CN112635750A - Phosphorus-doped ternary lithium ion positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Phosphorus-doped ternary lithium ion positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN112635750A CN112635750A CN202011403692.6A CN202011403692A CN112635750A CN 112635750 A CN112635750 A CN 112635750A CN 202011403692 A CN202011403692 A CN 202011403692A CN 112635750 A CN112635750 A CN 112635750A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 38
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 37
- 239000011572 manganese Substances 0.000 claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010406 cathode material Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 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
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000012266 salt solution Substances 0.000 description 11
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- 229960004838 phosphoric acid Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940073644 nickel Drugs 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene 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
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a phosphorus-doped ternary lithium ion positive electrode material, a preparation method thereof and a lithium ion battery. The preparation method comprises the following steps: step S1, dissolving a nickel source, a cobalt source, a manganese source and a phosphorus source into a solvent to obtain a mixed solution; step S2, under an inert environment, carrying out staged reaction on the mixed solution at different pH values to obtain a precursor; and step S3, mixing the precursor with a lithium source, and sintering to obtain the phosphorus-doped ternary lithium ion cathode material. The phosphorus-doped ternary lithium ion positive electrode material prepared by the method has uniform morphology, and aggregation phenomenon does not exist among particles, so that the first charge-discharge efficiency of the lithium ion battery and the cycle performance of the battery are improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a phosphorus-doped ternary lithium ion positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The nickel-cobalt-manganese ternary material is always a research hotspot in the new energy industry due to the high energy density, and particularly, the nickel-rich material with the nickel content of more than 80 percent becomes the mainstream of a new generation in the power battery industry at present. With LiCoO2Similarly, nickel-cobalt-manganese ternary materials have a layered structure. Ni, Mn and Co occupy the 3b position randomly and oxygen atom occupies the 6c position to form MO6Octahedron, Li atom occupying 3a position, forming LiO6And eight bodies. Li+Located between MO6 octahedral layers, can be reversibly intercalated and deintercalated between the layers.
The three elements of nickel, cobalt and manganese have different influences on the electrochemical performance of the material. The higher the nickel content, the greater the energy density, but this is accompanied by a number of problems. The nickel content is too high, and the nickel-cobalt-manganese ternary material prepared by sintering is easy to absorb water in the process of preparing the slurry, so that the water content of the slurry and the pole piece is increased, the requirement on the environment is extremely high, the difficulty of the preparation process is increased, and the synthesis difficulty of the lithium ion battery is improved. In addition, in the aspect of material crystals, positive quadrivalent nickel is easy to react with electrolyte, and as nickel element is separated out, the crystal structure of the material collapses, so that stress and microcracks are generated in the material, the contact area of the material and the electrolyte is further increased, and the irreversible capacity loss is further increased.
Therefore, the improvement of the stability of the crystal structure of the nickel-cobalt-manganese ternary material is indispensable, and the structural stability of the crystal material is improved mostly by adopting ion doping, coating modification and other modes at present. Ion doping is generally to dope ions with a radius close to that of ions in a material, and aims to stabilize the crystal structure of the material by improving the lattice energy of the material, so as to improve the cycle performance and the thermal stability of the material. The doping-improved elements are generally classified into metal ion doping, non-metal ion doping and composite doping. However, too high an amount of ion doping causes displacement imbalance, which in turn severely deteriorates the electrical properties of the material. The surface coating modification method is a modification technology for directly forming a stable protective layer on the surface of a material through a physical or chemical means so as to isolate the body material from being directly contacted with electrolyte. The purpose of surface coating is to keep the surface structure of the material stable, avoid direct contact of the material with electrolyte and inhibit the dissolution of transition metal ions at high potential. However, although different coating modification methods and materials improve the rate and the cycle performance to a certain extent, the coating modification methods and materials have a certain inhibiting effect on performance parameters such as initial discharge capacity.
Disclosure of Invention
The invention mainly aims to provide a phosphorus-doped ternary lithium ion positive electrode material, a preparation method thereof and a lithium ion battery, so as to solve the problem of poor cycle performance of a battery formed by the conventional nickel-cobalt-manganese ternary material.
