treatment is at least one of oxygen, air and vacuum; the heat treatment time is 5-48 hours. The phase structure, the component distribution, the morphology, the particle size and the like of the obtained material are different at different heat treatment temperatures, atmospheres and time, and have important influence on various performances of the electrode material.
The invention also discloses the layered lithium-rich manganese oxide cathode material prepared by adopting any one of the technical schemes.
The invention provides a lithium ion battery anode, which is prepared by taking the layered lithium-rich manganese oxide anode material as a lithium ion battery anode material, mixing the lithium-rich manganese oxide anode material with a conductive agent, carrying out ball milling to obtain a mixture, mixing the mixture and a binder to form slurry, coating the slurry on an aluminum foil, and drying the aluminum foil.
Preferably, the conductive agent is selected from at least one of graphite, acetylene black, Super P, carbon nanotube, graphene, and ketjen black.
Preferably, the content of the conductive agent is 2 wt% to 30 wt% based on the total weight of the paste.
Preferably, during ball milling, the mass ratio of ball materials is 5: 1-300: 1; the rotating speed of the ball mill is 100-800 r/min; the ball milling time is 0.5 to 48 hours; the ball milling atmosphere is selected from at least one of air, oxygen, nitrogen, hydrogen, argon, carbon dioxide and helium.
Preferably, the binder is an aqueous binder or a non-aqueous binder known to those skilled in the art, such as at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTEE), Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC), and Sodium Alginate (SA); based on the total weight of the slurry, the amount of the binder is 1 wt% to 30 wt%.
The third aspect of the present invention provides a lithium ion battery comprising a positive electrode, a negative electrode capable of deintercalating lithium ions, and an electrolyte interposed between the negative electrode and the positive electrode, wherein the positive electrode is the above-mentioned positive electrode of the lithium ion battery.
In the lithium ion battery of the present invention, the negative electrode material may be any of various conventional negative electrode active materials known to those skilled in the art, such as graphite, silicon and various silicon alloys, iron oxide, tin oxide and various tin alloys, titanium oxide, and the like. The electrolyte can adopt a conventional non-aqueous electrolyte commonly known by those skilled in the art, wherein the lithium salt in the electrolyte can be one or more of lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6) and lithium fluorohydroxysulfonate (LiC (SO2CF3) 3). The non-aqueous solvent can be one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC) and Vinylene Carbonate (VC).
The present invention will be described in detail below by way of examples. In the following examples, the examples and comparative examples are all commercially available products.
Example 1
Spray pyrolysis method for preparing excessive Ni-doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material:
adding acetates of Li, Ni, Co and Mn into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel acetate into the reaction solution according to the molar percentage (0, 2, 4,6 mol%) of the added Ni; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is subjected to heat treatment at 900 ℃ for 10 hours to obtain 0.5Li doped with excessive Ni2MnO3-0.5LiNi0.33Co0.33Mn0.33O2The anode materials are respectively marked as Ni-0, Ni-2, Ni-4 and Ni-6.
Mixing the LNCMO-Ni anode material and the binder according to a certain proportion, stirring for 4 hours by adopting magnetic force to obtain uniform slurry, and then uniformly coating the slurry on an aluminum foil to obtain the electrode material. The characterization cell adopts a 2025 button cell, the assembly process is completed in a glove box filled with Ar, and the water and oxygen contents are both less than 0.1 ppm. The positive electrode is the prepared electrode plate; the reference electrode and the counter electrode are metal Li sheets; the septum is Celgard-2400; the electrolyte was LiPF6(1mol/L)/EC + DEC + EMC (1:1:1), and the assembled cell was placed for testing.
