CN114824267B - Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof - Google Patents
Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114824267B CN114824267B CN202210324360.1A CN202210324360A CN114824267B CN 114824267 B CN114824267 B CN 114824267B CN 202210324360 A CN202210324360 A CN 202210324360A CN 114824267 B CN114824267 B CN 114824267B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 110
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title abstract description 24
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 64
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 48
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 32
- LIPIURJJRUOGSS-UHFFFAOYSA-N dodecyl hydrogen carbonate Chemical compound CCCCCCCCCCCCOC(O)=O LIPIURJJRUOGSS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005416 organic matter Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000010405 anode material Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 claims description 13
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000011572 manganese Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a layered lithium nickel manganese oxide positive electrode material, and a preparation method and application thereof. The surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic matters, the hydrophobic organic matters are coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film mode, and the hydrophobic organic matters comprise cholesterol dodecyl carbonate. According to the invention, the surface of the positive electrode is rendered hydrophobic by the special hydrophobic organic matter cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, stable Mn-C=O bonds are formed with the surface of the positive electrode material, thereby effectively improving the cycling stability and voltage drop of the lithium nickel manganese oxide positive electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a layered lithium nickel manganese oxide positive electrode material, a preparation method and application thereof.
Background
In recent years, new energy sources have highlighted explosive growth trends, and there is an urgent need for a positive electrode material with low cost, high energy density, high cycle performance and high safety. LiCoO as the positive electrode material in the market 2 And ternary materials (NCM), all of which cannot meet the above conditions at the same time, mainly because cobalt is an environmentally unfriendly element as well as the price of cobalt continues to rise. Ni in charge-discharge process in ternary material 2+ And Li (lithium) + The mixed discharge of the nickel-rich and manganese-rich layered oxygen has poor circulation stability, and in addition, the high nickel material has serious gas production problem and poor low-temperature performance, so that the development of the nickel-rich and manganese-rich layered oxygen is further restrictedThe compound (without cobalt) has specific capacity higher than 300mAh/g and energy density of 1000Wh/kg, and is considered as one of the most promising positive electrode materials in the next generation of lithium ion batteries. In addition, the cost is low, the environment is friendly, but the current lithium-rich manganese-based positive electrode material (without cobalt) has the problems of poor cycle stability and serious voltage drop, and the industrialization development of the lithium-rich manganese-based positive electrode material is seriously restricted.
CN113072101a discloses a cobalt-free positive electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Lithium source and precursor Ni x Mn y (OH) 2 Mixing with a doping agent, and carrying out primary heat treatment to obtain a matrix material; (2) And (3) mixing the substrate material obtained in the step (1) with a coating agent, and performing secondary heat treatment to obtain the cobalt-free anode material. The single cobalt-free material is adopted, so that the cycle stability is poor.
CN112133903a discloses a preparation method of a cobalt-free positive electrode material, which comprises the following steps (1) preparation of a cobalt-free positive electrode material precursor: (1a) Mixing nickel salt and manganese salt solution, adding nano additive, and performing ultrasonic treatment; (1b) Adding the mixed solution into a reaction kettle in a nitrogen atmosphere, adding a mixed alkali solution of strong alkali and ammonia water, adjusting the pH value to 9-12, reacting at 40-60 ℃, and washing, filtering and drying after the reaction is finished; (2) high-temperature sintering: and (3) uniformly mixing lithium hydroxide with the powder obtained in the step (1 b), calcining at the constant temperature of 700-1000 ℃ for 5-20 h, and naturally cooling to obtain the cobalt-free anode material. The lithium ion battery adopts a single cobalt-free material, and during the cyclic process, due to the release of lattice oxygen and the structural transformation, the lithium ion causes structural collapse during the intercalation and deintercalation process, wherein partial free lithium ion is deposited on the surface to cause poor cyclic stability, and the lithium ion battery is difficult to be applied commercially.