The preparation method of the phosphorus-doped ternary lithium ion cathode material provided by the invention comprises the following steps: step S1, dissolving a nickel source, a cobalt source, a manganese source and a phosphorus source into a solvent to obtain a mixed solution; step S2, under an inert environment, carrying out staged reaction on the mixed solution at different pH values to obtain a precursor; and step S3, mixing the precursor with a lithium source, and sintering to obtain the phosphorus-doped ternary lithium ion cathode material.
Further, the above-mentioned staged reaction of step S2 includes: the first stage reaction, the pH value of the mixed solution is adjusted to 11.8-12.5, and the reaction is fully carried out; and a second stage reaction, namely adjusting the pH value of the mixed solution to be between 11 and 11.8, and fully reacting, wherein preferably, the pH value of the first stage is controlled to be 12, and the pH value of the second stage is controlled to be 11.6.
In the specific embodiment provided by the invention, ammonia water is used for adjusting the pH value in the step S2; specifically, ammonia water with the concentration of 0.4-0.5mol/L is added into the mixed solution to carry out the first-stage reaction; adjusting the concentration of ammonia water to 0.5-0.65mol/L, adding the ammonia water into the mixed solution, and carrying out second-stage reaction until a reaction product with a target particle size is generated; preferably, the concentration of the ammonia water adopted in the first stage is 0.46 mol/L; the concentration of ammonia water used in the second stage is 0.60 mol/L.
Further, in the staged reaction, the flow rate of the mixed solution is 1.2-2.2L/h, the reaction temperature is 40-60 ℃, the stirring linear velocity is 1-4.2 pi m/s, and the inert environment is formed by high-purity inert gas with the flow rate of 1-2L/h; preferably, the flow rate of the mixed solution is 1.5-2.0L/h, the reaction temperature is 50-60 ℃, the stirring linear velocity is 1-3 pi m/s, and the flow rate of nitrogen is 1.2L/h.
Further, in the step S1, the molar ratio of the metal nickel, cobalt, and manganese in the nickel source, cobalt source, and manganese source is (0.80 to 0.86): (0.05-0.12): (0.01-0.05); preferably, the molar ratio of the metal nickel, cobalt and manganese in the nickel source, the cobalt source and the manganese source is 0.85: 0.10: 0.20.
in the specific embodiment provided by the invention, the nickel source, the cobalt source and the manganese source are respectively one or more mixtures of metal nickel, cobalt and manganese sulfate or nitrate, and the phosphorus source is phosphoric acid or phosphorous acid; the lithium source is one or more selected from lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
Further, the content of the phosphorus source is 2-8 wt% of the total mass of the nickel source, the cobalt source and the manganese source; preferably, the content of the phosphorus source is 4 wt% of the total mass of the nickel source, the cobalt source and the manganese source.
In a specific embodiment of the present invention, in step S3, the sintering conditions are as follows: in the oxygen atmosphere, firstly preserving heat for 4-6h in the environment of 450-520 ℃, then preserving heat for 12-18h in the environment of 700-850 ℃, and naturally cooling to obtain the phosphorus-doped ternary lithium ion cathode material.
The invention also aims to provide the phosphorus-doped ternary lithium ion cathode material prepared by the preparation method.
Furthermore, the D50 of the ternary lithium ion positive electrode material is 5-20 μm, and the specific surface area is about 10.5-15.5g/m2And has a mesoporous structure.
The invention further aims to provide a lithium ion battery, which contains the phosphorus-doped ternary lithium ion positive electrode material provided by the invention.