FIG. 1 shows XRD patterns of Ni-0, Ni-2, Ni-4, Ni-6 electrode materials. As shown in FIG. 1, all diffraction peaks can be associated with the hexagonal structure of LiMO2(R-3M) (PDF #85-1966) and monoclinic Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. Wherein the diffraction peak between 20 and 25 ° (2 θ) is Li2MO3Characteristic peak of phase is LiTM in Transition Metal (TM) layer in its structure2Ordered superstructures. In the figure, "R" and "M" under the diffraction index represent respectively LiMO of hexagonal structure2And monoclinic structure Li2MO3. The results of the study in chapter five have confirmed that the LNCMO positive electrode material is a hexagonal structure of LiMO2(R-3M) (PDF #85-1966) and monoclinic Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) composite materials dominated by nanoscale interactions. In addition, as can be seen from the XRD chart, the structure of the LNCMO positive electrode material does not change significantly as the Ni content increases.
FIG. 2(a) is a graph showing the cycling performance of Ni-0, Ni-2, Ni-4, Ni-6 electrode materials. As shown in the figure, increasing the Ni element content can effectively improve the cycle performance of the LNCMO positive electrode material. The results show that 200mA g-1Under the current density, the specific capacities of the first discharge of the Ni-0, Ni-2, Ni-4 and Ni-6 electrodes are respectively as follows: 226, 218, 206, 192mAh g-1(ii) a The discharge specific capacities after 150 cycles were respectively: 190, 188, 183, 181mAh g-1(ii) a The discharge capacity retention rates were respectively: 84, 86, 89 and 94 percent. The results show that the LNCMO cathode material is 200mA g-1The discharge specific capacity at current density decreases with increasing Ni content, but the capacity retention ratio thereofIncreasing with increasing Ni content. It can be seen that increasing the Ni content, while reducing the electrochemical capacity of the LNCMO positive electrode material, is effective in improving its cycling stability. Fig. 2(b) shows that increasing the Ni content can increase the discharge midpoint voltage of the LNCMO positive electrode material and can suppress voltage decay during cycling of the LNCMO positive electrode material.
FIG. 3(a) is a rate performance curve of Ni-0, Ni-2, Ni-4, Ni-6 electrode material, and the rate capacity retention at different rates is shown in FIG. 3 (b). The results show that the Ni-0 electrode material shows higher rate capacity below 1C rate, and the charge-discharge rate is higher>At 1C, the Ni electrode material showed a relatively high rate capability. When the high rate is 10C, the discharge rate capacity of the Ni-4 electrode material is 158mAh g-1While the discharge rate capacity of the Ni-0 electrode material is only 130mAh g-1. The results show that increasing the Ni content can improve the high rate performance of the LNCMO cathode material.
Example 2
Spray pyrolysis method for preparing excessive Ni-doped 0.7Li2MnO3-0.3LiNi0.33Co0.33Mn0.33O2(LNCMO-1) a positive electrode material.
Adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel acetate into the reaction solution according to the mole percentage (0, 2, 4,6 mol%) of the added Ni; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is subjected to heat treatment at 900 ℃ for 10 hours to obtain excessive Ni-doped LNCMO-1 cathode materials which are respectively marked as Ni-1-0, Ni-1-2, Ni-1-4 and Ni-1-6.
Electrode material preparation and cell assembly were the same as in example 1.
FIG. 4(a) is a graph showing the cycle performance of the electrode materials Ni-1-0, Ni-1-2, Ni-1-4, and Ni-1-6. As shown in the figure, the increase of the Ni element content can effectively improve the cycle performance of the LNCMO-1 cathode material. 200mA g-1Under the current density, the specific capacities of the first discharge of the Ni-1-0, Ni-1-2, Ni-1-4 and Ni-1-6 electrodes are respectively as follows: 203, 211, 224, 226mAh g-1(ii) a The discharge specific capacities after 150 cycles were respectively: 135,148,169, 190mAh g-1(ii) a The discharge capacity retention rates were respectively: 66.5,70.1,75.4, 84.1%. The results show that the LNCMO cathode material is 200mA g-1The specific discharge capacity under the current density is increased along with the increase of the content of the Ni element, and the capacity retention rate is increased along with the increase of the content of the Ni element.
FIG. 4(b) shows that increasing the Ni content can increase the discharge midpoint voltage of the LNCMO-1 positive electrode material and can suppress the voltage decay during cycling of the LNCMO-1 positive electrode material.
