CN118026281A - Preparation method of high-nickel positive electrode material - Google Patents
Preparation method of high-nickel positive electrode material Download PDFInfo
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- CN118026281A CN118026281A CN202410071701.8A CN202410071701A CN118026281A CN 118026281 A CN118026281 A CN 118026281A CN 202410071701 A CN202410071701 A CN 202410071701A CN 118026281 A CN118026281 A CN 118026281A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- 239000013067 intermediate product Substances 0.000 claims abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 description 18
- 238000005245 sintering Methods 0.000 description 16
- 229910004437 Li(Ni0.8Mn0.1Co0.1)O2 Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- 239000000543 intermediate Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- -1 nickel cobalt aluminum Chemical compound 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a preparation method of a high-nickel positive electrode material, and belongs to the technical field of materials. The preparation method of the high-nickel positive electrode material comprises the following steps: pre-oxidizing the high nickel hydroxide precursor by an oxidant to obtain an intermediate product; mixing the intermediate product with a lithium source, and performing heat treatment I in an oxygen-containing atmosphere to obtain a lithium-containing high-nickel oxide, namely a high-nickel anode material; the heat treatment I conditions include: the temperature is 120-300 ℃ and the time is 3-72 h. Preferably, the lithium-containing high nickel oxide is subjected to heat treatment II in an oxygen-containing atmosphere to obtain a high nickel cathode material, wherein the heat treatment II comprises the following conditions: 700-950 ℃ and 0.05-1 h. The preparation method can obviously reduce the high-temperature requirement of the synthesized high-nickel positive electrode material, has low energy consumption and low production cost, is compatible with the existing production equipment, is suitable for large-scale production, and the obtained high-nickel positive electrode material has the electrochemical performance equivalent to that of the material prepared by the traditional method.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a preparation method of a high-nickel positive electrode material.
Background
With the development and technological progress of human society, electric power becomes an important material foundation for the modern society industry and life. The lithium ion battery plays an important role in the fields of portable equipment, new energy automobiles and the like as a chargeable and dischargeable battery with the highest market share. The positive electrode material occupies about 40% of the manufacturing cost of the lithium ion battery, and thus it plays a decisive role in the cost of the entire battery. The performance and price of the positive electrode material directly affect the performance and cost of the lithium battery. Therefore, the positive electrode material plays a very important role in the lithium battery, and plays an important leading role in the development of the lithium battery industry. Among them, a high-nickel ternary lithium ion battery has been attracting attention in recent years due to its high energy density.
Common high-nickel ternary positive electrode materials are generally prepared by sintering hydroxide precursor mixed lithium salt for a long time (more than or equal to 10 hours) or even for multiple times under the condition of high-temperature (750-850 ℃) pure oxygen. The traditional high-temperature solid phase synthesis method needs to consume more water, electricity and oxygen, and the complicated and severe production process has higher requirements on equipment, and the labor and manufacturing cost are higher than those of the middle-low nickel ternary material. In addition, the yield of the high-nickel ternary material produced by the method is low, and the loss of raw materials is increased. These factors all greatly increase the production cost of the high nickel ternary cathode material. Therefore, the low-temperature preparation method for developing the high-nickel ternary material can greatly reduce the production cost of the material and is beneficial to industrial development.
Disclosure of Invention
In view of the above, the application provides a preparation method of a high-nickel cathode material, and mainly aims to solve the technical problems of high energy consumption and high cost of a high-temperature solid phase synthesis method of the high-nickel cathode material.
In one aspect, the application provides a method for preparing a high nickel positive electrode material, which comprises the following steps:
S1: pre-oxidizing the high nickel hydroxide precursor by an oxidant to obtain an intermediate product;
s2: mixing the intermediate product with a lithium source, and performing heat treatment I in an oxygen-containing atmosphere to obtain a lithium-containing high-nickel oxide, namely a high-nickel anode material; the conditions for the heat treatment I include: the temperature is 120-300 ℃ and the time is 3-72 h.
Optionally, the preparation method further includes step S3 after step S2: the lithium-containing high nickel oxide in the step S2 is subjected to heat treatment II in an oxygen-containing atmosphere to obtain the high nickel anode material; the conditions for heat treatment II include: the temperature is 700-950 ℃ and the time is 0.05-1 h.
