CN114171737A - Low-residual-alkali high-nickel cobalt-free positive electrode material and preparation method thereof - Google Patents
Low-residual-alkali high-nickel cobalt-free positive electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003513 alkali Substances 0.000 title claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000007774 positive electrode material Substances 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 229910005565 NiaMnb Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 6
- NDZRILJASQYFSY-UHFFFAOYSA-J [Zr+4].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O Chemical compound [Zr+4].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O NDZRILJASQYFSY-UHFFFAOYSA-J 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- SLCUWNKMVVOKON-UHFFFAOYSA-J dihydrogen phosphate;titanium(4+) Chemical compound [Ti+4].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O SLCUWNKMVVOKON-UHFFFAOYSA-J 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 2
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002585 base Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a low-residual alkali high-nickel cobalt-free anode material, the chemical expression of which is LixNiaMnbO2Wherein 0.75<a≤0.95，0.05≤b<0.25, a + b is 1, and x is more than or equal to 0.95 and less than or equal to 1.15. The invention adopts the strontium peroxide as the additive, which plays the roles of reducing residual alkali and fluxing; pure water is used as a water washing agent to wash away unreacted LiOH on the surface of the material, so that the surface residual alkali is reduced; meanwhile, the dihydric phosphate coating solution reacts with residual alkali on the surface of the material to achieve the purpose of reducing the residual alkali on the surface of the material, and the generated new substance is coated on the surface of the material to reduce the corrosion of the electrolyte to the base material and effectively inhibit side reaction. The high-nickel cobalt-free anode material prepared by the method has the advantages of low residual alkali, high capacity, good cycle performance and wide industrial application value.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a low-residual-alkali high-nickel cobalt-free positive electrode material and a preparation method thereof.
Background
Cobalt is one of important elements of the anode material of the power battery, so that the structure of the material can be stabilized, and the cycle and rate performance of the material can be improved. However, global cobalt metal has problems of unbalanced storage distribution, resource shortage and price rise, forcing global battery materials, battery suppliers and vehicle enterprises to want to reduce the content of cobalt in the ternary battery. Therefore, the high-nickel cobalt-free positive electrode material is produced at the same time, and the problem that global battery materials, battery suppliers and vehicle enterprises are restricted by cobalt resources is solved.
However, as the content of nickel increases, more alkaline substances, particularly LiOH and Li2CO3, are formed on the surface of the material, which leads to an increase in capacity fade, aggravates structural phase change, and affects the safety of the battery during use. Therefore, the reduction of the residual alkali content on the surface of the high nickel material is a technical problem which needs to be solved urgently.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a low residual alkali high nickel cobalt-free positive electrode material and a preparation method thereof, wherein strontium peroxide is used as an additive in the method, and has the functions of reducing residual alkali and fluxing; pure water is used as a water washing agent to wash away unreacted LiOH on the surface of the material, so that the surface residual alkali is reduced; meanwhile, the dihydric phosphate coating solution reacts with residual alkali on the surface of the material to achieve the purpose of reducing the residual alkali on the surface of the material, and the generated new substance is coated on the surface of the material to reduce the corrosion of the electrolyte to the base material and effectively inhibit side reaction. The high-nickel cobalt-free anode material prepared by the method has the advantages of low residual alkali, high capacity, good cycle performance and wide industrial application value.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low residual alkali high nickel cobalt-free anode material with chemical expression of LixNiaMnbO2Wherein 0.75<a≤0.95，0.05≤b<0.25，a+b＝1，0.95≤x≤1.15。
As another object of the present invention, the present invention further provides a preparation method of the low residual alkali high nickel cobalt-free cathode material, comprising the following steps:
s1: mixing and dispersing lithium oxide, nickel oxide, manganese oxide and strontium peroxide according to a proportion;
s2: sintering the uniformly dispersed materials under an oxygen atmosphere and a first temperature curve;
s3: stirring the sintered product in a stirrer filled with pure water;
s4: after stirring uniformly, adding the dihydric phosphate coating solution into a stirrer, and continuously stirring, filtering and drying;
s5: sintering the dried product under an air atmosphere and a second temperature curve; and finally, naturally cooling to room temperature, crushing and sieving to obtain the high-nickel cobalt-free cathode material.
As a preferred embodiment, in S1, Li: ni: the molar ratio of Mn is (0.95-1.15): (0.75-0.95): (0.05-0.25); mixing time of a high-speed mixer is 10-25 min; the strontium peroxide accounts for 0.05-2 wt% of the total amount of the lithium oxide, the nickel oxide and the manganese oxide.
