CN114142037A - Method for preparing ultra-high nickel anode material by adopting gradient lithium supplement and prepared ultra-high nickel anode material - Google Patents
Method for preparing ultra-high nickel anode material by adopting gradient lithium supplement and prepared ultra-high nickel anode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 115
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000013589 supplement Substances 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910013485 LiNixM1-xO2 Inorganic materials 0.000 claims description 6
- 229910013495 LiNixM1−xO2 Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000005406 washing Methods 0.000 abstract description 16
- 229910001868 water Inorganic materials 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical compound O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a method for preparing an ultra-high nickel anode material by adopting gradient lithium supplement and the prepared ultra-high nickel anode material, which are prepared by adopting a precursor, a lithium source and a doped coating substance. The traditional high nickel material generally adopts a water washing process to reduce the residual lithium on the surface of the material, but Li can be generated in the water washing process+/H+Exchange, impurities forming a MOOH phase on the surface of the material further form a MO phase after drying, which may result in an increase in charge resistance of the material, decrease in capacity of the material, and cause a reduction in cycle life of the material. The gradient lithium supplement method of the waterless washing process effectively solves the problem of high residual alkalinity on the surface of the ultra-high nickel material and effectively improves the problem of poor cycle performance of the ultra-high nickel material. Meanwhile, the process flow of the ultra-high nickel material prepared by the method is simple,the production cost can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a method for preparing an ultra-high nickel anode material by adopting gradient lithium supplement and the prepared ultra-high nickel anode material.
Background
With the improvement of the electric automobile endurance mileage, the quick charging technology and the safety of the electric automobile in the market, the lithium ion battery matched with the electric automobile is required to have higher energy density, large rate capability, high safety and long cycle service life. The high-nickel ternary positive electrode material in the current market has the advantages of high specific capacity, long cycle life and the like, and becomes a main positive electrode material in the market.
With the increase of Ni content, the cycle performance of the battery is deteriorated, the thermal stability and safety performance of the material are deteriorated, and LiNi is deteriorated during storagexCoyMnzO2Materials, especially X>Above 0.8 is easy to react with CO in air2And H2O reacts to generate Li on the surface of the material2CO3And LiOH. The generation of residual alkali not only makes the electrode easy to react with PVDF in the process of homogenizing the electrode, and increases the viscosity of slurry to cause gel, but also causes the increase of gas generation in the process of electrochemical reaction, thereby bringing about the potential safety hazard of the battery.
At present, the residual alkali on the surface of the ternary material is mainly reduced by adopting a water washing process in the industry, but Li in the surface layer of the ternary material can generate proton exchange with water in the water washing process, so that the performances of the material, such as capacity, circulation and the like, are deteriorated; meanwhile, the surface structure of the material is damaged by water washing, the specific surface area of the material is increased, side reactions of the material and electrolyte are increased, and the attenuation of the battery is accelerated. Meanwhile, in order to reduce the negative effects of water washing, the product after water washing needs to be subjected to heat treatment or coating to repair the surface structure of the material, but the process difficulty is increased and the processing cost is increased by the measure.
In addition, the roasting of the high-nickel material adopts a one-time lithium preparation method, and in the traditional one-time lithium preparation method, the high-temperature sintering can cause the volatilization of Li, so that the phenomenon of poor lithium is generated, and Ni is enabled to be2+With Li+And (4) mixing and discharging product cations. And because of the currently used oxyhydrogenThe loose packing density of lithium is low, so that the loading amount of materials is low in the roasting process, and the consistency of the roasted materials is poor.
The patent of CN109802123A discloses that a lithium source is added into an aqueous solution, and then the material is coated after being dried and baked to finally obtain a modified high-nickel cathode material. However, in the course of this method, H+/Li+Resulting in Li in the material lattice+And the dissolution of transition metal ions, seriously damaging the surface structure of the material. The patent of CN108878863A discloses that a lithium source is added into absolute ethyl alcohol to wash and coat the material, and then the material is sintered to obtain a high nickel cathode material. However, in this method, ethanol is used to wash the high nickel material, but the solubility of the alcohol solvent to lithium carbonate is very low, and the cost is high.