The performance of the lithium-containing high-nickel oxide of the step S2 product in the preparation method can be used for high-nickel anode materials; and when the lithium-containing high-nickel oxide is subjected to further short-time high-temperature annealing in the step S3, the electrochemical performance of the lithium-containing high-nickel oxide for the high-nickel positive electrode material is better.
Optionally, the temperature of the heat treatment I is selected from any value or a range of values between any two of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃,250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃;
The time of the heat treatment I is selected from any value or a range value between any two of 3h, 5h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h and 72 h;
Optionally, the temperature of the heat treatment II is selected from any value in 700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃、810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃、900℃、910℃、920℃、930℃、940℃、950℃ or a range of values between any two;
Optionally, the time of the heat treatment II is selected from any value in 0.05h、0.1h、0.15h、0.2h、0.25h、0.3h、0.35h、0.4h、0.45h、0.5h、0.55h、0.6h、0.65h、0.7h、0.75h、0.8h、0.85h、0.9h、0.95h、1h or a range of values between any two.
Optionally, in step S1, the oxidizing agent is at least one selected from sodium hypochlorite, sodium thiosulfate, hydrogen peroxide, potassium permanganate and potassium dichromate. The oxidant can also be selected from other applicable substances according to actual needs.
Optionally, in step S1, the pre-oxidizing conditions include:
the temperature is 25-80 ℃ and the time is 0.5-12 h;
optionally, the oxidizing agent oxidizes the high nickel hydroxide in an aqueous solution.
Optionally, the pre-oxidation temperature is selected from any value or range of values between any two of 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃,55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃;
the pre-oxidation time is selected from any value or range of values between any two of 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and 12h.
Optionally, in step S2, the lithium source is selected from lithium salts; the lithium salt is selected from lithium hydroxide and/or lithium carbonate. The lithium salt may be selected from other materials as needed.
Optionally, in step S2, the molar ratio of the lithium content in the lithium source to the metal content in the high nickel hydroxide precursor is 1.0 to 1.1.
Optionally, the molar ratio of the lithium content in the lithium source to the metal content in the high nickel hydroxide precursor is selected from any value or range of values between any two of 1, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1.
Optionally, in step S2, the oxygen-containing atmosphere includes an atmosphere containing oxygen with a volume fraction of 10% or more or an oxygen atmosphere.
Optionally, in step S2, the atmosphere containing oxygen in an amount of 10% or more by volume includes air or an atmospheric environment.
Optionally, in step S3, the oxygen-containing atmosphere is an oxygen atmosphere.
Optionally, in step S1, the high nickel hydroxide precursor is a high nickel ternary hydroxide precursor or a high nickel quaternary hydroxide precursor.
The high nickel hydroxide precursor of the application can be NiCoMn, niCoAl and other common ternary products, and is also applicable to NiCoMnAl and the like.
Optionally, in step S1, the metal hydroxide in the high nickel hydroxide precursor is a transition metal hydroxide; the metals in the metal hydroxides may be transition metals, or may include some non-transition metals, such as nickel cobalt aluminum.
Optionally, in step S1, the high nickel hydroxide precursor has a molecular formula:
(NiαMnβCoγ)(OH)2；
Wherein, alpha+beta+gamma=1 and 1 is more than or equal to alpha and more than or equal to 0.6.
The high nickel hydroxide precursor of the application is available in the market in the prior art.
Optionally, in step S3, the high-nickel cathode material is the high-nickel ternary cathode material, and the molecular formula of the high-nickel ternary cathode material is formula I:
Li (Ni αMnβCoγ)O2 formula I;
Wherein, alpha+beta+gamma=1 and 1 is more than or equal to alpha and more than or equal to 0.6.
Optionally, in step S3, the morphology of the high-nickel cathode material is a platelet cluster-shaped spherical secondary particle.
The high-nickel ternary positive electrode material is in the prior art.