Therefore, how to improve the cycle performance of the cobalt-free cathode material (layered lithium nickel manganese oxide cathode material) and reduce the voltage drop is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a layered lithium nickel manganese oxide positive electrode material, and a preparation method and application thereof. According to the invention, the surface of the positive electrode is rendered hydrophobic by the special hydrophobic organic matter cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, stable Mn-C=O bonds are formed with the surface of the positive electrode material, thereby effectively improving the cycling stability and voltage drop of the lithium nickel manganese oxide positive electrode material.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a layered lithium nickel manganese oxide positive electrode material, wherein the surface of the layered lithium nickel manganese oxide positive electrode material is coated with a hydrophobic organic matter, the hydrophobic organic matter is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the hydrophobic organic matter comprises cholesterol dodecyl carbonate.
According to the invention, the surface of the positive electrode is rendered hydrophobic by the special hydrophobic organic matter cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, and meanwhile, stable Mn-C=O bonds are formed with the surface of the positive electrode material, thereby effectively improving the cycling stability and voltage drop of the lithium nickel manganese oxide positive electrode material.
In the invention, cholesterol dodecyl carbonate has a stronger delocalized electron region, can absorb residual lithium on the surface of the lithium nickel manganese oxide positive electrode material, so that residual alkali of the lithium nickel manganese oxide positive electrode material is reduced, thereby improving the circulation stability, and the specific electron region can improve Li + The migration rate of the whole lithium nickel manganese oxide anode material is improved; and the cholesterol dodecyl carbonate and the surface of the lithium nickel manganese oxide positive electrode material form a special bonding mechanism, so that the phase change process of the positive electrode material in the battery cycle process can be inhibited, and a special elastic network can be formed on the uniform surface, so that the deformation of the positive electrode in the battery cycle process is weakened, and the voltage drop of the battery in the battery cycle process can be effectively reduced.
In the invention, the coating is membranous, a layer of film is formed on the surface of the positive electrode material, and compared with the conventional punctiform coating, the coating has the advantages of more uniform coating effect and effective blocking of the damage of the electrolyte to the positive electrode material.
Preferably, the thickness of the coating film of the hydrophobic organic substance is 10 to 50nm, for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or the like.
In the present invention, the thickness of the coating film of the hydrophobic organic substance is too thin, so that the purpose of alleviating the structural damage during the battery cycle cannot be achieved, and if the thickness of the coating film is too thick, the capacity of the positive electrode material is affected.
In a second aspect, the present invention provides a method for preparing the layered lithium nickel manganese oxide positive electrode material according to the first aspect, the method comprising the steps of:
(1) Mixing a nickel-manganese precursor with a lithium source, and sintering to obtain a pre-coated layered lithium nickel manganese oxide anode material;
(2) Mixing and coating the pre-coated layered lithium nickel manganese oxide anode material, hydrophobic organic matters and a solvent to obtain the layered lithium nickel manganese oxide anode material;
wherein the hydrophobic organic matter comprises cholesterol dodecyl carbonate.
According to the invention, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with the cholesterol dodecyl carbonate which is a special hydrophobic organic substance, and the surface of the positive electrode presents hydrophobicity, so that the electrochemical performance of the positive electrode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide (cobalt-free positive electrode material) in a high-moisture environment, and meanwhile, a stable Mn-C=O bond is formed with the surface of the positive electrode material, so that the cycling stability and voltage drop of the lithium nickel manganese oxide positive electrode material are effectively improved.
Preferably, the nickel manganese precursor includes a nickel manganese oxide precursor and a nickel manganese hydroxide precursor.
According to the invention, through mixing the nickel-manganese oxide precursor and the nickel-manganese hydroxide precursor, the growth process of crystal grains can be effectively controlled, and the sintered particles are less in agglomeration, so that the cycling stability of the positive electrode material is improved.
Preferably, the mass ratio of the nickel manganese oxide precursor and the nickel manganese hydroxide precursor is (0.2-1): 1, for example 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, or the like.
In the invention, the excessive mass ratio of the nickel-manganese oxide precursor to the nickel-manganese hydroxide precursor, namely more than 1:1, can cause serious particle agglomeration and uneven particle growth in the later sintering process, thereby affecting the cycle stability of the battery and increasing the gas production.
Preferably, the nickel manganese oxide precursor is obtained by presintering a nickel manganese hydroxide precursor.
Preferably, the temperature of the burn-in is 500 to 700 ℃, for example 500 ℃, 530 ℃, 550 ℃, 580 ℃, 600 ℃, 630 ℃, 650 ℃, 68 ℃, 0 or 700 ℃, etc.