By applying the technical scheme of the invention, a staged reaction method is creatively adopted, and the reaction conditions are accurately controlled, so that the prepared phosphorus-doped ternary lithium ion positive electrode material is microscopically uniform in shape, and the aggregation phenomenon does not exist among particles, thereby improving the first charge-discharge efficiency of the lithium ion battery and the cycle performance of the battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a SEM image of a phosphorous doped ternary cathode material prepared according to example 1 of the present invention; and
fig. 2 shows SEM images of phosphorus doped ternary cathode materials prepared according to comparative examples of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the current lithium ion positive electrode material has the problems of strict requirements on the preparation process and no great improvement on the cycle performance of the prepared battery. In order to solve the problem, the invention creatively improves the preparation process, carries out the doping reaction in stages, and forms the anode material with uniform shape by accurately controlling the reaction conditions of each stage. Specifically, the preparation method of the phosphorus-doped ternary lithium ion positive electrode material provided by the invention comprises the following steps: step S1, dissolving a nickel source, a cobalt source, a manganese source and a phosphorus source into a solvent to obtain a mixed solution; step S2, under an inert environment, carrying out staged reaction on the mixed solution at different pH values to obtain a precursor; and step S3, mixing the precursor with a lithium source, and sintering to obtain the phosphorus-doped ternary lithium ion cathode material.
By the preparation method provided by the invention, the doping reaction is carried out in stages under different pH values, and the pH value of the first stage is larger than that of the subsequent stage, so that the optimal value is selected by controlling the pH values of different stages.
Further, the above-mentioned staged reaction of step S2 includes: the first stage reaction, the pH value of the mixed solution is adjusted to 11.8-12.5, and the reaction is fully carried out; and the second stage reaction, namely adjusting the pH value of the mixed solution to 11-11.8 for full reaction. Preferably, the pH of the first stage is controlled at 12 and the pH of the second stage is controlled at 11.6. By controlling the reaction conditions, the prepared phosphorus-doped ternary cathode material is microscopically uniform in shape, and the problem of aggregation among particles does not exist.
In the specific embodiment provided by the invention, ammonia water or sodium hydroxide solution is used for adjusting the pH value of the doping reaction. The cathode ions generated by using the two solutions are easier to remove, and the product performance is not influenced. Specifically, according to the specific requirements of each stage, ammonia water with the concentration of 4-10mol/L or sodium hydroxide with the concentration of 3-6mol/L is diluted to prepare the pH value regulator. In one embodiment provided by the invention, ammonia water with the concentration of 0.4-0.5mol/L is adopted as a pH value regulator to carry out the first-stage reaction; then adjusting the concentration of ammonia water to 0.5-0.65mol/L, adding the ammonia water into the mixed solution, and carrying out second-stage reaction until a reaction product with a target particle size is generated; preferably, the concentration of the ammonia water adopted in the first stage is 0.46 mol/L; the concentration of ammonia water used in the second stage is 0.60 mol/L. The preferred process conditions allow for more precise and efficient control of the chemical reaction.
Further, in the staged reaction, the inert environment protection is formed by high-purity inert gas (nitrogen) with the flow rate of 1-2L/h, the flow rate of the mixed solution is controlled to be 1.2-2.2L/h, the reaction temperature is 40-60 ℃, and the stirring linear velocity is 1-4.2 pi m/s; preferably, the flow rate of the mixed solution is 1.5-2.0L/h, the reaction temperature is 50-60 ℃, the stirring linear velocity is 1-3 pi m/s, and the flow rate of nitrogen is 1.2L/h. The preferable process conditions can enable the precursor obtained by the reaction to have more excellent performance, so that the first charge-discharge efficiency of the lithium ion battery prepared from the precursor and the cycle performance of the battery are further improved.
Further, in the step S1, the molar ratio of the metal nickel, cobalt, and manganese in the nickel source, cobalt source, and manganese source is (0.80 to 0.86): (0.05-0.12): (0.01-0.05); preferably, the molar ratio of the metal nickel, cobalt and manganese in the nickel source, the cobalt source and the manganese source is 0.85: 0.10: 0.20.
in the specific embodiment provided by the invention, the nickel source, the cobalt source and the manganese source are respectively one or more mixtures of metal nickel, cobalt and manganese sulfate or nitrate, and the phosphorus source is phosphoric acid or phosphorous acid; the lithium source is one or more selected from lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
Further, the content of the phosphorus source is 2-8 wt% of the total mass of the nickel source, the cobalt source and the manganese source; preferably, the content of the phosphorus source is 4 wt% of the total mass of the nickel source, the cobalt source and the manganese source.