The application provides a specific preparation method of a high-nickel layered anode material, which comprises the following steps:
(1) Pre-oxidation: adding proper amount of oxidant and high nickel hydroxide precursor into proper amount of deionized water, stirring at constant temperature, and fully performing oxidation reaction; stirring at 300-2000rpm and 25-80 deg.c for 0.5-12 hr; separating and drying after the reaction to obtain pre-oxidized intermediate powder;
the low-temperature pre-oxidation adopts an oxidant to pre-oxidize the transition metal hydroxide in an aqueous solution, so that divalent nickel is oxidized into trivalent nickel, divalent manganese is oxidized into tetravalent manganese, and divalent cobalt is oxidized into tetravalent cobalt; the selected oxidizing agents include, but are not limited to, sodium hypochlorite, sodium thiosulfate, hydrogen peroxide, potassium permanganate, potassium dichromate and the like;
(2) And (3) sintering at low temperature: uniformly mixing the prepared intermediate powder with a proper amount of lithium salt, and placing the mixture in a muffle furnace for low-temperature sintering to obtain the lithium-containing layered transition metal oxide with poor crystallinity; the molar ratio of the lithium content in the lithium salt to the transition metal content in the precursor is 1.0-1.1; the sintering temperature is 120-300 ℃, and the heat preservation time is 3-72 hours; the lithium salts used include, but are not limited to, lithium hydroxide, lithium carbonate; the sintering atmosphere is air or oxygen;
(3) High-temperature annealing: the obtained lithium-containing layered transition metal oxide with poor crystallinity is placed in a muffle furnace to be annealed at a short time and high temperature in an oxygen atmosphere, so that the crystallinity of the lithium-containing layered transition metal oxide is improved; the annealing temperature is 700-950 ℃ and the annealing time is 0.05-1 hour.
In a second aspect, the application provides a high nickel ternary cathode material, which is prepared by the method.
In a third aspect, the present application provides a lithium battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte; the active material of the positive electrode comprises the high-nickel positive electrode material prepared by the method.
Compared with the prior art, the application has the following beneficial effects:
(1) The preparation method can obviously reduce the high-temperature requirement of the synthesized high-nickel anode material, has low energy consumption and reduces the production cost.
(2) The preparation method provided by the application is compatible with the existing production equipment, and is suitable for large-scale production.
(3) The high-nickel positive electrode material obtained by the preparation method has the electrochemical performance equivalent to that of the material prepared by the traditional method.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the high nickel hydroxide precursor (Ni 0.8Mn0.1Co0.1)(OH)2, pre-oxidized intermediates, and final product Li (Ni 0.8Mn0.1Co0.1)O2;
FIG. 2 is a scanning electron microscope image of the pre-oxidized intermediate in example 1 of the present application, with the scale being 2 microns;
FIG. 3 is a scanning electron microscope image of the final product Li (Ni 0.8Mn0.1Co0.1)O2, scale 2 μm) in example 1 of the present application;
Fig. 4 is a graph showing the first-turn charge-discharge curves of the final product Li (Ni 0.8Mn0.1Co0.1)O2 and commercial polycrystalline Li (Ni 0.8Mn0.1Co0.1)O2;
FIG. 5 is a cycle stability test of the final product Li (Ni 0.8Mn0.1Co0.1)O2 at 0.5C) in example 2 of the present application.
Detailed Description
The application will be further illustrated with reference to specific examples. The following description is given of several embodiments of the present application and is not intended to limit the application in any way, and although the application is disclosed in the preferred embodiments, it is not intended to limit the application, and any person skilled in the art will make some changes or modifications with the technical content disclosed in the above description equivalent to the equivalent embodiments without departing from the scope of the technical solution of the present application.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially and used without any particular treatment.
Example 1
(1) Pre-oxidation: adding 2g of oxidant sodium persulfate into 150mL of deionized water, stirring for 5 minutes in a magnetic stirring table, and keeping the stirring speed at 500 rpm for full dissolution; 4g of a high nickel ternary hydroxide precursor (Ni 0.8Mn0.1Co0.1)(OH)2 was added to the above solution, a beaker containing the mixed suspension was placed in a magnetic stirring water bath reactor, the stirring speed was kept at 500 rpm, the temperature was kept at 55℃for 4 hours, and the reaction was placed in a vacuum oven for overnight drying, the temperature was kept at 80℃to obtain an intermediate powder.