In the invention, the excessive temperature of presintering the nickel-manganese hydroxide precursor can cause metallic precipitation and oxygen loss, thereby generating irreversible circulating substances and further influencing the circulating performance and voltage drop of the positive electrode material.
Preferably, the burn-in time is 5 to 10 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like.
Preferably, the mixed feedstock of step (1) further comprises a dopant.
Preferably, the solvent of step (2) comprises tetrahydrofuran.
Preferably, the process of mixing and coating in the step (2) includes: firstly, dissolving the hydrophobic organic matters in a solvent to obtain a hydrophobic organic matter solution, and then adding the pre-coated layered lithium nickel manganese oxide positive electrode material in the step (1) for mixed coating;
preferably, the method of mixing and coating in step (2) comprises stirring.
Preferably, the temperature of the stirring is 25 to 80 ℃, for example 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like.
In the invention, the stirring temperature is too high, so that the electrochemical performance of the prepared positive electrode material is reversely reduced, namely organic matters are unfavorable for growing on the surfaces of particles at high temperature, and even if the organic matters grow on the surfaces of the particles, the surface coating is uneven due to the acceleration of high-temperature movement, so that the electrochemical performance of the prepared layered lithium nickel manganese oxide positive electrode material is reduced.
Preferably, the stirring time is 2 to 6 hours, for example 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, etc.
In the invention, the stirring time is too short, so that the reaction time is too short, thereby leading the organic matters to be coated uniformly with the cobalt-free lithium-rich positive electrode material, and finally leading the electrochemical performance to be reduced.
Preferably, the concentration of the hydrophobic organic solution is 1 to 3mol/L, for example 1mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, or the like.
In the invention, the concentration of the hydrophobic organic matter solution is too high, which can influence the uniform dispersion of the positive electrode material in the solution, thereby influencing the coating effect of the organic matter on single particles.
Preferably, after the step (2) of mixing and coating, suction filtration and drying are sequentially performed.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Mixing a nickel manganese oxide precursor and a nickel manganese hydroxide precursor with a lithium source and a doping agent according to the mass ratio of (0.2-1): 1, and sintering to obtain a pre-coated layered lithium nickel manganese oxide anode material;
(2) Firstly, dissolving the hydrophobic organic matters in a solvent to obtain a hydrophobic organic matter solution with the concentration of 1-3 mol/L, then adding the pre-coated layered lithium nickel manganese oxide positive electrode material obtained in the step (1), stirring for 2-6 hours at the temperature of 25-80 ℃, carrying out suction filtration, and drying to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic matter comprises cholesterol dodecyl carbonate; the nickel-manganese oxide precursor is obtained by presintering a nickel-manganese hydroxide precursor at 500-700 ℃ for 5-10 hours.
In a third aspect, the present invention also provides a lithium ion battery comprising a layered lithium nickel manganese oxide cathode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the surface of the positive electrode is rendered hydrophobic by the special hydrophobic organic matter cholesterol dodecyl carbonate coated on the surface of the layered lithium nickel manganese oxide positive electrode material, so that the electrochemical performance of the positive electrode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide positive electrode material in a high-moisture environment, meanwhile, stable Mn-C=O bonds are formed with the surface of the positive electrode material, the growth process of crystal grains is effectively controlled by mixing and collocating the precursors, the sintered particles are less in agglomeration, and the cycle stability and voltage drop of the lithium nickel manganese oxide positive electrode material are finally improved. The specific discharge capacity of the battery provided by the invention under 1C can reach more than 205.8mAh/g, the capacity retention rate after 50 weeks of circulation can reach more than 94.4%, and the voltage decay after 50 weeks is less than 3.85%; the precursor material is a mixed material of a hydroxide precursor and an oxide precursor, and after the presintering temperature, the concentration of hydrophobic organic matters and the stirring time in the coating process are further adjusted, the specific discharge capacity of the battery under 1C can reach more than 210.4mAh/g, the capacity retention rate after 50 weeks of circulation can reach more than 96.8%, and the voltage decay after 50 weeks is less than 2.81%.