In a specific embodiment of the present invention, in step S3, the sintering conditions are as follows: in the oxygen atmosphere, firstly preserving heat for 4-6h in the environment of 450-520 ℃, then preserving heat for 12-18h in the environment of 700-850 ℃, and naturally cooling to obtain the phosphorus-doped ternary lithium ion cathode material. In this step, the molar ratio of the precursor to the lithium source was set so that the molar ratio of the metal content in the precursor to the lithium source was 1: 1.03.
The phosphorus-doped ternary lithium ion positive electrode material D50 prepared by the method is 5-20 mu m, and the specific surface area is about 10.5-15.5g/m2And has a mesoporous structure. The specific surface area of the material is larger than that of the existing ternary lithium ion anode material, and the material has higher electronic conductivity.
In addition, the lithium ion battery containing the ternary lithium ion anode material provided by the invention has improved first charge-discharge efficiency and cycle performance of the battery.
According to the embodiment provided by the invention, the invention also provides a preparation system of the precursor of the ternary lithium ion cathode material. The system comprises a continuous reaction kettle and a PH online control device. And (3) placing the reaction mixed liquid in a continuous reaction kettle, and accurately regulating and controlling the pH value in the reaction process through a pH online control device until a reaction precursor product with the target granularity is generated. Wherein the pH on-line control device can be a nuclear instrument.
In order to further explain the objects, effects, and technical means adopted by the present invention in detail, the following description will be given with reference to specific embodiments.
Electrical property test:
drying the ternary positive electrode material to be tested, preparing the dried ternary positive electrode material, carbon black and PVP (polyvinylpyrrolidone) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, rolling the slurry to prepare a positive plate, assembling the positive plate, a metal lithium negative electrode, a polypropylene film and electrolyte into a button cell, and testing the electrochemical performance of the button cell.
Example 1
The preparation method of the phosphorus-doped ternary lithium ion positive electrode material provided by the embodiment comprises the following steps:
1) using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4The phosphorus source is 2 wt% of the total mass of the nickel source, the cobalt source and the manganese source, and the phosphorus source is a raw material, and the phosphorus source comprises the following components in percentage by weight: cobalt: molar ratio of manganese 0.8: 0.05: 0.01 is added into deionized water to prepare a mixed salt solution with the concentration of 2mol/L, and the mixed salt solution is placed in a continuous reaction kettle;
2) respectively preparing ammonia water and flake sodium hydroxide into 8mol L and 4mol/L for later use;
3) adopting a pH on-line control system and a continuous reaction kettle to carry out combined reaction for a period of time: forming an inert environment by high-purity inert gas with the flow rate of 0.6L/h, fixing the flow rate of the mixed salt solution to be 1.8L/h, the reaction temperature to be 50 ℃, the stirring linear speed to be 1.6 pi m/s, protecting by adopting high-purity nitrogen protective gas, adjusting the concentration of ammonia water to be 0.35mol/L, controlling the pH value to be 11.6, after reacting for 20min, adjusting the concentration of ammonia water to be 0.4mol/L, and reducing the pH value to be 10.6;
4) aging the product in the reaction kettle at 50 ℃ for 4h, and then performing filter pressing, washing and drying to obtain a precursor product;
5) mixing lithium hydroxide and 3g of precursor product according to the molar ratio of metal of 1.03, putting the mixture into a tubular furnace for heat treatment, keeping the temperature at 400 ℃ for 3h in an oxygen atmosphere, then heating to 600 ℃ for 10h, and naturally cooling along with the furnace to obtain the phosphorus-doped ternary cathode material.
Example 2
The preparation method provided in this example is different from that of example 1 in that:
adjusting the concentration of ammonia water to 0.4mol/L, controlling the pH value to 11.8, and after reacting for 20min, adjusting the concentration of ammonia water to 0.5mol/L and reducing the pH value to 11.