(2) And (3) sintering at low temperature: and (3) fully grinding 1g of the intermediate powder and 0.24g of lithium hydroxide, putting into a corundum crucible, sintering at a low temperature in a box-type muffle furnace, keeping the sintering temperature at 150 ℃, and reacting for 12 hours to obtain the lithium-containing layered transition metal oxide with poor crystallinity.
(3) High-temperature annealing: transferring the corundum crucible into a tube furnace in oxygen atmosphere for high-temperature annealing; the annealing temperature is 800 ℃, the annealing time is 30 minutes, and the final high-nickel ternary cathode material Li (Ni 0.8Mn0.1Co0.1)O2) is obtained.
The high nickel hydroxide precursor (Ni 0.8Mn0.1Co0.1)(OH)2, pre-oxidized intermediate, and final product Li (Ni 0.8Mn0.1Co0.1)O2) in example 1 was subjected to X-ray powder diffraction detection, and the detection results are shown in fig. 1.
The pre-oxidized intermediate and final product Li (Ni 0.8Mn0.1Co0.1)O2) in example 1 were subjected to scanning electron microscopy, and the detection results are shown in fig. 2 and 3.
Example 2
(1) Pre-oxidation: adding 2g of oxidant sodium persulfate into 150mL of deionized water, stirring for 5 minutes in a magnetic stirring table, and keeping the stirring speed at 500 rpm for full dissolution; 4g of a high nickel ternary hydroxide precursor (Ni 0.9Mn0.05Co0.05)(OH)2 was added to the above solution, a beaker containing the mixed suspension was placed in a magnetic stirring water bath reactor, the stirring speed was kept at 500 rpm, the temperature was kept at 55℃for 4 hours, and the reaction was placed in a vacuum oven for overnight drying, the temperature was kept at 80℃to obtain an intermediate powder.
(2) And (3) sintering at low temperature: and (3) fully grinding 1g of the intermediate powder and 0.24g of lithium hydroxide, putting into a corundum crucible, sintering at a low temperature in a box-type muffle furnace, keeping the sintering temperature at 150 ℃, and reacting for 12 hours to obtain the lithium-containing layered transition metal oxide with poor crystallinity.
(3) High-temperature annealing: transferring the corundum crucible into a tube furnace in oxygen atmosphere for high-temperature annealing; the annealing temperature is 800 ℃, the annealing time is 30 minutes, and the final high-nickel ternary cathode material Li (Ni 0.9Mn0.05Co0.05)O2) is obtained.
Example 3
(1) Pre-oxidation: adding 2g of oxidant hydrogen peroxide into 150mL of deionized water, stirring for 5 minutes in a magnetic stirring table, and keeping the stirring speed at 500 rpm for full dissolution; 4g of a high nickel ternary hydroxide precursor (Ni 0.9Mn0.05Co0.05)(OH)2 was added to the above solution, a beaker containing the mixed suspension was placed in a magnetic stirring water bath reactor, the stirring speed was kept at 500 rpm, the temperature was kept at 55℃for 4 hours, and the reaction was placed in a vacuum oven for overnight drying, the temperature was kept at 80℃to obtain an intermediate powder.
(2) And (3) sintering at low temperature: 1g of intermediate powder and 0.24g of lithium hydroxide are fully ground, the mixture is put into a corundum crucible, sintered at a low temperature in a box-type muffle furnace, the sintering temperature is kept at 150 ℃, and the mixture reacts for 12 hours to obtain the lithium-containing layered transition metal oxide with poor crystallinity.
(3) High-temperature annealing: the corundum crucible is further transferred into a tube furnace in an oxygen atmosphere for high-temperature annealing. The annealing temperature is 800 ℃, the annealing time is 30 minutes, and the final high-nickel ternary cathode material Li (Ni 0.9Mn0.05Co0.05)O2) is obtained.