Drawings
Fig. 1 is a TEM image of a layered lithium nickel manganese oxide positive electrode material provided in example 1.
Fig. 2 is a TEM image of the layered lithium nickel manganese oxide positive electrode material provided in comparative example 2.
Fig. 3 is a graph showing the discharge curves of the batteries provided in example 1 and comparative examples 1 to 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, wherein the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic matter cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the layered lithium nickel manganese oxide positive electrode materialThe chemical formula is Li 1.23 Ni 0.35 Mn 0.65 O 2 Wherein the film thickness of the coating layer was 20nm.
The preparation method of the layered lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Cobalt-free precursor (Ni 0.35 Mn 0.65 (OH) 2 ) Presintering for 6h at 650 ℃ in a sintering furnace to obtain presintering precursor Ni 0.35 Mn 0.65 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking presintered Ni 0.35 Mn 0.65 O 2 And Ni 0.35 Mn 0.65 (OH) 2 (the mass ratio of the oxide precursor to the hydroxide precursor is 1:1), and Li 2 CO 3 (Li/Me may be 1.23) and WO 3 Uniformly stirring (doping amount is 2000 ppm) by using a hand-held stirrer, then placing the mixed materials into a crucible, placing the crucible into a sintering furnace, sintering for 10 hours at 870 ℃, taking the sintered materials, crushing, and sieving by using a 400-mesh screen to obtain the pre-coated layered lithium nickel manganese oxide anode material;
(2) Dissolving cholesterol dodecyl carbonate into tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing 1mo/L of cholesterol dodecyl carbonate matrix solution, taking pre-coated layered lithium nickel manganese oxide anode material, putting the pre-coated layered lithium nickel manganese oxide anode material into the prepared cholesterol dodecyl carbonate matrix solution, and stirring for 2 hours at 30 ℃; and after the stirring is finished, filtering the stirred solution by a suction filter, putting the solution into a vacuum drying oven, drying the solution at 100 ℃ for 12 hours, and sieving the solution by a 400-mesh screen to obtain the layered lithium nickel manganese oxide anode material.
Fig. 1 shows a TEM image of the layered lithium nickel manganese oxide cathode material provided in example 1, and it can be seen from fig. 1 that the coating in the present invention is a distinct membranous coating.
Example 2
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, wherein the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic matter cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the chemical formula of the layered lithium nickel manganese oxide positive electrode material is as followsLi 1.2 Ni 0.45 Mn 0.55 O 2 Wherein the film thickness of the coating layer was 30nm.
The preparation method of the layered lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Cobalt-free precursor (Ni 0.45 Mn 0.55 (OH) 2 ) Presintering for 10h at 500 ℃ in a sintering furnace to obtain presintering precursor Ni 0.45 Mn 0.55 O 2 (II), (III), (V), (; taking presintered Ni 0.45 Mn 0.55 O 2 And Ni 0.45 Mn 0.55 (OH) 2 (the mass ratio of the oxide precursor to the hydroxide precursor is 0.2:1), and Li 2 CO 3 (Li/Me may be 1.2) and ZrO 2 Uniformly stirring the materials (doping amount is 1500 ppm) by using a hand-held stirrer, putting the mixed materials into a crucible, putting the crucible into a sintering furnace, sintering for 8 hours at 900 ℃, taking the sintered materials, crushing, and sieving by using a 400-mesh screen to obtain the pre-coated layered lithium nickel manganese oxide anode material;
(2) Dissolving cholesterol dodecyl carbonate into tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing 2mo/L of cholesterol dodecyl carbonate matrix solution, taking pre-coated layered lithium nickel manganese oxide anode material, putting the pre-coated layered lithium nickel manganese oxide anode material into the prepared cholesterol dodecyl carbonate matrix solution, and stirring for 6 hours at 50 ℃; and after the stirring is finished, filtering the stirred solution by a suction filter, putting the solution into a vacuum drying oven, drying the solution at 100 ℃ for 12 hours, and sieving the solution by a 400-mesh screen to obtain the layered lithium nickel manganese oxide anode material.