Example 3
The preparation method provided in this example is different from that of example 1 in that:
adjusting the concentration of ammonia water to 0.5mol/L, controlling the pH value to 12.5, and after reacting for 20min, adjusting the concentration of ammonia water to 0.65mol/L, and reducing the pH value to 11.8.
Example 4
The preparation method provided in this example is different from that of example 1 in that:
using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4As raw materials, according to the weight ratio of metallic nickel: cobalt: molar ratio of manganese 0.86: 0.12: 0.05 was added to deionized water.
Example 5
The preparation method provided in this example is different from that of example 1 in that:
an inert environment is formed by high-purity inert gas with the flow rate of 1L/h, the flow rate of the fixed mixed salt solution is 1.2L/h, the reaction temperature is 40 ℃, and the stirring linear velocity is 1 pi m/s.
Example 6
The preparation method provided in this example is different from that of example 1 in that:
an inert environment is formed by high-purity inert gas with the flow rate of 2L/h, the flow rate of the fixed mixed salt solution is 2.2L/h, the reaction temperature is 60 ℃, and the stirring linear velocity is 4.2 pi m/s.
Example 7
The preparation method provided in this example is different from that of example 1 in that:
and (3) keeping the temperature of 450 ℃ for 4h in an oxygen atmosphere, heating to 700 ℃ and keeping the temperature for 12h, and then naturally cooling along with the furnace to obtain the phosphorus-doped ternary cathode material.
Example 8
The preparation method provided in this example is different from that of example 1 in that:
and (3) keeping the temperature of 520 ℃ for 6h in an oxygen atmosphere, heating to 850 ℃ and keeping the temperature for 18h, and then naturally cooling along with the furnace to obtain the phosphorus-doped ternary cathode material.
Example 9
The preparation method provided in this example is different from that of example 1 in that:
the content of the phosphorus source is 8 wt% of the total mass of the nickel source, the cobalt source and the manganese source.
Example 10
1) Using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4The phosphorus source is 4 wt% of the total mass of the nickel source, the cobalt source and the manganese source, and the content of the phosphorus source is calculated according to the weight percentage of the metal nickel: cobalt: molar ratio of manganese 0.85: 0.10: 0.05 is added into deionized water to prepare a mixed salt solution with the concentration of 2mol/L, and the mixed salt solution is placed in a continuous reaction kettle;
2) respectively preparing ammonia water and flake sodium hydroxide into 8mol L and 4mol/L for later use;
3) adopting a pH on-line control system and a continuous reaction kettle to carry out combined reaction for a period of time: fixing the flow rate of the mixed salt solution at 1.8L/h, the reaction temperature at 50 ℃, the stirring linear velocity at 1.6 pi m/s, adopting high-purity nitrogen protective gas for protection, adjusting the concentration of ammonia water to 0.46mol/L, controlling the pH value to 12, adjusting the concentration of ammonia water to 0.60mol/L after reacting for 20min, and reducing the pH value to 11.6;
4) aging the product in the reaction kettle at 50 ℃ for 4h, and then performing filter pressing, washing and drying to obtain a precursor product;
5) mixing lithium hydroxide and 3g of precursor product according to the molar ratio of metal of 1.03, putting the mixture into a tubular furnace for heat treatment, keeping the temperature at 500 ℃ for 5h in an oxygen atmosphere, heating to 800 ℃ and keeping the temperature for 15h, and naturally cooling along with the furnace to obtain the phosphorus-doped ternary cathode material.
As can be seen from the SEM image shown in FIG. 1, the phosphorus-doped ternary cathode material prepared in the present example has uniform morphology, a particle size (D50) of 5-20 μm, and a specific surface area of about 10.5-15.5g/m2And has a mesoporous structure. The charge and discharge capacity of 0.2C of the lithium ion battery prepared by the sample is 230.1mAh/g and 201.3mAh/g respectively, and the first charge and discharge efficiency is 87.5%.