Example 4 (testing the electrochemical Properties of the cathode Material of example 1)
The high nickel ternary cathode material prepared in example 1 was made into a pole piece and assembled into a button cell for electrochemical testing, specifically the following steps:
(1) The conductive carbon black (ACETYLENE BLACK) and the high nickel ternary cathode material obtained in example 1 were dried in a vacuum oven at a temperature of 80 ℃ for 0.5 hours. The dried conductive carbon black and the positive electrode material are uniformly mixed in a mortar, and are transferred to a slurry mixing container together with a pre-prepared polyvinylidene fluoride (PVDF) solution. Wherein the mass ratio of PVDF to N-methylpyrrolidone (NMP) in the PVDF solution is 1:24, a step of detecting the position of the base; the mass ratio of the conductive carbon black to PVDF of the positive electrode material is 8:1:1.
(2) Placing the slurry mixing container into a defoaming stirrer, and setting the procedures of stirring for 19 minutes (mixing) and defoaming for 1 minute (defoaming); transferring the mixed slurry to an aluminum foil, and uniformly coating by using a 200 mu m coating scraper; drying in a vacuum oven at 105deg.C overnight.
(3) And (3) battery assembly: in a glove box protected by argon, a metal lithium is used as a negative electrode to be matched with a prepared positive electrode plate, and a model 2032 button cell is assembled by adopting a TINCEL electrolyte and a Celgard 2500 diaphragm.
(4) Electrochemical testing: performing charge and discharge test on the assembled battery in a new Wei battery test cabinet, wherein the voltage range is 3.0-4.4V (vs Li/Li+), and the current is 0.2C and 0.5C (1C=200mAg-1); the detection results are shown in fig. 4 and 5.
The present application uses commercial polycrystalline Li (Ni 0.8Mn0.1Co0.1)O2 as a control, electrodes and assembled cells were prepared under the same conditions, and electrochemical tests were performed under the same conditions, the results of which are shown in fig. 4.
As can be seen from the comparison of fig. 4: the high-nickel ternary cathode material Li (Ni 0.8Mn0.1Co0.1)O2 and the polycrystalline Li (Ni 0.8Mn0.1Co0.1)O2) used in commercialization (811) at present have similar charge-discharge curve shapes, which shows that the electrochemical properties of the two materials are similar, and further proves that the electrochemical properties of the commercial polycrystalline Li (Ni 0.8Mn0.1Co0.1)O2) can be completely achieved by the high-nickel ternary cathode material (Li (αMnβCoγ)O2, alpha+beta+gamma=1, alpha > 0.6) synthesized by the innovative method of pre-oxidizing a high-nickel hydroxide precursor with an oxidant (25-80 ℃ for 0.5-12 h), then sintering the high-nickel ternary cathode material at low temperature (120-300 ℃ for 3-72 h) and finally annealing the high-nickel ternary cathode material at high temperature (700-950 ℃ for 0.05-1 h).
As shown in the test results of FIG. 5, the capacity retention rate of the high-nickel ternary cathode material Li (Ni 0.8Mn0.1Co0.1)O2 after 75 cycles of 0.5C charge and discharge) prepared in the embodiment 1 of the application reaches 90.9%, which shows that the material has stable performance and is suitable for the positive-stage material of the lithium battery.
Comparative example 1 (traditional high temperature solid phase Synthesis method)
And mixing the high-nickel ternary positive electrode material precursor with a lithium source in a molar ratio of 1:1, and performing sintering treatment at 800 ℃ for 17 hours to obtain the high-nickel ternary positive electrode material.
Comparative example 1 the same electrochemical performance test method as example 1 material: the electrode and assembled cell were prepared under the same conditions and electrochemical tests were performed under the same conditions.
Test results: the positive electrode material prepared in comparative example 1 has a capacity retention rate of less than 90% after 75 cycles of charge and discharge test.
As is clear from comparison, the total time from pre-oxidation, low-temperature sintering and high-temperature annealing in the preparation of the positive electrode material is 16.5 hours, the heat treatment of the positive electrode material in the comparative example 1 is 17 hours at 800 ℃, the high-temperature sintering time of the positive electrode material in the application is only 30 minutes at 800 ℃, compared with the whole heat, the heat loss of the embodiment 1 of the application is far smaller than that of the comparative example 1, the heat treatment time of the embodiment 1 is similar to that of the comparative example 1, but the electrochemical performance of the anode material prepared by the application is better than that of the comparative example 1; further proved by the application, compared with the traditional high-temperature solid phase synthesis method, the preparation method has smaller heat loss, lower cost and better product performance under similar heat treatment time.
