CN113555544A - Al-Ti-Mg element co-doped and LATP coated high-voltage spinel LNMO positive electrode material and preparation method thereof - Google Patents
Al-Ti-Mg element co-doped and LATP coated high-voltage spinel LNMO positive electrode material and preparation method thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 95
- 239000011029 spinel Substances 0.000 title claims abstract description 95
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 69
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 97
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 123
- 239000011777 magnesium Substances 0.000 claims description 118
- 239000007787 solid Substances 0.000 claims description 64
- 239000011572 manganese Substances 0.000 claims description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 38
- 238000000227 grinding Methods 0.000 claims description 31
- 238000007873 sieving Methods 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 229910013716 LiNi Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 238000007605 air drying Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 15
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 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 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 49
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 229910018575 Al—Ti Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- CMXQQXNDMXGZEE-UHFFFAOYSA-K O.O.O.O.O.O.O.O.O.[Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O CMXQQXNDMXGZEE-UHFFFAOYSA-K 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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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- 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
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Abstract
The invention discloses an Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The positive electrode material and the preparation method thereof are characterized in that the raw materials are added into an agate ball milling tank, and absolute ethyl alcohol is added and mixed uniformly to form suspension; performing ball milling on the suspension to obtain slurry; pre-burning the dried slurry; sintering the precursor powder obtained after pre-sintering for the second time to obtain a positive electrode material; mixing LATP with anode material, heating and stirring, and sintering at high temperature to obtain Al-Ti-Mg co-doped materialHeteroand LATP-coated high-pressure spinel LiNi0.5Mn1.5O4And (3) a positive electrode material. According to the invention, through the synergistic effect of multi-element co-doping and the protection effect of LATP coating on the material, the stability of the material structure is enhanced, and the structural damage of the material in the circulation process is effectively inhibited, so that the capacity retention rate and the high rate performance of long-term circulation are improved.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium battery cathode materials, and particularly relates to Al-Ti-Mg element co-doped and LATP-coated high-voltage spinel LiNi0.5Mn1.5O4A positive electrode material and a preparation method thereof.
Background
With the demands of economic globalization and improvement of energy supply, sustainable energy is the key to future energy development, and lithium ion batteries are gradually the research hotspots in the field of new energy. Lithium ion batteries are now widely used in portable electronic devices, power cars and grid energy storage systems. The lithium ion battery is developed to the present, people have higher and higher performance requirements, and many enterprises and scientific research institutes in the world have developed researches on the positive electrode material with higher energy density and higher voltage so as to meet the performance requirements of different fields on the lithium ion battery.
High pressure spinel LiNi0.5Mn1.5O4The working voltage of the (LNMO) anode material is 4.7V, and the use requirement of high-power electric equipment can be met. Meanwhile, the LNMO synthetic raw material does not contain cobalt, so that the cost is reduced, and the non-toxicity of the material is ensured. The energy density of LNMO was 650Wh kg-1Compared with the traditional positive electrode material LiCoO2(540Wh·kg-1)，LiMn2O4(500Wh·kg-1)，LiFePO4(500Wh·kg-1) Is higher. But tend to distort the structure of the LNMO under high voltage operating conditions. And meanwhile, the side reaction between the LNMO and the electrolyte can be accelerated, so that the cycle and rate performance of the battery are negatively influenced.
Al, Ti and Mg are nontoxic and relatively cheap metal elements, and researches show that Mn can be effectively inhibited by doping Al in LNMO3+Disproportionation; the doping of Ti can reduce impurity Li generated in the high-temperature sintering process of LNMOxNi1-x(ii) a Electrode polarization can be reduced and LNMO electron conductivity can be improved by doping with Mg.
Disclosure of Invention
The invention aims to aim at high-pressure spinel LiNi0.5Mn1.5O4The problems of low long-time cycle stability and poor high rate performance of the cathode material are solved. The invention provides an Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4And (3) a positive electrode material.
In order to realize the purpose, the invention is implemented by the following technical scheme:
Al-Ti-Mg element co-doped and LATP coated high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.5-aMn1.5-bAlxTiyMgzO4(0.001≤x≤0.06；0.001≤y≤0.05; 0.001≤z≤0.05)，LATP（LiaAlbTic(PO4)d) Coating thickness 1-100nm (coating amount: 0.001wt% to 2 wt%).