Example 11
The preparation method provided in this example is different from that of example 10 in that:
nickel nitrate, cobalt nitrate, manganese nitrate and H phosphate3PO4Is used as a raw material.
Example 12
The preparation method provided in this example is different from that of example 10 in that:
the flow rate of the fixed mixed salt solution is 1.2L/h, the reaction temperature is 40 ℃, and the stirring linear velocity is 3.0 pi m/s.
Example 13
The preparation method provided in this example is different from that of example 10 in that:
using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4As raw materials, according to the weight ratio of metallic nickel: cobalt: molar ratio of manganese 0.8: 0.1: 0.1 to deionized water.
Example 14
The preparation method provided in this example is different from that of example 10 in that:
using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4As raw materials, according to the weight ratio of metallic nickel: cobalt: molar ratio of manganese 0.6: 0.2: 0.2 to deionized water.
Comparative example
1) Using nickel sulfate, cobalt sulfate, manganese sulfate and phosphoric acid H3PO4As raw materials, according to the weight ratio of metallic nickel: cobalt: molar ratio of manganese 0.85: 0.10: 0.05 is added into deionized water to prepare a mixed salt solution with the concentration of 2mol/L, and the mixed salt solution is placed in a continuous reaction kettle;
2) respectively preparing ammonia water and flake sodium hydroxide into 8mol L and 4mol/L for later use;
3) adopting a pH on-line control system and a continuous reaction kettle to carry out combined reaction for a period of time: the flow rate of the fixed mixed salt is 1.8L/h, the reaction temperature is 50 ℃, the stirring linear velocity is 1.6 pi m/s, high-purity nitrogen protective gas is adopted for protection, the concentration of ammonia water is adjusted to be 0.46mol/L, and the pH value is controlled to be 11.6.
4) Aging the product in the reaction kettle at 50 ℃ for 4h, and then performing filter pressing, washing and drying to obtain a precursor product;
5) mixing lithium hydroxide and 3g of precursor product according to the molar ratio of metal of 1.03, putting the mixture into a tubular furnace for heat treatment, keeping the temperature at 500 ℃ for 5h in an oxygen atmosphere, heating to 800 ℃ and keeping the temperature for 15h, and naturally cooling along with the furnace to obtain the phosphorus-doped ternary cathode material.
The difference between the comparative example and the example is that the concentration of ammonia water is adjusted by adopting a one-step method, and the pH value is controlled as follows: the concentration of ammonia water is directly adjusted to be 0.46mol/L, and the pH value is controlled to be 11.6. The phosphorus-doped ternary cathode material prepared in the comparative example is in an agglomerated state, the particle size (D50) of the phosphorus-doped ternary cathode material is about 5.5-22 mu m, and the specific surface area of the phosphorus-doped ternary cathode material is about 10.5-15.5g/m2And has a mesoporous structure. The lithium ion battery prepared by the lithium ion battery has 0.2C charge-discharge capacities of 230.8mAh/g and 200.6mAh/g respectively, and the first charge-discharge efficiency is 86.9%.
Compared with the example 1, the microstructure of the ternary cathode material doped with phosphorus in the comparative example is in an agglomerated state, the microstructure of the ternary cathode material doped with phosphorus in the example 1 is in a uniform state, and the first charge-discharge efficiency and the capacity retention rate after 50 weeks of 1C cycle in the examples 1 to 4 are higher than those of the comparative example.
Physical properties of the phosphorus-doped ternary cathode materials prepared in inventive examples 1-14 and comparative example are shown in table 1.
TABLE 1
From the experimental data of the above examples and comparative examples, it can be seen that the phosphorus-doped lithium ion cathode material with uniform morphology is prepared by a staged reaction method, and the first charge-discharge efficiency and the capacity retention rate after 50 weeks of 1C cycle of the battery prepared from the phosphorus-doped lithium ion cathode material are higher than those of the existing battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A preparation method of a phosphorus-doped ternary lithium ion positive electrode material is characterized by comprising the following steps:
step S1, dissolving a nickel source, a cobalt source, a manganese source and a phosphorus source into a solvent to obtain a mixed solution;
step S2, under an inert environment, carrying out staged reaction on the mixed solution at different pH values to obtain a precursor;
and step S3, mixing the precursor with a lithium source, and sintering to obtain the phosphorus-doped ternary lithium ion cathode material.
