CN114940519B - Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material - Google Patents
Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material, which comprises the steps of mixing a high-nickel ternary precursor with a lithium source, a fluxing agent and a doping agent, and then performing primary sintering under a sintering atmosphere to obtain a monocrystal ternary positive electrode material base material, wherein the primary sintering is to heat up to a first sintering temperature for a certain time, and then heat up to a second sintering temperature for a certain time; crushing, sieving, washing, suction filtering and drying the obtained monocrystal ternary anode material base material to obtain a dried product; and (3) performing secondary sintering on the dried product to obtain a secondary sintering product, mixing the secondary sintering product with a coating agent, and performing tertiary sintering to obtain the monocrystal nickel cobalt lithium manganate ternary anode material. The invention can reduce sintering temperature, reduce sintering energy consumption, lighten lithium-nickel mixed discharge under conventional high-temperature sintering, and improve electrochemical performance of the material.
Description
Technical Field
The invention belongs to the technical field of ternary positive electrode materials of lithium ion batteries, and relates to a preparation method of a high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material.
Background
The lithium ion battery has the advantages of high working voltage, light weight, high energy density, long cycle life and the like, and is widely applied to the fields of electric automobiles, digital cameras, mobile phones, notebook computers and the like. The positive electrode material is used as a core material in the lithium ion battery, so that the energy density and the cost of the battery are determined to a great extent, and the performance of the battery is directly influenced.
The ternary positive electrode material is the positive electrode material of the power battery with the largest market share at present, and has become one of the main choices in the power battery industry. Currently, the technology of nickel-rich, high voltage, low cobalt, high power, safety and high cycle number has been a trend of ternary positive electrode material products. The conventional secondary particle aggregate ternary positive electrode material is composed of a plurality of primary particles, and in the circulation process, the whole secondary sphere is easy to crack and break due to the continuous shrinkage and expansion of the particle volume, so that the electrochemical environment of the battery is changed drastically, the circulation life is shortened, and the battery performance is also deteriorated. The monocrystal ternary anode material can obtain more excellent cycle stability, structural stability and high temperature resistance, so that the monocrystal ternary anode material has better safety performance.
At present, the method for preparing the monocrystal NCM ternary positive electrode material firstly uses a polycrystal precursor prepared by a higher-temperature sintering coprecipitation method, the sintering temperature is high, the heat preservation time is long, the energy consumption is higher, the particle size distribution of the prepared monocrystal material is wider, serious agglomeration is easy to occur among primary particles, the dispersibility is poor, the tap density is low, and the lithium nickel is seriously mixed and discharged under high-temperature sintering, so that the electrochemical performance is also poor; in another method, fluxing agent is used for auxiliary sintering, but most of the monocrystalline materials prepared by the prior art are monocrystalline-like, and a small amount of agglomerates in the monocrystalline-like materials like conventional secondary particles of the positive electrode materials can crack, pulverize and the like in the later period, so that the cycle performance of the materials is finally poor, and the electrochemical performance is poor. Therefore, the morphology and the dispersibility of the material are also to be improved, and the material also has the problems of certain lithium nickel mixed arrangement and insufficient crystallinity. In addition, the fluxing agent NaF, li is adopted 2 SO 4 、Al 2 O 3 、Na 2 SO 4 、B 2 O 3 NaCl, mgO, etc., are liable to introduce uncontrollable impurity elements or cause excessive doping of other elements, and these fluxes are disadvantageous for subsequent removal.
Disclosure of Invention
The invention aims to provide a preparation method of a high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material, which solves the problems of high sintering temperature, higher energy consumption or uncontrollable impurity introduction of the existing monocrystal NCM ternary cathode material, poor shape and dispersion of the prepared monocrystal material, low tap density, poor capacity and initial efficiency and the like.
The technical scheme adopted by the invention is that the preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material comprises the following specific operation steps:
step 1: mixing the high-nickel ternary precursor with a lithium source, a doping agent and a fluxing agent, then sintering in an oxygen atmosphere, heating to a first sintering temperature of 200-600 ℃ for 2-24 hours, heating to a second sintering temperature of 400-900 ℃ for 2-24 hours, cooling at a cooling rate of 0.5-10 ℃/min after sintering, and crushing after discharging the product from a furnace to obtain a monocrystalline NCM substrate;
step 2: adding deionized water into the monocrystalline NCM substrate obtained in the step 1 for washing, stirring for 5-60 min, and carrying out suction filtration, drying and sieving after the completion;
step 3: carrying out secondary sintering on the dried material in the step 2 in air or oxygen atmosphere, wherein the sintering temperature is 200-800 ℃, the sintering time is 1-24 hours, cooling along with a furnace after sintering is finished, and sieving after discharging the product from the furnace to obtain the monocrystalline NCM anode material;
step 4: mixing the monocrystalline NCM positive electrode material in the step 3 with a coating agent, and then sintering for three times in air or oxygen atmosphere at the sintering temperature of 100-600 ℃ for 2-15 h, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the monocrystalline NCM product.