Furthermore, the doping amount of Al, Ti and Mg is preferably 0.01-0.05, 0.01-0.04 and 0.01-0.04.
Further, LATP (Li)aAlbTic(PO4)d) The coating thickness is preferably 3 to 20nm (coating amount: 0.01wt% to 1 wt%).
Further, the particle size of the positive electrode material is 0.1-30 μm; the particle size distribution of the positive electrode material is D50 of 0.5-15 μm.
Further, the material 20o-80oX of (2)The main diffraction peaks of RD are mainly: is located at 18.7oPeak (111) and peak at 36.7oPeak of (311), intensity ratio I(111)/I(311)Between 1.8 and 2.8 and at 36.7oPeak (311) of (D) and peak position at 44.8oPeak of (400), intensity ratio I(311)/I(400)Between 0.5 and 1.5.
Further, the tap density of the cathode material is 0.5-2.8g/cm3。
Further, the electrolyte used by the battery system of the positive electrode material is LiPF-containing electrolyte6And VC, wherein the content of VC in the electrolyte is 0.01-10 wt%.
Further, the crystal structure of the cathode material is an octahedron structure.
The Al-Ti-Mg element co-doped and LATP coated high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material characterized by comprising the steps of:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into absolute ethyl alcohol, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material;
(6) co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Positive electrode material and coating material for corresponding coating thicknessAdding LATP in a certain amount range into a beaker, dissolving in a heating type constant temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
In the step (1), the lithium source is one or more of lithium carbonate, lithium acetate and lithium nitrate; the nickel source is nickel oxide or nickel acetate tetrahydrate; the manganese source is one or more of manganese oxide, manganese dioxide and manganese tetraoxide; the aluminum source is aluminum oxide or aluminum acetate nonahydrate; the titanium source is titanium dioxide; the magnesium source is magnesium oxide.
In the step (1), the molar ratio of corresponding elements of lithium, nickel, manganese, aluminum, titanium and magnesium in the lithium source, the nickel source, the manganese source, the aluminum source, the titanium source and the magnesium source is 1:0.45:1.45:0.05 (0.01-0.04): 0.01-0.04)
In the step (2), the ball milling equipment is a planetary ball mill, the medium is agate beads, the ball-material ratio is 75:1, absolute ethyl alcohol is used as a dispersing agent, the ball milling speed is 400r/min, and the ball milling time is 5 hours.
And (3) the working temperature of the air-blast drying box in the step (3) is 120 ℃, and the drying time is 4 hours.
In the step (4), the pre-sintering temperature is 500 ℃, the heating rate before 100 ℃ is 2 ℃/min, and the heating rate is 100-500 DEG Co℃The heating rate is 5 ℃/min, and the sintering time is 5 hours.
The single aperture of the screen used for the screening in steps (5) and (7) was 0.074 mm.
In the step (6), the stirring speed of the heating type constant temperature magnetic stirrer is 40r/min, and the heating temperature is 120 ℃.
In the step (7), the sintering temperature is 950 ℃, the heating rate before 100 ℃ is 2 ℃/min, the heating rate between 100 ℃ and 950 ℃ is 5 ℃/min, and the sintering time is 5 hours.
The invention has the following remarkable advantages:
the invention adopts a high-temperature solid phase method to prepare high-pressure spinel LiNi which is co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4The anode material utilizes the synergistic effect of Al-Ti-Mg ternary element doping to enhance the structural stability of the material, and meanwhile, the LATP coated anode material can effectively inhibit the side reaction of the anode material and an electrolyte, so that the structural distortion of the material under the working conditions of long-time circulation and high rate is inhibited, and the capacity retention rate and the high rate performance are improved. The invention has the advantages of simple and easily obtained raw materials, no toxicity, stable preparation process, air sintering atmosphere, low cost and industrial prospect.
Drawings
FIG. 1 is a graph of 300 cycles at 30 ℃ and 1C for example 8 of the present invention and comparative examples 1, 2 and 3;
FIG. 2 is a graph showing cycle performance at different rates of 60 ℃ of example 8 of the present invention and comparative examples 1, 2 and 3;
FIG. 3 is an SEM photograph of example 8 of the present invention.