In a preferred embodiment, the first temperature profile in S2 is performed in an oxygen-containing atmosphere, the temperature is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃/min, and the temperature is maintained for 6-12 h.
As a preferred embodiment, the ratio of pure water in S3: powder (0.75-1) is 1; stirring for 3-5 min.
In a preferred embodiment, the dihydrogen phosphate in S4 is any one of magnesium dihydrogen phosphate, titanium dihydrogen phosphate, and zirconium dihydrogen phosphate; the mass of the coating liquid is 0.2-0.5% of that of the cobalt-free base material; stirring for 15-20 min; the pumping filtration time is 0.5-1.5 h; the drying time is 2-3 h.
In a preferred embodiment, the second temperature profile in S5 is performed in an air atmosphere, the temperature is raised to 280-350 ℃ at a temperature raising rate of 3-10 ℃/min, and the temperature is maintained for 4-6 h.
The invention has the beneficial effects that:
1) strontium oxide is used as an additive to play roles in reducing residual alkali and fluxing.
2) Pure water is used as a water washing agent to wash away unreacted LiOH on the surface of the material, so that the surface residual alkali is reduced.
3) The dihydrogen phosphate solution is used as the coating solution and reacts with the residual alkali on the surface of the material, so that the purpose of reducing the residual alkali on the surface of the material is achieved, the generated new substance is coated on the surface of the material, the corrosion of the electrolyte on the base material is reduced, and the side reaction is effectively inhibited.
The high-nickel cobalt-free anode material prepared by the method has the advantages of low residual alkali, high capacity, good cycle performance and wide industrial application value.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A low residual alkali high nickel cobalt-free anode material and a preparation method thereof comprise the following steps:
weighing oxides of lithium, nickel and manganese in calculated amount, wherein Li: ni: the molar ratio of Mn is 0.95: 0.76: 0.24, weighing 0.05 wt% of strontium peroxide, and adding into a high-speed mixer for mixing for 10 min. Sintering the uniformly mixed materials for the first time under the condition of oxygen atmosphere, heating the materials from room temperature to 600 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 12 hours; adding the sintered product into a sealed stirrer filled with pure water, stirring for 3min at the water content ratio of 0.75:1, adding the zirconium dihydrogen phosphate coating solution, continuously stirring for 15min, performing suction filtration for 0.5h, and drying for 2 h. Sintering the dried substance in air atmosphere, heating to 280 ℃ from room temperature at the heating rate of 3 ℃/min, and keeping the temperature for 6 h; and finally, naturally cooling to room temperature, crushing and sieving to obtain the sample 1 of the embodiment.
Example 2
A low residual alkali high nickel cobalt-free anode material and a preparation method thereof comprise the following steps:
weighing oxides of lithium, nickel and manganese in calculated amount, wherein Li: ni: the molar ratio of Mn is 1.05: 0.80: 0.20, weighing 1 wt% of strontium peroxide, adding into a high-speed mixer, and mixing for 20 min. Sintering the uniformly mixed materials for the first time under the condition of oxygen atmosphere, heating the materials from room temperature to 700 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 10 hours; adding the sintered product into a sealed stirrer filled with pure water, stirring for 4min at the water content ratio of 0.9:1, adding the zirconium dihydrogen phosphate coating solution, continuously stirring for 18min, performing suction filtration for 1h, and drying for 2.5 h. Sintering the dried substance in air atmosphere, heating to 300 ℃ from room temperature at the heating rate of 5 ℃/min, and keeping the temperature for 5 h; finally, the mixture is naturally cooled to room temperature, and the sample 2 of the example is obtained after crushing and sieving
Example 3
A low residual alkali high nickel cobalt-free anode material and a preparation method thereof comprise the following steps:
weighing oxides of lithium, nickel and manganese in calculated amount, wherein Li: ni: the molar ratio of Mn is 1.15: 0.95: 0.05, weighing 1 wt% of strontium peroxide, and adding into a high-speed mixer for mixing for 25 min. Sintering the uniformly mixed materials for the first time under the condition of oxygen atmosphere, heating the materials from room temperature to 800 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 6 hours; adding the sintered product into a sealed stirrer filled with pure water, stirring for 5min at the water content ratio of 1:1, adding the zirconium dihydrogen phosphate coating solution, continuously stirring for 20min, performing suction filtration for 1.5h, and drying for 3 h. Sintering the dried substance in air atmosphere, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, and keeping the temperature for 4 h; finally, the mixture is naturally cooled to room temperature, and the sample 3 of the example is obtained after crushing and sieving
Comparative example 1
The molar ratio of the raw materials is 1: 0.95 mixing precursor Ni0.76Mn0.24(OH)2Mixing with lithium carbonate, adding into high-speed mixer, mixing thoroughlyThe material feeding time is 20min, and a raw material mixture is obtained; continuously sintering the mixed materials in an oxygen atmosphere, heating the mixed materials to 800 ℃ from room temperature, and keeping the temperature for 8 hours; and naturally cooling to room temperature, taking out the powder, crushing and sieving to obtain a comparative example sample 1.