The present invention is also characterized in that,
the lithium source in the step 1 is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate.
The molar ratio of lithium ions in the lithium source to the high-nickel ternary precursor in the step 1 is 0.8-1.3.
The mass ratio of the doping agent to the precursor in the step 1 is 100-5000 ppm; the fluxing agent is LiBr, naBr, KBr, liNO 3 One or more of the following; the proportion of the fluxing agent accounting for the total of the lithium source and the fluxing agent is 0.1-80 wt%.
And (3) heating to the first sintering temperature and the second sintering temperature in the step (1) at a heating rate of 0.5-10 ℃/min.
The metal element in the doping agent in the step 1 is one or more than one of Mg, zr, W, ti, Y, sr, al, mo, V.
In the step 2, the mass ratio of the deionized water to the positive electrode material is 1:1-5:1.
The coating agent in the step 4 is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
The beneficial effects of the invention are as follows:
according to the preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material, firstly, the fluxing agent and the lithium source are caused to form a eutectic at a specific lower temperature through sectional heat preservation, so that lithium ions can be diffused at a relatively lower temperature, and the heat preservation at the specific temperature can effectively promote the lithium ions to be fully diffused for a period of time, so that monocrystal particles are caused to be uniformly generated and grown. Then further promoting the monocrystal particles to grow up at a higher temperature to form a final product, and the XRD result shows that the product has high crystallinity and shows a complete lattice structure. The sintering system can show that the invention can also effectively reduce the sintering energy consumption, and lighten the lithium nickel mixed discharge under the conventional high-temperature sintering, thereby improving the electrochemical performance of the material.
The bromide fluxing agent or the fluxing agent combination containing bromide has higher solubility at normal temperature, is beneficial to removing residual fluxing agent by subsequent water washing, not only can not introduce impurity elements, but also can reduce washing water, ensures the performance of single crystal materials, and reduces the consumption of washing water and the cost of subsequent wastewater treatment; meanwhile, the ionic radius of anions in the fluxing agent is larger, impurities are not introduced due to the fact that anions are embedded into a layered structure of the monocrystalline material, electrostatic repulsion is generated between monocrystalline particles due to the adsorption of the anions on the surfaces of different monocrystalline particles, so that the dispersibility of the monocrystalline material is improved, the prepared high-nickel monocrystalline ternary cathode material has good dispersibility, and compared with a contrast electron microscope, few agglomerates exist, so that the material has higher tap density, and finally the battery has higher volumetric specific energy. In addition, ions in the fluxing agent can influence the morphology of the single crystal, and specific adsorption on different crystal faces of the single crystal is realized by controlling the combination of the fluxing agent, so that the single crystal NCM positive electrode material with different morphologies, such as octahedron shape, is obtained. In addition, the invention can also achieve the purpose of controlling the grain diameter by changing the combination and the dosage of the fluxing agent.
Drawings
FIG. 1 is an SEM image of a single crystal NCM prepared according to example 1 of the present invention.
FIG. 2 is a SEM image at a magnification of single crystal NCM prepared according to example 1 of the present invention.
FIG. 3 is an XRD pattern of single crystal NCM prepared in example 1 of the present invention.
FIG. 4 is an SEM image of single crystal NCM prepared according to example 2 of the present invention.
FIG. 5 is an SEM image of single crystal NCM prepared according to example 3 of the present invention.
FIG. 6 is an SEM image of single crystal NCM prepared according to comparative example 1 of the present invention.
FIG. 7 is an SEM image of single crystal NCM prepared according to comparative example 2 of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is given with reference to the accompanying drawings, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the protection scope of the present invention is not limited to the following examples.
The preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material comprises the following steps of:
(1) Mixing a high-nickel ternary precursor with a lithium source, a fluxing agent and a doping agent according to a certain proportion, sintering the mixture at a lower temperature according to a certain heating rate under an oxygen atmosphere and a certain heat preservation time, then raising the temperature, sintering according to a certain heat preservation time, cooling to a tapping temperature according to a certain cooling rate after sintering, and crushing a ternary positive electrode material of a final sintered product;
(2) Stirring and washing the crushed product with deionized water according to a certain mass ratio for a certain time to remove residual fluxing agent, and carrying out suction filtration, drying and sieving after washing;
(3) Carrying out secondary sintering on the product obtained in the step (2) in an oxygen atmosphere according to a certain temperature and heat preservation time system, crushing and sieving the product to obtain the monocrystal high-nickel ternary anode material;
(4) And (3) sintering the monocrystalline cathode material obtained in the step (3) and a coating agent for the third time according to a certain temperature and heat preservation time system in an oxygen atmosphere, and then crushing and sieving the sintered monocrystalline cathode material to obtain the final product high-nickel monocrystalline ternary cathode material.