Example 3
The embodiment provides a layered lithium nickel manganese oxide positive electrode material, wherein the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic matter cholesterol dodecyl carbonate, the cholesterol dodecyl carbonate is coated on the surface of the layered lithium nickel manganese oxide positive electrode material in a film form, and the chemical formula of the layered lithium nickel manganese oxide positive electrode material is Li 1.3 Ni 0.6 Mn 0.4 O 2 Wherein the film thickness of the coating layer was 40nm.
The preparation method of the layered lithium nickel manganese oxide positive electrode material comprises the following steps:
(1) Cobalt-free precursor (Ni 0.6 Mn 0.4 (OH) 2 ) Presintering for 10h at 500 ℃ in a sintering furnace to obtain presintering precursor Ni 0.6 Mn 0.4 O 2 (II), (III), (V), (; taking presintered Ni 0.6 Mn 0.4 O 2 And Ni 0.6 Mn 0.4 (OH) 2 (the mass ratio of oxide precursor to hydroxide precursor is 0.65:1), and LiOH (Li/Me may be 1.3) and ZrO 2 Uniformly stirring the materials (doping amount is 1500 ppm) by using a hand-held stirrer, putting the mixed materials into a crucible, putting the crucible into a sintering furnace, sintering for 10 hours at 850 ℃, taking the sintered materials, crushing, and sieving by using a 400-mesh screen to obtain the pre-coated layered lithium nickel manganese oxide anode material;
(2) Dissolving cholesterol dodecyl carbonate into tetrahydrofuran solution in a glove box, stirring for 2 hours, preparing 3mo/L of cholesterol dodecyl carbonate matrix solution, taking pre-coated layered lithium nickel manganese oxide anode material, putting the pre-coated layered lithium nickel manganese oxide anode material into the prepared cholesterol dodecyl carbonate matrix solution, and stirring for 4 hours at 80 ℃; and after the stirring is finished, filtering the stirred solution by a suction filter, putting the solution into a vacuum drying oven, drying the solution at 100 ℃ for 12 hours, and sieving the solution by a 400-mesh screen to obtain the layered lithium nickel manganese oxide anode material.
Example 4
The difference between this example and example 1 is that the burn-in temperature in step (1) of this example was 750 ℃.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the molar concentration of the matrix solution of cholesterol dodecyl carbonate in step (2) of this example was 5mol/L.
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the stirring temperature after the addition of the precoat material in step (2) of this example was 100 ℃.
The remaining preparation methods and parameters were consistent with example 1.
Example 7
The difference between this example and example 1 is that the stirring time after the addition of the precoat material in step (2) of this example was 0.5h.
The remaining preparation methods and parameters were consistent with example 1.
Example 8
The difference between this comparative example and example 1 is that Ni was directly added in the step (1) of this comparative example 0.35 Mn 0.65 (OH) 2 Precursor and Li 2 CO 3 (Li/Me may be 1.23) and WO 3 (doping amount 2000 ppm), i.e. only hydroxide precursor was used.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that step (2) was not performed in the preparation method of this comparative example, i.e., the surface of the positive electrode material was not coated.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The difference between the comparative example and example 1 is that the coating process in the step (2) of the comparative example is to take 80g of the pre-coating material in the step (1) and 0.2702g of Al 2 O 3 And (3) after uniformly mixing, placing the mixture into a box-type atmosphere furnace, calcining for 5 hours at 700 ℃, and sieving after sintering to obtain the common oxide coated layered lithium nickel manganese oxide anode material.
The remaining preparation methods and parameters were consistent with example 1.
Fig. 2 shows a TEM image of the layered lithium nickel manganese oxide positive electrode material provided in comparative example 2, and it can be seen by combining fig. 1 and fig. 2 that the layered lithium nickel manganese oxide positive electrode material coated on the surface of cholesterol dodecyl carbonate is successfully synthesized, and is a film-shaped coating, which is obviously different from a conventional dot-shaped coating, because both hydrophobic and elastic organic matters have a certain lithium philicity with the organic matters coating the positive electrode material, the residual lithium on the surface of the lithium-rich material can be reduced to a certain extent, and on the other hand, even coating occurs in M-c=o bonding, so that structural damage and irreversible phase change processes in the battery cycle process can be fixed, thereby improving the cycle stability and weakening the voltage attenuation.