Example 3
Spray pyrolysis method for preparing excessive Ni element doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) Positive electrode Material-nitrate salt
Adding the nitrates of Li, Ni, Co and Mn into a certain amount of deionized water according to the stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel nitrate into the reaction solution according to the additional mole percentage (0, 2, 4,6 mol%) of the Ni element; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is subjected to heat treatment at 900 ℃ for 10 hours to obtain an excess Ni-doped LNCMO cathode material, which is marked as Ni-1-0, Ni-1-2, Ni-1-4 and Ni-1-6 electrodes, and the preparation and the battery assembly of the electrode are the same as those in the embodiment 1.
As shown in FIG. 5, all diffraction peaks can be associated with the hexagonal structure of LiMO2(R-3M) (PDF #85-1966) and monoclinic Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. Wherein the diffraction peak between 20 and 25 ° (2 θ) is Li2MO3Characteristic peak of phase is LiTM in Transition Metal (TM) layer in its structure2Ordered superstructures. In the figure, "R" and "M" under the diffraction index represent respectively LiMO of hexagonal structure2And monoclinic structure Li2MO3. The results of the study in chapter five have confirmed that the LNCMO positive electrode material is a hexagonal structure of LiMO2(R-3M) (PDF #85-1966) and monoclinic Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) composite materials dominated by nanoscale interactions. In addition, as can be seen from the XRD chart, the structure of the LNCMO positive electrode material does not change significantly as the Ni content increases.
FIG. 6(a) is a graph showing the cycle performance of the electrode materials Ni-1-0, Ni-1-2, Ni-1-4, and Ni-1-6. Fig. 6(b) shows that increasing the Ni element content can increase the discharge midpoint voltage of the LNCMO positive electrode material and can suppress voltage decay during cycling of the LNCMO positive electrode material.
Example 4
Spray pyrolysis method for preparing excessive Ni-doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material-different heat treatment temperatures.
Adding the nitrates of Li, Ni, Co and Mn into a certain amount of deionized water according to the stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel nitrate into the reaction solution according to the additional mole percentage (6 mol%) of the Ni element; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. And carrying out heat treatment on the obtained precursor at 400, 500, 600, 700, 800, 900, 1000 and 1100 ℃ for 10 hours to obtain the excess Ni-doped LNCMO cathode material.
Electrode preparation and cell assembly were the same as in example 1.
Fig. 7 is a cycle performance curve of the LNCMO cathode material with different heat treatment temperatures, and the result shows that the heat treatment temperature has a great influence on the cycle stability and the cycle capacity of the LNCMO cathode material. Under the current density of 20 milliampere/gram, after 40 cycles, the specific discharge capacities of the LNCMO anode materials with different heat treatment temperatures are 69.8, 145.9, 182.2, 212.9, 215.3, 277.4, 214.8 and 175.4 milliampere hours/gram respectively; the capacity retention rates were 36.8, 66.9, 77.1, 83.4, 90.6, 96.2, 80.4, 83.3%, respectively. The results show that the LNCMO cathode material obtained by the heat treatment at 900 ℃ has the highest cycle capacity.
Fig. 8 is a midpoint voltage decay curve during cycling for different heat treatment temperatures of the LNCMO cathode material at a current density of 20 ma/g. As can be seen from the curveAs the cycle progresses, the midpoint voltage gradually shifts toward the low potential. The first discharge midpoint voltages of the LNCMO anode material at different heat treatment temperatures are respectively as follows: 3.20, 3.41, 3.57, 3.58, 3.62, 3.66, 3.64, 3.49 volts; after 40 cycles, the midpoint voltage holding ratios are respectively as follows: 76.8, 76.9, 74.7, 77.6, 80.2, 78.6, 78.0, 90.8%. From the data results, it can be seen that the midpoint potential of the LNCMO positive electrode material increases as the temperature increases as a whole from 400 to 900 ℃; the reduction of the midpoint potential at 1000 ℃ and 1100 ℃ is due to LiM in the LNCMO cathode material2O4As a result of spinel phase formation.
Example 5
Spray pyrolysis method for preparing excessive Ni element doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material.
Adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel acetate into the reaction solution according to the mole percentage (6 mol%) of the added Ni element; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. And carrying out heat treatment on the obtained precursor for 10 hours in an oxygen atmosphere at 900 ℃ to obtain the excessive Ni-doped LNCMO cathode material.
Electrode preparation and cell assembly were the same as in example 1.
Fig. 9 shows that increasing the Ni element content can increase the discharge midpoint voltage of the LNCMO positive electrode material and can suppress voltage decay during cycling of the LNCMO positive electrode material.
Example 6
Spray pyrolysis method for preparing excessive Ni element doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material.
Adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then adding nickel acetate into the reaction solution according to the additional mole percentage (6 mol%) of the Ni element; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. And carrying out heat treatment on the obtained precursor for 48 hours in an air atmosphere at 900 ℃ to obtain the LNCMO anode material doped with the excessive Ni element.
Electrode preparation and cell assembly were the same as in example 1.
Fig. 10 shows that increasing the Ni element content can increase the discharge midpoint voltage of the LNCMO positive electrode material and can suppress voltage decay during cycling of the LNCMO positive electrode material.
Example 7
Preparation of Ni element doped 0.5Li by sol-gel method2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material.
Adding Li, Ni, Co and Mn acetates into a certain amount of ethanol solution according to a stoichiometric ratio, then respectively adding nickel acetate into the reaction solution according to the additional mol percent (6 mol%) of Ni element, adding the nickel acetate into the reaction solution, magnetically stirring until sol is formed, and then drying for 12 hours at 120 ℃ to obtain a gel precursor. And carrying out heat treatment on the obtained precursor at 900 ℃ for 10 hours to obtain the LNCMO anode material doped with the excessive Ni element.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
Fig. 11 is a midpoint voltage decay curve during the cycle of LNCMO prepared by a sol-gel method and a 6% Ni-doped anode material with a molar percentage of 20 ma/g current density. The result shows that the excessive Ni element doping can effectively inhibit the voltage attenuation in the circulation process of the LNMCO anode material.
Example 8
Coprecipitation method for preparing excessive Ni element doped 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO) positive electrode material.
Adding Li, Ni, Co and Mn acetate into a certain amount of deionized water solution according to a stoichiometric ratio, then respectively adding lithium acetate and nickel acetate into the reaction solution according to the additional mole percentage (6 mol%) of a Ni element, adding the mixture into the reaction solution, adjusting the pH value to 10 by adopting ammonia water, mechanically stirring for 10 hours until a reactant is precipitated, then removing the reaction solution by suction filtration, and drying the product at 120 ℃ for 12 hours to obtain a precursor. And carrying out heat treatment on the obtained precursor at 900 ℃ for 10 hours to obtain the LNCMO anode material doped with different Ni elements.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
Fig. 12 is a midpoint voltage decay curve during cycling for LNCMO prepared by co-precipitation and a Ni-doped anode material with a molar percentage of 6% at a current density of 20 ma/g. The result shows that the excessive Ni element doping can effectively inhibit the voltage attenuation in the circulation process of the LNMCO anode material.
Example 9
A Ni-doped LNCMO cathode material with a molar percentage of 6% was prepared according to the preparation method in example 1.
Mixing the LNCMO @ Er2O3 positive electrode material and a binder according to a certain proportion, stirring for 4 hours by adopting magnetic force to obtain uniform slurry, and then uniformly coating the slurry on an aluminum foil to obtain the electrode material. The characterization battery adopts a 18650 battery, the assembly process is completed in a glove box filled with Ar, and the water and oxygen contents are both less than 0.1 ppm. The positive electrode is the prepared electrode plate; the reference electrode and the counter electrode are graphite sheets; the septum is Celgard-2400; the electrolyte was LiPF6(1mol/L)/EC + DEC + EMC (1:1:1), and the assembled cell was placed for testing.