Therefore, the method develops a simple and easy technology which is convenient for industrialization, reduces the influence of the residual alkali on the surface of the ultra-high nickel material on the service performance of the battery, and has important economic value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing an ultra-high nickel cathode material by adopting gradient lithium supplement and the prepared ultra-high nickel cathode material, thereby simplifying the washing process in the preparation engineering; the process of the gradient lithium supplement is adopted, the problem of residual alkali on the surface of the ultra-high nickel material is effectively solved, the box loading amount of the material in the production process is increased, and the discharge capacity and the cycle retention rate of the high nickel material are increased. The method has the characteristics of simplicity, feasibility and low cost, and has wide application prospect.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing an ultra-high nickel cathode material by adopting gradient lithium supplement is disclosed, wherein the cathode material is prepared from a precursor, a lithium source and a coating substance, and the steps are as follows:
(1) preparation of substrate a: mixing a precursor containing Ni and a lithium-containing compound according to a molar ratio of 1: 0.5-0.9, uniformly mixing, and roasting at the temperature of 450-650 ℃ to obtain a base material A;
(2) the substrate A and the lithium-containing compound are mixed according to a molar ratio of 1: uniformly mixing the raw materials in a ratio of 0.1-0.5, supplementing lithium for the second time, and roasting the mixture at the temperature of 500-800 ℃ to obtain a mixture B;
(3) uniformly mixing the coating substance with the mixture B according to the mass ratio of 0.5-5%, roasting, and crushing to obtain the final ultra-high nickel cathode material LiNixM1-xO2Wherein the coating substance contains one of elements of Ti, Al, Mg, Si, B, Ba and Ce.
The chemical general formula of the precursor in the step (1) is NixM1-X(OH)2,Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
The molecular formula of the ultra-high nickel anode material is LiNixM1-xO2Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
In the step (1), the lithium-containing compound is any one or a combination of several of lithium carbonate, lithium hydroxide, lithium oxide, lithium nitrate, lithium acetate, lithium sulfate and lithium chloride.
The roasting temperature of the step (1) is 450-650 ℃, the roasting time is 2-20 h, and the heating rate is 1.0-5.0 ℃/min.
In the step (2), the roasting temperature is 500-800 ℃, the roasting time is 8-30 h, and the heating rate is 1.0-5.0 ℃/min.
In the step (3), the roasting temperature is 200-800 ℃, the roasting time is 2-20 h, and the heating rate is 1.0-5.0 ℃/min.
The ultrahigh nickel cathode material is prepared by the method for preparing the ultrahigh nickel cathode material by adopting the gradient lithium supplement.
The invention has the beneficial effects that:
(1) compared with the traditional primary high-temperature sintering process, the gradient lithium supplement technology adopted by the invention has the advantages that the lithium is deficient for the first time, the free lithium can be effectively inhibited from being enriched on the surface of the material, the lithium ions can be effectively and rapidly diffused into the crystal through secondary lithium supplement sintering, the enrichment of the lithium on the surface of the material is greatly reduced, the purpose of reducing the residual alkali on the surface of the high-nickel anode material is realized, the stability and the processing performance of the anode slurry are improved, the problem of gas generation in the use process of the obtained battery can be effectively inhibited by adopting the anode slurry, and the safety performance of the battery is improved. Meanwhile, the problems of low product loading amount and poor product roasting consistency are solved.
(2) Compared with the existing high-nickel material washing process, the gradient lithium supplementing technology adopted by the invention solves the problems of material capacity, circulation and other performance deterioration caused by the damage of the surface structure of the material due to the washing process, simplifies the process flow, realizes the washing-free process of the ultra-high-nickel anode material and reduces the production cost.
Drawings
FIG. 1 is a view showing LiNi in comparative example 10.92Co0.4Mn0.4O2SEM image of the positive electrode material.
FIG. 2 is an alumina-coated LiNi of example 10.92Co0.4Mn0.4O2SEM image of the positive electrode material.
FIG. 3 is a boron oxide-coated LiNi of example 30.9Co0.6Mn0.4O2SEM image of the positive electrode material.
FIG. 4 is a graph comparing the first charge/discharge point curves of example 3 and comparative example 2.
Fig. 5 is a graph comparing charge and discharge cycles of example 3 and comparative example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
The invention discloses a method for preparing an ultra-high nickel cathode material by gradient lithium supplement, wherein the cathode material is prepared from a precursor, a lithium source and a coating substance, and the steps are as follows:
(1) preparation of substrate a: mixing a precursor containing Ni and a lithium-containing compound according to a molar ratio of 1: 0.5-0.9, uniformly mixing, and roasting at the temperature of 450-650 ℃ to obtain a base material A;
(2) the substrate A and the lithium-containing compound are mixed according to a molar ratio of 1: uniformly mixing the raw materials in a ratio of 0.1-0.5, supplementing lithium for the second time, and roasting the mixture at the temperature of 500-800 ℃ to obtain a mixture B;
(3) uniformly mixing the coating substance with the mixture B according to the mass ratio of 0.5-5%, roasting, and crushing to obtain the final ultra-high nickel cathode material LiNixM1-xO2Wherein the coating substance contains one of elements of Ti, Al, Mg, Si, B, Ba and Ce.