Detailed Description
The invention provides an Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The present invention is further described with reference to the following specific examples, so as to make the objects, technical solutions and effects of the present invention clearer and clearer. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Experiment raw materials:
(1) shanghai Aladdin Biotechnology GmbH: nickel oxide (AR); titanium dioxide (TiO)2Not less than 99%); alumina (AR); (2) shanghai Michelin Biochemical technology, Inc.: manganese monoxide (MnO = 99%), (3) magnesium oxide (MgO = 99.9%) (3) seikong science gmbh: li2CO3(AR); (4) san ming city new energy industry technology research institute: LATP (AR).
Manufacturing and testing the button half cell:
1. material drying (vacuum oven 110 degree drying 12 hours)
2. Weighing the ingredients (material: conductive agent: binder):
material conductive agent binder (LNMO: conductive carbon: binder) =90:5:5, solid content in binder 0.1g (binder with PVDF: NMP =1:9, wherein PVDF content is 10%)
3. Mixed material (material: conductive agent: binder) + NMP:
step (1): pouring the weighed powder material and the conductive agent into a centrifugal tank, and mixing for 1 time;
step (2): adding a binder and a proper amount of NMP, and mixing for 2 times;
mixing centrifuge parameters (Step 1: revolution 960 time 150s, Step2: revolution 1280 time 120s, Step3: revolution 1460 time 90 s).
4. Coating preparation:
step (1): transferring the slurry transferred by the mixer into a coating machine for coating operation;
step (2): putting the coated aluminum foil into a vacuum oven (110 ℃) for 2 hours;
and (3): compacting the dried aluminum foil by using a roller press;
and (4): the rolled aluminum foil was placed in a vacuum oven (110 ℃ C.) for 12 hours.
5. Manufacturing a battery;
step (1): cutting the rolled and dried pole piece by a sheet cutter to obtain a phi 14mm wafer;
step (2): weighing the cut pole piece by using a balance, and making a corresponding record;
and (3): continuously putting the pole piece into a vacuum oven to be dried (110 ℃) for 3 hours;
and (4): and putting the pole piece into a glove box for assembly, and assembling the battery. (the amount of the electrolyte is slightly adjusted according to the active quality of the pole piece);
and 5: and sealing the assembled battery by using a sealing machine.
6. And (3) testing the battery performance:
the battery capacity, cycle and rate performance are tested by Shenzhen New Wille electronics Limited (CT-4000).
Example 1:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.01:0.04, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.01Mg0.04O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 1-20nm (the coating mass is 0.001wt% -0.5wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 114.1mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 65% after 300 cycles at the test temperature of 30 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are respectively 114.2mAh/g, 112.2mAh/g, 113.7mAh/g, 111.2mAh/g, 105.9mAh/g, 101.1mAh/g, 92.1mAh/g and 113.7 mAh/g.
Example 2:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.01:0.04, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.01Mg0.04O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4And a coating layer with a thickness of 20-50nm (coating mass: 0.5wt% -1wt%)Adding needed LATP into a beaker, dissolving in a heating constant-temperature magnetic stirrer by taking absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 114.9mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 70% after 300 cycles at the test temperature of 30 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are respectively 114.8mAh/g, 112.7mAh/g, 114.2mAh/g, 111.7mAh/g, 106.7mAh/g, 101.8mAh/g, 92.3mAh/g and 114.1 mAh/g.
Example 3:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.01:0.04, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained materialThen, Al-Ti-Mg co-doped high-pressure spinel LiNi is obtained0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.01Mg0.04O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding LATP required for 50-100nm of coating layer thickness (coating mass: 1-2 wt%) into a beaker, dissolving in a heating type constant temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 113.8mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 68 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are respectively 114.0mAh/g, 111.6mAh/g, 113.9mAh/g, 111.2mAh/g, 106.1mAh/g, 101.9mAh/g, 91.2mAh/g and 113.9 mAh/g.
Example 4:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.02:0.03, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.02Mg0.03O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 1-20nm (the coating mass is 0.001wt% -0.5wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 114.8mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 71.2 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are respectively 114.6mAh/g, 109.7mAh/g, 112.3mAh/g, 105.2mAh/g, 101.7mAh/g, 92.7mAh/g and 113.3 mAh/g.
Example 5:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.02:0.03, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.02Mg0.03O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 20-50nm (the coating mass is 0.5-1 wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The positive electrode material is assembled into a button cell (CR 20) by using the manufacturing method of the button half cell35) And the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.2mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 72.3 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 115.2mAh/g, 113.1mAh/g, 114.4mAh/g, 112.1mAh/g, 107.1mAh/g, 102.1mAh/g, 93.3mAh/g and 114.9mAh/g respectively.