As shown in fig. 13, when the first discharge capacity of the full cell using graphite as the negative electrode of the 6% Ni-doped LNCMO positive electrode material reaches 2295 ma, the capacity retention rate after 300 cycles is 92.9%. When the full cell taking the unmodified LNCMO as the anode and the graphite as the cathode is 2543 milliamperes of first discharge capacity, the capacity retention rate is only 76.6 percent after 300 cycles. The more remarkable result is that the initial discharge midpoint potential of the full cell taking 6% Ni-doped LNCMO anode material and graphite as the cathode is 3.63 volts, the initial discharge midpoint potential after 300 cycles is 3.46 volts, and the midpoint potential retention rate is 95.3%. However, the first discharge midpoint potential of the unmodified full cell was only 3.50 volts, and after 300 cycles was 2.98 volts, the midpoint potential retention rate was only 85.1%.
The above results fully indicate that the doping modification of the excess Ni element to the LNCMO positive electrode material can effectively inhibit the capacity/voltage decay in the cycle process, i.e., effectively improve the energy density of the battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of preparing a layered lithium-rich manganese oxide positive electrode material, comprising the steps of: in the preparation process of the precursor of the layered lithium-rich manganese oxide anode material of the lithium ion battery, the raw material precursor of the modified material is added, and then the layered lithium-rich manganese oxide anode material is obtained through high-temperature heat treatment.
2. The method of claim 1, wherein the layered lithium-rich manganese oxide cathode material is xLi2MnO3-(1-x)LiMO2Wherein M is at least one selected from Ni, Co, Mn, Cr and Fe; 0. ltoreq. x.ltoreq.1, preferably 0.1. ltoreq. x.ltoreq.0.8.
3. The preparation method according to claim 1, wherein the modified material of the layered lithium-rich manganese oxide positive electrode material is metallic Ni;
preferably, the raw material precursor of the modification material is added in an amount such that the molar ratio of the doping amount of the metallic nickel to the layered lithium-rich manganese oxide positive electrode material is 0.01-0.1, preferably 0.01-0.06.
4. The method according to claim 1, wherein the precursor is prepared by at least one method selected from the group consisting of a spraying method, a coprecipitation method, a sol-gel method, a combustion method, a solid phase method, and a molten salt method;
preferably, the atmosphere of the high-temperature heat treatment is at least one of oxygen, air and vacuum; the temperature of the heat treatment is 400-1400 ℃; the heat treatment time is 0.5 to 72 hours.
5. The preparation method according to claim 1, wherein the raw materials used for the layered lithium-rich manganese oxide positive electrode material precursor and the raw material precursor of the modification material are each independently selected from at least one of acetate, nitrate, sulfate, carbonate, oxalate, and metal oxide.
6. A layered lithium-rich manganese oxide positive electrode material prepared by the method of any one of claims 1 to 5.
7. A lithium ion battery positive electrode, characterized in that: the method comprises the steps of taking the anode material as defined in claim 6 as an anode material, mixing the anode material with a conductive agent, carrying out ball milling to obtain a mixture, mixing the mixture and a binder to form slurry, coating the slurry on an aluminum foil, and drying to obtain the lithium ion battery anode.
8. The positive electrode for a lithium ion battery according to claim 7, wherein the conductive agent is at least one selected from graphite, acetylene black, Super P, carbon nanotube, graphene, and Ketjen;
based on the total weight of the slurry, the content of the conductive agent is 2 to 30 weight percent;
preferably, the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose and sodium alginate;
based on the total weight of the slurry, the amount of the binder is 1 wt% to 30 wt%.
9. The lithium ion battery anode according to claim 7, wherein the mass ratio of the ball materials is 5: 1-300: 1 during ball milling; the rotating speed of the ball mill is 100-800 r/min; the ball milling time is 0.5 to 48 hours; the ball milling atmosphere is selected from at least one of air, oxygen, nitrogen, hydrogen, argon, carbon dioxide and helium.
10. A lithium ion battery, characterized by: the lithium ion battery comprises a positive electrode, a negative electrode capable of releasing and absorbing lithium ions and an electrolyte between the negative electrode and the positive electrode, wherein the positive electrode is the lithium ion battery positive electrode as claimed in any one of claims 7 to 9.
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