Wherein in the step (1), the high-nickel ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 ，x＞0.6，y＞0，1-x-y＞0。
Preferably, in the step (1), the sintering atmosphere is air or oxygen, the first heat preservation temperature is 200-600 ℃, the sintering time is 2-24 h, the second heat preservation temperature is 400-900 ℃, and the sintering time is 2-24 h; the heating rate is 0.5-10 ℃/min, and the cooling rate is 0.5-10 ℃/min; the lithium source is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate, and the metal element in the doping agent is one or more of Mg, zr, W, ti, Y, sr, al, mo, V; the molar ratio of the lithium source to the precursor is 0.8-1.3, and the mass ratio of the doping agent to the precursor is 100-5000 ppm; the fluxing agent is LiBr, naBr, KBr, liNO 3 One or more of the fluxing agents accounts for 0.1 to 80 weight percent of the total of the lithium source and the cosolvent.
Preferably, in the step (2), the mass ratio of the deionized water to the positive electrode material is 1:1-5:1, and the water washing time is 5-60 min.
Preferably, in the step (3), the sintering atmosphere is air or oxygen, the sintering temperature is 200-800 ℃, and the sintering time is 1-24 h.
Preferably, in the step (4), the sintering atmosphere is air or oxygen, the sintering temperature is 100-600 ℃, the sintering time is 2-15 h, and the coating agent is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
The invention reduces the sintering temperature by bromide fluxing agent, combines a specific sectional heat preservation one-time sintering system, and reduces the problem of lithium nickel mixed discharge generated by high-temperature sintering of single crystal materials; and the dispersibility of the monocrystalline material is improved by the electrostatic repulsion effect generated by the adsorption of anions in the fluxing agent on the surfaces of the monocrystalline particles, and the morphology and the particle size of the monocrystalline material are controlled by regulating and controlling the combination and the dosage of the fluxing agent. Finally, the dispersibility and tap density of the monocrystal high-nickel ternary cathode material can be improved, and the electrochemical performance of the material is improved.
Example 1:
the preparation method of the high-nickel single-crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps:
(1) A certain amount of precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 Mixing the mixture with a lithium source (lithium hydroxide), zirconium dioxide and LiBr+KBr (molar ratio 9:1), wherein the molar ratio of lithium ions in the lithium source to a precursor is 1.3:1, the mass ratio of the dopant zirconium dioxide to the precursor is 5000ppm, and the molar ratio of the fluxing agent LiBr+KBr in the lithium source and the cosolvent is 80wt%; then sintering in oxygen atmosphere, heating to 600 ℃ at 10 ℃/min for 24 hours, heating to 900 ℃ at 10 ℃/min for 24 hours, cooling at 10 ℃/min after sintering, and crushing after discharging the product to obtain the monocrystalline NCM anode material initially;
(2) Taking a primary sintered monocrystalline NCM positive electrode material, adding deionized water with a mass ratio of 5:1 for washing, stirring for 60min, and carrying out suction filtration, drying and sieving after the completion;
(3) Carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain a monocrystalline NCM anode material;
(4) Mixing single crystal NCM positive electrode material with 5000ppm H 3 BO 3 And (3) mixing, sintering for three times in an oxygen atmosphere at 600 ℃ for 15 hours, cooling with a furnace after sintering, and sieving after discharging the product from the furnace to obtain a single crystal NCM product (shown in figures 1-3).