Comparative example 2
And mixing the precursor of the high-nickel ternary positive electrode material with a lithium source in a molar ratio of 1:1, and performing sintering treatment at 800 ℃ for 22 hours to obtain the high-nickel ternary positive electrode material.
Comparative example 2 the same electrochemical performance test method as example 1 material: the electrode and assembled cell were prepared under the same conditions and electrochemical tests were performed under the same conditions.
Test results: the charge-discharge performance of the positive electrode material prepared in comparative example 2 was similar to that of the positive electrode material of example 1 of the present application; the electrochemical performance of the positive electrode material prepared under the conditions of low heat loss and short heat treatment time is similar to that of the positive electrode material prepared under the conditions of high heat loss and long heat treatment time in comparative example 2; it was further demonstrated that the present application has less heat loss and shorter heat treatment time than comparative example 2 in the case of obtaining a cathode material of similar properties, which generally reduces the production cost and energy consumption of the cathode material.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The preparation method of the high-nickel positive electrode material is characterized by comprising the following steps of:
S1: pre-oxidizing the high nickel hydroxide precursor by an oxidant to obtain an intermediate product;
S2: mixing the intermediate product with a lithium source, and performing heat treatment I in an oxygen-containing atmosphere to obtain a lithium-containing high-nickel oxide, namely a high-nickel anode material;
wherein the conditions of the heat treatment I include: the temperature is 120-300 ℃ and the time is 3-72 h.
2. The method for preparing a high nickel positive electrode material according to claim 1, further comprising step S3 after step S2: the lithium-containing high nickel oxide in the step S2 is subjected to heat treatment II in an oxygen-containing atmosphere to obtain the high nickel anode material;
Wherein the conditions of the heat treatment II include: the temperature is 700-950 ℃ and the time is 0.05-1 h.
3. The method for preparing a high nickel anode material according to claim 1, wherein in step S1, the oxidizing agent is at least one selected from the group consisting of sodium hypochlorite, sodium thiosulfate, hydrogen peroxide, potassium permanganate and potassium dichromate.
4. The method for preparing a high nickel positive electrode material according to claim 1, wherein in step S1, the pre-oxidation conditions include: the temperature is 25-80 ℃ and the time is 0.5-12 h.
5. The method for producing a high nickel positive electrode material according to claim 1, wherein in step S2, the lithium source is selected from lithium hydroxide and/or lithium carbonate.
6. The method for producing a high nickel positive electrode material according to claim 1, wherein in step S2, a molar ratio of a lithium content in the lithium source to a metal content in the high nickel hydroxide precursor is 1.0 to 1.1.
7. The method for producing a high nickel positive electrode material according to claim 2, wherein in step S2, the oxygen-containing atmosphere includes an atmosphere containing oxygen in an amount of 10% or more by volume or an oxygen atmosphere;
Preferably, in step S3, the oxygen-containing atmosphere is an oxygen atmosphere;
Preferably, in step S1, the oxidizing agent oxidizes the high nickel hydroxide in an aqueous solution.
8. The method for preparing a high nickel positive electrode material according to claim 1, wherein in step S1, the high nickel hydroxide precursor is a high nickel ternary hydroxide precursor;
Preferably, in step S1, the metal hydroxide in the high nickel hydroxide precursor is a transition metal hydroxide.
9. The method for preparing a high-nickel positive electrode material according to claim 1, wherein in step S3, the high-nickel positive electrode material is a high-nickel ternary positive electrode material, and the molecular formula is as follows:
Li (Ni αMnβCoγ)O2 formula I;
Wherein, alpha+beta+gamma=1 and 1 is more than or equal to alpha and more than or equal to 0.6.
10. The method for preparing a high-nickel positive electrode material according to claim 1, wherein in the step S3, the morphology of the high-nickel positive electrode material is a spherical secondary particle in a form of a lamellar cluster.
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