The chemical general formula of the precursor in the step (1) is NixM1-X(OH)2,Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
The molecular formula of the ultra-high nickel anode material is LiNixM1-xO2Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
In the step (1), the lithium-containing compound is any one or a combination of several of lithium carbonate, lithium hydroxide, lithium oxide, lithium nitrate, lithium acetate, lithium sulfate and lithium chloride.
The roasting temperature of the step (1) is 450-650 ℃, the roasting time is 2-20 h, and the heating rate is 1.0-5.0 ℃/min.
In the step (2), the roasting temperature is 500-800 ℃, the roasting time is 8-30 h, and the heating rate is 1.0-5.0 ℃/min.
In the step (3), the roasting temperature is 200-800 ℃, the roasting time is 2-20 h, and the heating rate is 1.0-5.0 ℃/min.
The ultrahigh nickel cathode material is prepared by the method for preparing the ultrahigh nickel cathode material by adopting the gradient lithium supplement.
Comparative example 1
1000g of Ni0.92Co0.04Mn0.04(OH)2And 472g of LiOH. H2O, placing the mixture in a box type furnace,roasting at 780 ℃ for 15h, wherein the heating rate is 2.5 ℃/min, and the oxygen flow is 6m3And h, crushing and sieving the mixed material after roasting to obtain LiNi0.92Co0.04Mn0.04O2.And (3) a positive electrode material. FIG. 1 shows that LiNi was obtained as described above0.92Co0.04Mn0.04O2The surface of the positive electrode material is smooth and round as seen in the SEM image.
Comparative example 2
1000g of Ni0.96Co0.02Mn0.02(OH)2And 468g of LiOH. H2O is evenly mixed, the mixture is placed in a box type furnace and roasted for 12 hours at the temperature of 720 ℃, the heating rate is 2.5 ℃/min, the oxygen flow is 6m3And h, crushing and sieving the mixed material after roasting to obtain LiNi0.96Co0.02Mn0.02O2And (3) a positive electrode material.
500g of LiNi will be obtained0.96Co0.02Mn0.02O2Adding the anode material into 500g of deionized water, fully stirring for 5min at the stirring speed of 300r/min, separating solid from liquid by a vacuum pump, and drying in a vacuum oven at 120 ℃ for 4h to obtain a sample after washing.
Mixing 500g of the dried sample with 5g H3BO3After uniform mixing, the mixture is placed in a box-type furnace and roasted for 6h at 350 ℃, the heating rate is 2.5 ℃/min, the oxygen flow is 6m3And h, sieving the roasted material with a 325-mesh sieve to obtain the boron oxide coated LiNi0.96Co0.02Mn0.02O2And (3) a positive electrode material.
Example 1
(1) 1000g of Ni0.92Co0.04Mn0.04(OH)2And 227.72 gLiOH. H2O is evenly mixed, the mixture is placed in a box type furnace and roasted for 6h at the temperature of 550 ℃, the heating rate is 2.5 ℃/min, and the oxygen flow is 6m3H, crushing and mixing the mixed material after roasting to obtain Li0.5Ni0.92Co0.04Mn0.04O2And (3) a positive electrode material.
(2) Mixing the base material Li0.5Ni0.92Co0.04Mn0.04O2And 227.72 gLiOH. H2Mixing O, placing the mixture in a box furnace, roasting at 750 deg.C for 12 hr, heating at 2.5 deg.C/min, and oxygen flow of 6m3And h, crushing the mixed material after roasting to obtain LiNi0.92Co0.04Mn0.04O2And (3) a positive electrode material.
(3) 1000g of LiNi0.92Co0.04Mn0.04O2And 10g of Al2O3After uniform mixing, the mixture is placed in a box-type furnace and roasted for 6h at the temperature of 600 ℃, the heating rate is 2.5 ℃/min, and the oxygen flow is 6m3And h, sieving the roasted material with a 325-mesh sieve to obtain the alumina-coated LiNi0.92Co0.04Mn0.04O2And (3) a positive electrode material.
(4) FIG. 1 shows the above-mentioned LiNi coated with alumina0.92Co0.4Mn0.4O2The SEM image of the cathode material shows that the surface of the cathode material is provided with a dense coating layer.