2. The method as claimed in claim 1, wherein the step S2 staged reaction comprises:
the first stage reaction, the pH value of the mixed solution is adjusted to 11.8-12.5, and the reaction is fully carried out; and
the second stage reaction, the pH value of the mixed solution is adjusted to 11 to 11.8, the reaction is fully carried out,
preferably, the pH value of the first stage is controlled at 12, and the pH value of the second stage is controlled at 11.6.
3. The method according to claim 2, wherein the pH is adjusted with ammonia water; wherein the content of the first and second substances,
adding ammonia water with the concentration of 0.4-0.5mol/L into the mixed solution to carry out the first-stage reaction; and
adjusting the concentration of ammonia water to 0.5-0.65mol/L, adding the ammonia water into the mixed solution, and carrying out the second-stage reaction until a reaction product with a target particle size is generated;
preferably, the concentration of ammonia water adopted in the first stage is 0.46 mol/L; the concentration of ammonia water adopted in the second stage is 0.60 mol/L.
4. The method according to claim 3, wherein in the staged reaction, the flow rate of the mixed solution is 1.2 to 2.2L/h, the reaction temperature is 40 to 60 ℃, the stirring linear velocity is 1 to 4.2 π m/s, and the inert atmosphere is formed by a high purity inert gas at a flow rate of 1 to 2L/h;
preferably, the flow rate of the mixed solution is 1.5-2.0L/h, the reaction temperature is 50-60 ℃, the stirring linear velocity is 1-3 pi m/s, and the flow rate of nitrogen is 1.2L/h.
5. The method according to any one of claims 1 to 4, wherein in the step S1, the molar ratio of the metals nickel, cobalt and manganese in the nickel source, cobalt source and manganese source is (0.80-0.86): (0.05-0.12): (0.01-0.05); preferably, the molar ratio of the metal nickel, cobalt and manganese in the nickel source, the cobalt source and the manganese source is 0.85: 0.10: 0.20.
6. the preparation method according to claim 5, wherein the nickel source, the cobalt source and the manganese source are one or more mixtures of sulfates or nitrates of metallic nickel, cobalt and manganese respectively, and the phosphorus source is phosphoric acid or phosphorous acid; the lithium source is selected from one or more of lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
7. The method according to claim 6, wherein the content of the phosphorus source is 2 to 8 wt% of the total mass of the nickel source, the cobalt source and the manganese source; preferably, the content of the phosphorus source is 4 wt% of the total mass of the nickel source, the cobalt source and the manganese source.
8. The method according to claim 1, wherein in the step S3, the sintering conditions are: in the oxygen atmosphere, firstly preserving heat for 4-6h in the environment of 450-520 ℃, then preserving heat for 12-18h in the environment of 700-850 ℃, and naturally cooling to obtain the phosphorus-doped ternary lithium ion cathode material.
9. The phosphorus-doped ternary lithium ion positive electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The ternary lithium ion positive electrode material according to claim 9, wherein the ternary lithium ion positive electrode material has a D50 of 5 to 20 μm and a specific surface area of about 10.5 to 15.5g/m2And has a mesoporous structure.
11. A lithium ion battery comprising the phosphorus-doped ternary lithium ion positive electrode material according to claim 9 or 10.
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| CN117239087A (en) * | 2023-09-25 | 2023-12-15 | 巴斯夫杉杉电池材料有限公司 | Modified ternary positive electrode material and preparation method thereof |
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| CN117239087A (en) * | 2023-09-25 | 2023-12-15 | 巴斯夫杉杉电池材料有限公司 | Modified ternary positive electrode material and preparation method thereof |
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