Example 6:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.02:0.03, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.02Mg0.03O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding LATP required for 50-100nm of coating layer thickness (coating mass: 1-2 wt%) into a beaker, dissolving in a heating type constant temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat and a horseSintering in a muffle furnace in air atmosphere, grinding and sieving the obtained material to obtain Al-Ti-Mg co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.0mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 71.9 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 113.8mAh/g, 111.6mAh/g, 112.1mAh/g, 110.8mAh/g, 105.5mAh/g, 101.5mAh/g, 92.7mAh/g and 113.9mAh/g respectively.
Example 7:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.03:0.02, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.03Mg0.02O4。
（6）Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 1-20nm (the coating mass is 0.001wt% -0.5wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.6mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 72.9 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 115.2mAh/g, 113.3mAh/g, 115.1mAh/g, 112.2mAh/g, 107.9mAh/g, 101.8mAh/g, 94.3mAh/g and 114.4mAh/g respectively.
Example 8:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.03:0.02, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.03Mg0.02O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 20-50nm (the coating mass is 0.5-1 wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. At 0.2C and the test temperature of 30 ℃, the discharge capacity of the first circle is measured to be 133.4 mAh/g; the capacity retention rate is 77.9 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured specific discharge capacities are 135mAh/g, 134.6mAh/g, 133.1mAh/g, 131.6mAh/g, 129.1mAh/g, 124.4mAh/g, 115.5mAh/g and 133.6mAh/g respectively.
Example 9:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.03:0.02, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.03Mg0.02O4。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding LATP required for 50-100nm of coating layer thickness (coating mass: 1-2 wt%) into a beaker, dissolving in a heating type constant temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.5mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 73.8 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. The test temperature is 60 ℃ at different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1CThe measured specific discharge capacities were 114.2mAh/g, 113.3mAh/g, 114.4mAh/g, 112.1mAh/g, 107.3mAh/g, 102.5mAh/g, 92.8mAh/g, and 114.8mAh/g, respectively.
Example 10:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.04:0.01, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.04Mg0.01。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 1-20nm (the coating mass is 0.001wt% -0.5wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element is used togetherDoped and LATP coated high voltage spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.8mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 70.8 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 115.5mAh/g, 113.1mAh/g, 115.0mAh/g, 111.4mAh/g, 106.2mAh/g, 101.7mAh/g, 93.3mAh/g and 114.9mAh/g respectively.
Example 11:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.04:0.01, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.45Ti0.04Mg0.01。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding the required LATP with the thickness of a coating layer of 20-50nm (the coating mass is 0.5-1 wt%), adding the LATP into a beaker, dissolving the LATP in a heating type constant-temperature magnetic stirrer by taking absolute ethyl alcohol as a solvent, and stirring until the LATP is not dissolvedEvaporating the ethanol until the ethanol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 115.8mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 73.5 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 115.6mAh/g, 114.2mAh/g, 115.5mAh/g, 112.5mAh/g, 107.9mAh/g, 102.2mAh/g, 95.3mAh/g and 115.5mAh/g respectively.
Example 12:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into ethanol according to the mol ratio of 1:0.45:1.45:0.05:0.04:0.01, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4Positive electrode material, chemistryIs of the formula LiNi0.45Al0.05Mn1.45Ti0.04Mg0.01。
(6) Co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Adding LATP required for 50-80nm of coating layer thickness (coating mass: 1-2 wt%) into a beaker, dissolving in a heating type constant temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti-Mg element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. The discharge capacity of the first circle is measured to be 114.2mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 71.2 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured specific discharge capacities are 113.8mAh/g, 112.7mAh/g, 114.9mAh/g, 111.6mAh/g, 108.2mAh/g, 101.2mAh/g, 94.9mAh/g and 114.0mAh/g respectively.
Comparative example 1:
the procedure described in example 1 was followed for LiNi only0.5Mn1.5O4(no doping) was performed to prepare and test electrochemical properties. The discharge capacity of the first circle is measured to be 118.5mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 46.1 percent when the test temperature is 30 ℃ at 1C and the cycle is 300 circles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are respectively 119.4mAh/g, 120.2mAh/g, 119.8mAh/g, 117.8mAh/g, 114.2mAh/g, 101.5mAh/g, 75.9mAh/g and 115.6 mAh/g.