Example 2:
the preparation method of the high-nickel single-crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps:
(1) Precursor Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 Mixing the mixture with a lithium source (lithium hydroxide), tungsten trioxide and NaBr, wherein the molar ratio of lithium ions in the lithium source to a precursor is 1.06:1, the mass ratio of the dopant tungsten trioxide to the precursor is 2000ppm, and the molar ratio of a fluxing agent LiBr+KBr (molar ratio of 1:1) to the sum of the lithium source and the cosolvent is 15wt%. Then sintering in oxygen atmosphere, firstly heating to a first sintering temperature of 480 ℃ at 4 ℃/min for 16 hours, heating to a second sintering temperature of 750 ℃ at 4 ℃/min for 12 hours, cooling with a furnace at 3 ℃/min after sintering, and crushing after discharging the product from the furnace to obtain the monocrystalline NCM anode material;
(2) Taking a certain amount of once sintered monocrystalline NCM positive electrode material, adding deionized water with a mass ratio of 3:1 for washing, stirring for 40min, and carrying out suction filtration, drying and sieving after the completion;
(3) Carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 650 ℃, the sintering time is 8 hours, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain a monocrystalline NCM anode material;
(4) Single crystal NCM cathode material with 300ppm Al 2 O 3 Mixing, sintering in oxygen atmosphere for three times at 300 deg.c for 6 hr, cooling in furnace, and dischargingThe mixture was then screened to give a single crystal NCM product (as shown in FIG. 4).
Example 3:
the preparation method of the high-nickel single-crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps:
(1) A certain amount of precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 With lithium source (lithium carbonate), magnesium oxide, liNO 3 +NaBr, wherein the molar ratio of lithium ions in the lithium source to the precursor is 0.8:1, the mass ratio of the dopant magnesium oxide to the precursor is 100ppm, and the fluxing agent LiNO 3 The molar ratio of +NaBr to the sum of the lithium source and the co-solvent was 0.5wt%. Then sintering in oxygen atmosphere, heating to a first sintering temperature of 200 ℃ at 0.5 ℃/min for 2 hours, heating to a second sintering temperature of 400 ℃ at 0.5 ℃/min for 2 hours, cooling at a cooling rate of 0.5 ℃/min after sintering, and crushing after discharging the product from the furnace to obtain the monocrystalline NCM anode material;
(2) Taking a certain amount of once sintered monocrystalline NCM positive electrode material, adding deionized water with a mass ratio of 1:1 for washing, stirring for 5min, and carrying out suction filtration, drying and sieving after the completion;
(3) Carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 200 ℃, the sintering time is 1h, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain a monocrystalline NCM anode material;
(4) Mixing single crystal NCM positive electrode material with 500ppm Li 3 PO 4 And (3) mixing, sintering for three times in an oxygen atmosphere at 100 ℃ for 2 hours, cooling with a furnace after sintering, and sieving after discharging the product from the furnace to obtain a single crystal NCM product (shown in figure 5).
Comparative example 1:
the preparation method of the monocrystal ternary material by conventional high-temperature sintering comprises the following steps:
(1) Precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 Mixing with lithium source (lithium hydroxide) and zirconium dioxide, wherein the molar ratio of lithium ion to precursor in the lithium source is 1.3:1, and the dopant is oxidizedThe mass ratio of zirconium to the precursor was 5000ppm. Then sintering in oxygen atmosphere at 900 ℃ for 24 hours, cooling along with a furnace after sintering, and crushing the product after discharging from the furnace to obtain the monocrystalline NCM anode material;
(2) Carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain a monocrystalline NCM anode material;
(3) Mixing single crystal NCM positive electrode material with 5000ppm H 3 BO 3 And (3) mixing, sintering for three times in an oxygen atmosphere at 600 ℃ for 15 hours, cooling with a furnace after sintering, and sieving after discharging the product from the furnace to obtain a single crystal NCM product (shown in figure 6).
Comparative example 2:
the method comprises the following steps:
(1) A certain amount of precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 With lithium source (lithium hydroxide), yttrium oxide, na 2 SO 4 Mixing, wherein the molar ratio of lithium ions in a lithium source to a precursor is 1.3:1, the mass ratio of the dopant yttrium oxide to the precursor is 5000ppm, and the fluxing agent Na is 2 SO 4 The molar ratio of the lithium source and the cosolvent is 60wt%. Then sintering in oxygen atmosphere at 900 ℃ for 24 hours, cooling along with a furnace after sintering, and crushing the product after discharging from the furnace to obtain the monocrystalline NCM anode material;
(2) Taking a certain amount of once sintered monocrystalline NCM positive electrode material, adding deionized water with a mass ratio of 5:1 for washing, stirring for 60min, and carrying out suction filtration, drying and sieving after the completion;
(3) Carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain a monocrystalline NCM anode material;
(4) Mixing single crystal NCM positive electrode material with 5000ppm H 3 BO 3 Mixing, sintering in oxygen atmosphere for three times at 600 deg.c for 15 hrCooling with the furnace after the completion of the formation, and sieving the product after the product is discharged from the furnace to obtain a single crystal NCM product (shown in figure 7).