Fig. 3 shows a comparative graph of discharge curves of the batteries provided in example 1 and comparative examples 1-2, and it can be seen from fig. 3 that the discharge capacity of the battery obtained from the layered lithium nickel manganese oxide positive electrode material provided by the present invention is higher.
Comparative example 3
The difference between this comparative example and example 8 is that step (2) was not performed in the preparation method of this comparative example, i.e., the surface of the positive electrode material was not coated.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 4
The difference between this comparative example and example 8 is that the coating process in step (2) of this comparative example is to take 80g of the pre-coating material in step (1) and 0.2702g of Al 2 O 3 And (3) after uniformly mixing, placing the mixture into a box-type atmosphere furnace, calcining for 5 hours at 700 ℃, and sieving after sintering to obtain the common oxide coated layered lithium nickel manganese oxide anode material.
The remaining preparation methods and parameters were consistent with example 1.
The positive electrode materials provided in examples 1 to 8 and comparative examples 1 to 4 were subjected to a slurry coating, wherein the positive electrode material was superconductive carbon black SP, polyvinylidene fluoride glue solution=90:5:5, and pvdf glue solution had a solid content of 6.05%. And buckling and assembling the prepared pole piece by adopting a BR2032 shell.
The positive electrode materials provided in examples 1 to 8 and comparative examples 1 to 4 were subjected to electrochemical performance tests under the following conditions: the charge and discharge test was performed at a charge and discharge current of 1C, and the capacity retention after 50 weeks and the voltage decay after 50 weeks were obtained, and the results are shown in table 1.
TABLE 1
As is clear from the data obtained in examples 1 and 4, too high a burn-in temperature caused metallic precipitation and oxygen loss, and the generation of irreversible circulating substances reduced the circulating stability and increased the voltage drop.
As is clear from the data of examples 1 and 5, too high a concentration of the hydrophobic organic solution is detrimental to uniform dispersion of the positive electrode material particles in the hydrophobic organic solution, resulting in uneven coating and reduced cycle stability.
From the data of example 1 and example 6, it is understood that the temperature during stirring is too high, and the electrochemical properties of the positive electrode material thus obtained are degraded.
As is clear from the data of example 1 and example 7, the stirring time is too short, resulting in a reaction time period and thus an organic matter that does not reach completion of uniform coating with the lithium nickel manganese oxide cathode material, resulting in a decrease in electrochemical performance.
From the data of examples 1 and 8, it is apparent that the use of the pre-firing precursor and the hydroxide precursor in combination can effectively control the growth process of the crystal grains, and the sintered particles are less agglomerated, thereby improving the cycle stability.
As is clear from the data results of example 1 and comparative example 1 (example 8 and comparative example 2), without coating, it was not possible to achieve improvement in the cycling stability of the cobalt-free lithium-rich material during the cycling of the battery and reduction in the voltage drop caused by the structural transformation of the cobalt-free lithium-rich cathode material.
From the data of example 1 and comparative example 2 (example 8 and comparative example 4), it is understood that the cathode material coated with the hydrophobic organic compound in the present invention has higher cycle performance and lower voltage decay amplitude than the dot-shaped coating of the conventional oxide.
In conclusion, the surface of the layered lithium nickel manganese oxide anode material is coated with the cholesterol dodecyl carbonate which is a special hydrophobic organic substance, and the surface of the anode presents hydrophobicity, so that the electrochemical performance of the anode material is reduced due to water absorption on the surface of the layered lithium nickel manganese oxide (cobalt-free anode material) in a high-moisture environment, and meanwhile, stable Mn-C=O bonds are formed with the surface of the anode material, so that the cycling stability and voltage drop of the lithium nickel manganese oxide anode material are effectively improved. The specific discharge capacity of the battery provided by the invention under 1C can reach more than 205.8mAh/g, the capacity retention rate after 50 weeks of circulation can reach more than 94.4%, and the voltage decay after 50 weeks is less than 3.85%; the precursor material is a mixed material of a hydroxide precursor and an oxide precursor, and after the presintering temperature, the concentration of hydrophobic organic matters and the stirring time in the coating process are further adjusted, the specific discharge capacity of the battery under 1C can reach more than 210.4mAh/g, the capacity retention rate after 50 weeks of circulation can reach more than 96.8%, and the voltage decay after 50 weeks is less than 2.81%.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (18)
1. The layered lithium nickel manganese oxide positive electrode material is characterized in that the surface of the layered lithium nickel manganese oxide positive electrode material is coated with hydrophobic organic matters, the surface of the layered lithium nickel manganese oxide positive electrode material is coated with the hydrophobic organic matters in a film mode, and the hydrophobic organic matters comprise cholesterol dodecyl carbonate.