Comparative example 2:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source and a titanium source into ethanol according to the mol ratio of 1:0.45:1.47:0.05:0.03, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain the Al-Ti element co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.45Al0.05Mn1.47Ti0.03O4。
(6) The Al-Ti element co-doped high-pressure spinel LiNi obtained in the step (5)0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 20-50nm (the coating mass is 0.5-1 wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) and (4) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in an air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with the Al-Ti element and coated with the LATP0.5Mn1.5O4And (3) a positive electrode material.
The obtained Al-Ti element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.And 95V. The discharge capacity of the first circle is measured to be 128.7mAh/g at the test temperature of 30 ℃ at 0.2 ℃; the capacity retention rate is 65.3 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured specific discharge capacities are respectively 128.2mAh/g, 128.4mAh/g, 12128.2mAh/g, 125.8mAh/g, 122.8mAh/g, 113.8mAh/g, 95.8mAh/g and 126.4 mAh/g.
Comparative example 3:
(1) adding a lithium source, a nickel source and a manganese source into ethanol according to the mol ratio of 1:0.5:1.5, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) and (5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in an air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material having the chemical formula LiNi0.5Mn1.5O4。
(6) Leading the high-pressure spinel LiNi obtained in the step (5) to be0.5Mn1.5O4Adding the needed LATP with the thickness of a coating layer of 20-50nm (the coating mass is 0.5-1 wt%) into a beaker, taking absolute ethyl alcohol as a solvent, placing the mixture into a heating type constant-temperature magnetic stirrer for dissolving, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
the obtained Al-Ti element co-doped and LATP-coated high-pressure spinel LiNi0.5Mn1.5O4The button cell (CR 2035) is assembled by using the manufacturing method of the button half cell, and the charge-discharge voltage range is 3.2-4.95V. At 0.2C, a test temperature of 30 ℃ andthe first circle discharge capacity is 124.8 mAh/g; the capacity retention rate is 61.8 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 125.3mAh/g, 125.2mAh/g, 125.1mAh/g, 124.4mAh/g, 118.9mAh/g, 108.9mAh/g, 90.8mAh/g and 124.7mAh/g respectively.
TABLE 1 first-cycle discharge capacity at room temperature of example 8 of the present invention and comparative examples 1, 2 and 3
The comparison shows that the discharge specific capacity of the embodiment 8 is obviously improved compared with the discharge specific capacities of the comparative example 1 and the comparative example 2; FIG. 3 comparison of 300 cycles of data for example 8 and comparative examples 1, 2, and 3 at 1C shows that example 8 has superior capacity retention, an improvement of approximately 32% over doped and coated LNMO and an improvement of approximately 13% over Al-Ti doped and LATP coated LNMO; figure 2 comparison of the 60C high temperature rate data for example 8 and comparative examples 1, 2, and 3 shows that the 10C high rate performance improvement for example 8 is significant. The SEM image of fig. 3 also shows that the material prepared has an octahedral structure of high pressure spinel LNMO. The above results all confirm that the co-doping of the Al-Ti-Mg element can utilize the strong chemical bond energy of the Al-O bond, Ti-O bond, and Mg-O bond, and through the synergistic effect of the three elements (the strong chemical bond energy of the three elements is utilized to enhance the structural stability of the LNMO material and effectively reduce the dissolution of the transition metal in the LNMO structure) and the appropriate coating thickness of LATP, the structural stability of the material under the conditions of high temperature, high rate, and long time circulation is improved, the distortion and damage of the structure are effectively inhibited, and the side reaction of the positive electrode material and the electrolyte under the test conditions of high temperature and high rate of the battery is alleviated, thereby improving the circulation stability and the performance of high temperature and high rate.
The above-mentioned preferred embodiments, further illustrating the objects, technical solutions and advantages of the present invention, should be understood that the above-mentioned are only preferred embodiments of the present invention and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. Al-Ti-Mg element co-doped and LATP coated high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material characterized in that: the chemical formula of the anode material is LiNi0.5-aMn1.5-bAlxTiyMgzO4Wherein x is more than or equal to 0.001 and less than or equal to 0.06; y is more than or equal to 0.001 and less than or equal to 0.05; z is more than or equal to 0.001 and less than or equal to 0.05, and the LATP coating amount is 0.001-2 wt%.