2025 fastening electricity production test was performed on the above-described examples 1 to 3 and comparative example 1, and the results are shown in the following table under the test voltage conditions (3.0 to 4.3) V.
The result shows that the high-nickel cobalt-free cathode material prepared by the method has low residual alkali, high capacity and good cycle performance.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (7)
1. The low residual alkali high nickel cobalt-free anode material is characterized in that the chemical expression is LixNiaMnbO2Wherein 0.75<a≤0.95，0.05≤b<0.25，a+b＝1，0.95≤x≤1.15。
2. The preparation method of the low residual alkali high nickel cobalt-free cathode material as claimed in claim 1, characterized by comprising the following steps:
s1: mixing and dispersing lithium oxide, nickel oxide, manganese oxide and strontium peroxide according to a proportion.
S2: and sintering the uniformly dispersed materials under an oxygen atmosphere and a first temperature curve.
S3: the sintered product was stirred in a stirrer containing pure water.
S4: after stirring evenly, adding the dihydric phosphate coating solution into a stirrer, and continuing stirring, filtering and drying.
S5: sintering the dried product under an air atmosphere and a second temperature curve; and finally, naturally cooling to room temperature, crushing and sieving to obtain the high-nickel cobalt-free cathode material.
3. The production method according to claim 2, wherein in S1, Li: ni: the molar ratio of Mn is (0.95-1.15): (0.75-0.95): (0.05-0.25); mixing time of a high-speed mixer is 10-25 min; the strontium peroxide accounts for 0.05-2 wt% of the total amount of the lithium oxide, the nickel oxide and the manganese oxide.
4. The preparation method of claim 2, wherein the first temperature profile in S2 is performed in an oxygen-containing atmosphere, the temperature is raised from room temperature to 600-800 ℃ at a temperature raising rate of 3-10 ℃/min, and the temperature is maintained for 6-12 h.
5. The method according to claim 2, wherein the ratio of pure water in S3: powder (0.75-1) is 1; stirring for 3-5 min.
6. The method according to claim 2 to 5, wherein the dihydrogen phosphate in S4 is any one of magnesium dihydrogen phosphate, titanium dihydrogen phosphate, and zirconium dihydrogen phosphate; the mass of the coating liquid is 0.2-0.5% of that of the cobalt-free base material; stirring for 15-20 min; the pumping filtration time is 0.5-1.5 h; the drying time is 2-3 h.
7. The preparation method of claim 2, wherein the second temperature profile in S5 is performed in an air atmosphere, the temperature is raised to 280-350 ℃ at a temperature raising rate of 3-10 ℃/min, and the temperature is maintained for 4-6 h.
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| CN115483378A (en) * | 2022-09-22 | 2022-12-16 | 中南大学 | Method for reducing residual alkali on surface of high-nickel ternary electrode material |
| CN115924992A (en) * | 2022-12-26 | 2023-04-07 | 蜂巢能源科技股份有限公司 | Preparation method of cobalt-free anode material, cobalt-free anode material and lithium ion battery |
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| CN113060774A (en) * | 2021-03-26 | 2021-07-02 | 蜂巢能源科技有限公司 | A kind of cobalt-free cathode material and its preparation method and application |
| CN113328069A (en) * | 2021-05-11 | 2021-08-31 | 电子科技大学 | Lithium phosphate coated high-nickel cathode material of lithium ion battery and preparation method of lithium phosphate coated high-nickel cathode material |
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| CN115483378A (en) * | 2022-09-22 | 2022-12-16 | 中南大学 | Method for reducing residual alkali on surface of high-nickel ternary electrode material |
| CN115924992A (en) * | 2022-12-26 | 2023-04-07 | 蜂巢能源科技股份有限公司 | Preparation method of cobalt-free anode material, cobalt-free anode material and lithium ion battery |
| CN115924992B (en) * | 2022-12-26 | 2024-04-19 | 蜂巢能源科技股份有限公司 | Preparation method of cobalt-free positive electrode material, cobalt-free positive electrode material and lithium ion battery |
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