The results of the performance tests of the products obtained in examples and comparative examples are shown in the following table:
as can be seen from the table, the positive electrode material prepared by the method has good tap density, first charge and discharge efficiency, discharge capacity and capacity retention rate, and is greatly improved compared with comparative examples 1-2.
Claims (4)
1. The preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material is characterized by comprising the following specific operation steps:
step 1: mixing the high-nickel ternary precursor with a lithium source, a doping agent and a fluxing agent, then sintering in an oxygen atmosphere for one time, heating to a first sintering temperature of 200-600 ℃ for 2-24 hours, and promoting the fluxing agent and the lithium source to form a eutectic substance so as to fully diffuse lithium ions, thereby promoting uniform generation and growth of monocrystalline particles; heating to the second sintering temperature of 400-900 ℃ for 2-24 hours, cooling at a cooling rate of 0.5-10 ℃/min after sintering, and crushing after discharging the product from the furnace to obtain the monocrystalline NCM anode material;
the molar ratio of lithium ions in the lithium source to the high-nickel ternary precursor is 0.8-1.3;
the mass ratio of the dopant to the precursor is 100-5000 ppm; the fluxing agent is LiBr or LiBr and NaBr, KBr, liNO 3 Is a composition of (a); the proportion of the fluxing agent to the sum of the lithium source and the fluxing agent is 0.1-80 wt%;
the high-nickel ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 ，x>0.6，y>0，1-x-y>0；
In the step 1, the temperature is raised to the first sintering temperature and the second sintering temperature at a temperature raising rate of 0.5-10 ℃/min;
step 2: adding deionized water into the monocrystalline NCM positive electrode material obtained in the step 1 for washing, wherein the mass ratio of the deionized water to the monocrystalline NCM positive electrode material obtained in the step 1 is 1:1-5:1; washing with water, stirring for 5-60 min, and carrying out suction filtration, drying and sieving after completion;
step 3: carrying out secondary sintering on the product obtained in the step 2 in air or oxygen atmosphere, wherein the sintering temperature is 200-800 ℃, the sintering time is 1-24 hours, cooling along with a furnace after sintering is finished, and sieving the product after discharging from the furnace to obtain the monocrystalline NCM anode material;
step 4: mixing the monocrystalline NCM positive electrode material in the step 3 with a coating agent, performing three times of sintering under the air or oxygen atmosphere, wherein the sintering temperature is 100-600 ℃, the sintering time is 2-15 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the product;
the method can achieve the purpose of controlling the particle size by changing the combination and the dosage of the fluxing agent.
2. The method for preparing a ternary positive electrode material of high-nickel monocrystal nickel cobalt lithium manganate according to claim 1, wherein the lithium source in the step 1 is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate.
3. The method for preparing a ternary positive electrode material of high-nickel monocrystal nickel cobalt lithium manganate according to claim 1, wherein the metal element in the doping agent in the step 1 is one or more of Mg, zr, W, ti, Y, sr, al, mo, V.
4. The method for preparing a ternary positive electrode material of high-nickel monocrystal nickel cobalt lithium manganate according to claim 1, wherein the coating agent in the step 4 is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
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| CN115432750B (en) * | 2022-10-21 | 2023-11-21 | 清远佳致新材料研究院有限公司 | Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof |
| CN115504524B (en) * | 2022-10-24 | 2024-02-20 | 中国石油大学(华东) | Single-crystal high-nickel material, and preparation method and application thereof |
| CN115367816B (en) * | 2022-10-27 | 2023-02-03 | 宜宾锂宝新材料有限公司 | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN115911337B (en) * | 2023-01-06 | 2023-06-23 | 宜宾锂宝新材料有限公司 | High-nickel positive electrode material, preparation method thereof and battery |
| CN116282215B (en) * | 2023-02-24 | 2023-11-24 | 金驰能源材料有限公司 | High-nickel layered positive electrode material, preparation method thereof and lithium ion battery |
| CN116199278B (en) * | 2023-05-05 | 2023-08-04 | 四川新能源汽车创新中心有限公司 | Preparation method of ternary positive electrode material of lithium battery |
| CN116750810A (en) * | 2023-07-11 | 2023-09-15 | 广东省科学院资源利用与稀土开发研究所 | Single-crystal type high-nickel ternary positive electrode material for high-voltage lithium ion battery and preparation method thereof |
| CN116605926B (en) * | 2023-07-20 | 2023-10-20 | 新乡天力锂能股份有限公司 | Preparation method of gamma pure-phase alumina coated high-nickel single-crystal positive electrode material |
| CN117038956B (en) * | 2023-10-09 | 2024-01-23 | 浙江帕瓦新能源股份有限公司 | Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery |
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