2. Al-Ti-Mg co-doped and LATP-coated high-pressure spinel LiNi according to claim 10.5Mn1.5O4A positive electrode material characterized in that: x is more than or equal to 0.01 and less than or equal to 0.05; y is more than or equal to 0.01 and less than or equal to 0.04; z is more than or equal to 0.01 and less than or equal to 0.04.
3. Al-Ti-Mg co-doped and LATP-coated high-pressure spinel LiNi according to claim 10.5Mn1.5O4A positive electrode material characterized in that: the LATP coating amount is 0.01wt% to 1 wt%.
4. Al-Ti-Mg co-doped and LATP-coated high-pressure spinel LiNi according to claim 10.5Mn1.5O4A positive electrode material characterized in that: the particle size of the anode material is 0.1-30 μm, and the crystal structure is an octahedral structure.
5. Al-Ti-Mg co-doped and LATP-coated high-pressure spinel LiNi of claims 1-40.5Mn1.5O4The preparation method of the cathode material is characterized by comprising the following steps:
(1) adding a lithium source, a nickel source, a manganese source, an aluminum source, a titanium source and a magnesium source into absolute ethyl alcohol, and uniformly mixing to form a suspension;
(2) performing ball milling on the suspension obtained in the step (1) to obtain slurry;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, putting the porcelain boat into a muffle furnace, and presintering the porcelain boat in an air atmosphere to obtain Al-Ti-Mg co-doped high-pressure spinel LiNi0.5Mn1.5O4Precursor powder of a positive electrode material;
(5) putting the precursor powder obtained in the step (4) into a porcelain boat, putting the porcelain boat into a muffle furnace, carrying out secondary sintering in air atmosphere, grinding and sieving the obtained material to obtain the Al-Ti-Mg element co-doped high-pressure spinel LiNi0.5Mn1.5O4A positive electrode material;
(6) co-doping Al-Ti-Mg element obtained in the step (5) with high-pressure spinel LiNi0.5Mn1.5O4Dissolving the positive electrode material and the LATP in the coating mass range required by the thickness of the corresponding coating layer in a heating type constant-temperature magnetic stirrer by using absolute ethyl alcohol as a solvent, and stirring until the absolute ethyl alcohol is completely evaporated to obtain solid powder;
(7) putting the solid powder obtained in the step (6) into a porcelain boat, putting the porcelain boat into a muffle furnace, sintering the porcelain boat in air atmosphere, grinding and sieving the obtained material to obtain the high-pressure spinel LiNi co-doped with Al-Ti-Mg element and coated with LATP0.5Mn1.5O4And (3) a positive electrode material.
6. The method of claim 5, wherein: in the step (1), the molar ratio of corresponding elements of lithium, nickel, manganese, aluminum, titanium and magnesium in the lithium source, the nickel source, the manganese source, the aluminum source, the titanium source and the magnesium source is 1:0.45:1.45:0.05 (0.01-0.04) to (0.01-0.04).
7. The method of claim 5, wherein: in the step (4), the pre-sintering temperature is 500 ℃, the heating rate before 100 ℃ is 2 ℃/min, the heating rate between 100 ℃ and 500 ℃ is 5 ℃/min, and the sintering time is 5 hours.
8. The method of claim 5, wherein: in the step (6), the stirring speed of the heating type constant temperature magnetic stirrer is 40r/min, and the heating temperature is 120 ℃.
9. The method of claim 5, wherein: in the step (7), the sintering temperature is 950 ℃, the heating rate before 100 ℃ is 2 ℃/min, the heating rate between 100 ℃ and 950 ℃ is 5 ℃/min, and the sintering time is 5 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114335470A (en) * | 2021-12-29 | 2022-04-12 | 北京卫蓝新能源科技有限公司 | Modified positive electrode material and preparation method and application thereof |
| CN114335470B (en) * | 2021-12-29 | 2023-03-10 | 北京卫蓝新能源科技有限公司 | Modified positive electrode material and preparation method and application thereof |
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| CN115425214A (en) * | 2022-09-29 | 2022-12-02 | 合肥国轩高科动力能源有限公司 | Coating modified high-nickel ternary cathode material, and preparation method and application thereof |
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