Example 2
(1) 1000g of Ni0.9Co0.06Mn0.04(OH)2And 408.7g of LiOH. H2O is evenly mixed, the mixture is placed in a box type furnace and roasted for 6h at the temperature of 550 ℃, the heating rate is 2.5 ℃/min, and the oxygen flow is 6m3H, crushing and mixing the mixed material after roasting to obtain Li0.9Ni0.9Co0.06Mn0.04O2And (3) a positive electrode material.
(2) Mixing the base material Li0.9Ni0.9Co0.06Mn0.04O2And 46.8g of LiOH. H2Mixing O, placing the mixture in a box furnace, roasting at 750 deg.C for 12 hr, heating at 2.5 deg.C/min, and oxygen flow of 6m3And h, crushing the mixed material after roasting to obtain LiNi0.9Co0.06Mn0.04O2And (3) a positive electrode material.
(3) 1000g of LiNi0.9Co0.06Mn0.04O2With 15g TiO2After being mixed evenlyPlacing the mixture in a box furnace, roasting at 550 deg.C for 6h, with a heating rate of 2.5 deg.C/min and an oxygen flow of 6m3And h, sieving the roasted material with a 325-mesh sieve to obtain the titanium oxide coated LiNi0.9Co0.06Mn0.04O2And (3) a positive electrode material.
Example 3
(1) 1000g of Ni0.96Co0.02Mn0.02(OH)2And 409.8 gLiOH. H2O is evenly mixed, the mixture is placed in a box type furnace and roasted for 6h at the temperature of 600 ℃, the heating rate is 2.5 ℃/min, the oxygen flow is 6m3H, crushing and mixing the mixed material after roasting to obtain Li0.9Ni0.96Co0.02Mn0.02O2Positive electrode material
(2) Mixing the base material Li0.9Ni0.96Co0.02Mn0.02O2And 45.5g of LiOH. H2O is evenly mixed, the mixture is placed in a box type furnace and roasted for 12 hours at the temperature of 720 ℃, the heating rate is 2.5 ℃/min, the oxygen flow is 6m3And h, crushing the mixed material after roasting to obtain LiNi0.96Co0.02Mn0.02O2And (3) a positive electrode material.
(3) 1000g of LiNi0.96Co0.02Mn0.02O2And 10g H3BO3After uniform mixing, the mixture is placed in a box-type furnace and roasted for 6h at 350 ℃, the heating rate is 2.5 ℃/min, the oxygen flow is 6m3And h, sieving the roasted material with a 325-mesh sieve to obtain the boron oxide coated LiNi0.96Co0.02Mn0.02O2And (3) a positive electrode material.
(4) FIG. 2 shows the above-mentioned LiNi coated with boron oxide0.96Co0.02Mn0.02O2The SEM image of the cathode material shows that the surface of the cathode material is provided with a dense coating layer.
The PH value of the positive electrode material prepared in the present case was measured as follows: weighing 5.00 +/-0.05 g of powder sample, dispersing the powder sample in 50.00 +/-0.10 g of deionized water, stirring for 10min to obtain a clear solution, placing the clear solution into the clear solution by using a regulated acidimeter, wherein the glass beads with the pH value recorded in the test must be submerged in the clear solution, and the reading at this moment is the pH value of the sample.
The test method of the lithium residue on the surface of the cathode material prepared in the case of the invention is as follows: weighing 5.000 +/-0.050 g of powder, dispersing the powder in 45g of deionized water, fully stirring for 10min, and filtering by using filter paper to obtain the powder in which LiOH and Li are dissolved2CO3The clear aqueous solution of (a); A0.1M HCl solution was prepared using concentrated HCl. Titration was carried out on a potentiometric titrator using 0.1MHCl as titrant and MR and BTB as indicators, the amount of HCl consumed was found exactly according to the indicator or the change in potential, and the corresponding volume was recorded. According to the volume of HCl consumed, LiOH and Li are calculated2CO3The content of (a).
From the above table, the test of the residual lithium on the surface of the ultra-high nickel cathode material of the gradient lithium supplement method of the waterless washing process adopted by the invention shows that: residual Li of ultra-high nickel material prepared by one-step roasting method in embodiment 1 and comparative example 1+0.287%, significantly higher than 0.195% of example 1, far beyond the customer specification, is not able to homogenize. Residual Li of example 3+0.213%, although the comparative example 2 was subjected to washing with water of Li+: much higher than 0.141%, but the residual Li of the material produced by this process+The% can also meet the requirement of the client index.