2. The layered lithium nickel manganese oxide positive electrode material according to claim 1, wherein the thickness of the coating film of the hydrophobic organic substance is 10 to 50nm.
3. A method for preparing the layered lithium nickel manganese oxide positive electrode material according to claim 1 or 2, comprising the steps of:
(1) Mixing a nickel-manganese precursor with a lithium source, and sintering to obtain a pre-coated layered lithium nickel manganese oxide anode material;
(2) Mixing and coating the pre-coated layered lithium nickel manganese oxide anode material, hydrophobic organic matters and a solvent to obtain the layered lithium nickel manganese oxide anode material;
wherein the hydrophobic organic matter comprises cholesterol dodecyl carbonate.
4. The method of preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the nickel manganese precursor comprises a nickel manganese oxide precursor and a nickel manganese hydroxide precursor.
5. The method for producing a layered lithium nickel manganese oxide positive electrode material according to claim 4, wherein the mass ratio of the nickel manganese oxide precursor to the nickel manganese hydroxide precursor is (0.2 to 1): 1.
6. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 4, wherein the nickel manganese oxide precursor is obtained by pre-sintering a nickel manganese hydroxide precursor.
7. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 6, wherein the pre-sintering temperature is 500 to 700 ℃.
8. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 6, wherein the pre-firing time is 5 to 10 hours.
9. The method of preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the mixed raw material of step (1) further comprises a dopant.
10. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the process of the mixed coating in the step (2) comprises: dissolving the hydrophobic organic matters in a solvent to obtain a hydrophobic organic matter solution, and then adding the pre-coated layered lithium nickel manganese oxide positive electrode material obtained in the step (1) for mixed coating.
11. The method for producing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the solvent of step (2) comprises tetrahydrofuran.
12. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the method for mixed coating in the step (2) comprises stirring.
13. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 12, wherein the temperature of stirring is 25 to 80 ℃.
14. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 12, wherein the stirring time is 2 to 6 hours.
15. The method for producing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the concentration of the hydrophobic organic substance solution is 1 to 3mol/L.
16. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, wherein the step (2) is performed with suction filtration and drying in sequence after the mixed coating.
17. The method for preparing a layered lithium nickel manganese oxide positive electrode material according to claim 3, comprising the steps of:
(1) Mixing a nickel manganese oxide precursor and a nickel manganese hydroxide precursor with a lithium source and a doping agent according to the mass ratio of (0.2-1): 1, and sintering to obtain a pre-coated layered lithium nickel manganese oxide anode material;
(2) Firstly, dissolving the hydrophobic organic matters in a solvent to obtain a hydrophobic organic matter solution with the concentration of 1-3 mol/L, then adding the pre-coated layered lithium nickel manganese oxide positive electrode material obtained in the step (1), stirring for 2-6 hours at the temperature of 25-80 ℃, carrying out suction filtration, and drying to obtain the layered lithium nickel manganese oxide positive electrode material;
wherein the hydrophobic organic matter comprises cholesterol dodecyl carbonate; the nickel-manganese oxide precursor is obtained by presintering a nickel-manganese hydroxide precursor at 500-700 ℃ for 5-10 hours.
18. A lithium ion battery comprising the layered lithium nickel manganese oxide positive electrode material according to claim 1 or 2.
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| CN109119607A (en) * | 2018-08-04 | 2019-01-01 | 浙江瓦力新能源科技有限公司 | A kind of polypyrrole nanotube cladding nickel lithium manganate cathode material and preparation method thereof |
| CN112820865A (en) * | 2021-02-05 | 2021-05-18 | 合肥国轩高科动力能源有限公司 | Preparation method of double-layer surface-coated high-nickel ternary single crystal positive electrode material |
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