The method for testing the electrochemistry of the anode material prepared by the invention comprises the following steps: the cycle performance is tested by using a CR2032 type twisted buckle type battery, and three materials of a positive electrode material, conductive SP and a binder PVDF are mixed according to a ratio of 90: 5: 5, adding an NMP solution, uniformly mixing by dispersing and stirring for 2h to prepare slurry, coating the slurry on aluminum foil paper, cutting the aluminum foil paper into pole pieces with the diameter of 14mm, taking metal lithium as a negative electrode, and forming the half cell in an argon glove box. The charge and discharge test is carried out at room temperature, the voltage range is 2.8V-4.3V, the current density is 20mA/g (0.1C), and the first charge and discharge are carried out; the voltage range is 2.5V-4.25V, the current density is 60mA/g (0.3C), and the charging and discharging cycle is carried out for 50 circles. FIG. 4 is a graph comparing the charge and discharge curves of the samples of example 3 and comparative example 2. FIG. 5 is a graph comparing the cycle performance of example 3 with that of comparative example 2.
As can be seen from the above table, the electrochemical test of the ultra-high nickel cathode material of the gradient lithium supplement method of the waterless washing process adopted by the invention shows that the capacity of the ultra-high nickel cathode material is higher than that of the comparative example 7mAh/g and the 50-cycle retention rate is higher by 5% compared with the conventional one-time sintering in the same Ni content in the example 1 and the comparative example 1. Example 3 comparative example 2, compared with the existing washing process, the capacity is 5mAh/g higher, and the circulation is 9% higher. Therefore, the ultrahigh nickel layered cathode material improved by the method has higher reversible specific capacity and cycle stability, and the electrochemical performance of the ultrahigh nickel cathode material of the lithium ion battery is obviously improved.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.
Claims (8)
1. The method for preparing the ultra-high nickel cathode material by adopting gradient lithium supplement is characterized in that the cathode material is prepared from a precursor, a lithium source and a coating substance, and the steps are as follows:
(1) preparation of substrate a: mixing a precursor containing Ni and a lithium-containing compound according to a molar ratio of 1: 0.5-0.9, uniformly mixing, and roasting at the temperature of 450-650 ℃ to obtain a base material A;
(2) the substrate A and the lithium-containing compound are mixed according to a molar ratio of 1: uniformly mixing the raw materials in a ratio of 0.1-0.5, supplementing lithium for the second time, and roasting the mixture at the temperature of 500-800 ℃ to obtain a mixture B;
(3) uniformly mixing the coating substance with the mixture B according to the mass ratio of 0.5-5%, roasting, and crushing to obtain the final ultra-high nickel cathode material LiNixM1-xO2Wherein the coating substance contains one of elements of Ti, Al, Mg, Si, B, Ba and Ce.
2. The method for preparing the ultra-high nickel cathode material by adopting gradient lithium supplement as claimed in claim 1, wherein the chemical general formula of the precursor in step (1) is NixM1-X(OH)2,Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
3. The method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement as claimed in claim 1, wherein the molecular formula of the ultra-high nickel cathode material is LiNixM1-xO2Wherein M is at least one of Co, Mn, Al, Ti, Zr, Mg, W, Mo, Y, Ta and Nb, and X is more than or equal to 0.9 and less than or equal to 1.0.
4. The method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement as claimed in claim 1, wherein the lithium-containing compound in step (1) is any one or a combination of lithium carbonate, lithium hydroxide, lithium oxide, lithium nitrate, lithium acetate, lithium sulfate and lithium chloride.
5. The method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement as claimed in claim 1, wherein the roasting temperature in the step (1) is 450-650 ℃, the roasting time is 2-20 h, and the temperature rise rate is 1.0-5.0 ℃/min.
6. The method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement as claimed in claim 1, wherein in the step (2), the roasting temperature is 500 ℃ to 800 ℃, the roasting time is 8h to 30h, and the temperature rise rate is 1.0 ℃/min to 5.0 ℃/min.
7. The method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement as claimed in claim 1, wherein in the step (3), the roasting temperature is 200 ℃ to 800 ℃, the roasting time is 2h to 20h, and the temperature rise rate is 1.0 ℃/min to 5.0 ℃/min.
8. The ultra-high nickel cathode material prepared by the method for preparing the ultra-high nickel cathode material by adopting the gradient lithium supplement according to any one of claims 1 to 7.
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