CN114447315A - Ultra-small particle size single crystal nickel-cobalt-manganese ternary cathode material and preparation method thereof - Google Patents
Ultra-small particle size single crystal nickel-cobalt-manganese ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a single crystal nickel-cobalt-manganese ternary cathode material with ultra-small grain diameter and a preparation method thereof, and the method comprises the following steps: uniformly mixing a nickel-cobalt-manganese ternary precursor, a lithium source and a modification auxiliary agent, and calcining at 800-920 ℃ for at least 5 hours to obtain an oxidation-modified ternary cathode material; crushing the oxidation-modified ternary cathode material to obtain powder A; adding the powder A into water containing a sulfate type coating agent, carrying out water washing coating modification, filtering to obtain powder B, and carrying out secondary calcination on the powder B at 500-700 ℃ for at least 3h to obtain powder C; and crushing the powder C again to obtain the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material with the grain size of less than 2 mu m. The invention prepares the ternary single crystal type anode material with D50 less than 2 mu m and good dispersibility, and improves the gram capacity and rate capability of the material.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a single crystal nickel-cobalt-manganese ternary cathode material with an ultra-small particle size and a preparation method thereof.
Background
Lithium ion batteries, which are the most popular new energy batteries at present, have become mainstream batteries through more than 30 years of industrial application, and are classified as batteries for electric tools to be applied to 3C digital electronic products and electric tools; the vehicle power battery is applied to electric vehicles, and the battery for energy storage is applied to power companies. At present, ternary (nickel-cobalt-manganese) lithium batteries show excellent comprehensive performance in the aspects of energy density, discharge voltage and the like, and are generally concerned by people.
The most interesting of the present is that ternary (nickel cobalt manganese) positive electrode materials are divided into two types: one is micron-sized secondary spherical particles formed by agglomeration of nano-scale small crystal grains, commonly called secondary spheres or polycrystal, the grain size of the polycrystal product is D50 which is more than or equal to 6um, the current Ni83 system has better charging and discharging capacity (0.2C charging and discharging) of 232mAh/g and 209mAh/g, and the first efficiency is more than or equal to 88 percent. However, in the process of charging and discharging, the volume shrinkage and expansion of primary particles are obvious, and spheres are easy to break, so that the safety is poor, and the single crystal material cannot break spheres, so that the safety is greatly superior to that of polycrystal. The existing market is mainly large-particle ternary nickel-cobalt-manganese single crystal type anode materials, D50 is usually between 3 and 5 mu m, in the existing electrochemical performance, the charge and discharge capacity (0.2C charge and discharge) is 228mAh/g and 201mAh/g, and the first effect is more than or equal to 88%. It can be seen that the safety of single crystals is obtained at the expense of a certain capacity, especially the discharge capacitance, which is an important condition for examining the electrochemical performance of materials. Therefore, the significance of obtaining single crystal materials with high capacity and high multiplying power is great.
The prior art and the prior art can realize the ternary (nickel cobalt manganese) single crystal type anode material with D50 more than 3 mu m, but the preparation of the ternary (nickel cobalt manganese) single crystal type anode material with D50 less than 2 mu m and good dispersibility in the prior synthesis system still has great technical difficulty.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a single crystal nickel-cobalt-manganese ternary cathode material with ultra-small particle size and a preparation method thereof, and the prepared ternary cathode material is a ternary single crystal oxide with the particle size of less than 2 mu m and can improve the rate capability and capacity of a battery.
In order to achieve the technical purpose, the technical scheme of the ternary cathode material is as follows:
the method comprises the following steps:
(1) uniformly mixing a nickel-cobalt-manganese ternary precursor, a lithium source and a modification auxiliary agent, and calcining at 800-920 ℃ for at least 5 hours to obtain an oxidation-modified ternary cathode material;
(2) crushing the oxidation-modified ternary cathode material to obtain powder A;
(3) adding the powder A into water containing a sulfate type coating agent, carrying out water washing coating modification, filtering to obtain powder B, and carrying out secondary calcination on the powder B at 500-700 ℃ for at least 3h to obtain powder C;
(4) and crushing the powder C again to obtain the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material with the grain size of less than 2 mu m.
Further, Ni is adopted as the nickel-cobalt-manganese ternary precursor0.83Co0.12Mn0.05(OH)2D50 of the nickel-cobalt-manganese ternary precursor is 2-5 um; the lithium source is lithium hydroxide with D50 being 2-5 um; the modifying auxiliary agent is at least one of oxide, hydroxide and fluoride containing Zr, Mg, Ti, Ce, Mo, Al, W, Nb, B or Sr elements, and the D50 of the modifying auxiliary agent is 10-100 nm.
Further, the molar ratio of the nickel-cobalt-manganese ternary precursor to the lithium source is 100: (103-110), wherein the addition amount of the modification auxiliary agent is 100-5000 ppm of the total mass of the nickel-cobalt-manganese ternary precursor and the lithium source.
Further, the step (2) is carried out to obtain powder A with the particle size D50 of less than 1 μm.
Further, in the step (3), the coating agent is at least one of sulfates of Co, Al, W, Ce, Nb, B, Ti, Mg and Zr.
Further, the solid-to-liquid ratio of the powder A to water in the step (3) is 1 g: (1-2) mL; the adding amount of the coating agent is 500ppm to 5000ppm of the mass of the powder A.
Further, the washing temperature in the step (3) is 0-50 ℃, and the stirring speed is 500 r/min.
Further, after uniformly mixing the nickel-cobalt-manganese ternary precursor, the lithium source and the modification auxiliary agent in the step (1), sintering at 230-780 ℃ for 4-8 h, heating to 800-920 ℃ and calcining for 7-15 h;
in the step (3), the powder B is sintered for 3-7 hours at 200-400 ℃, then heated to 500-700 ℃ and sintered for 5-10 hours.
Further, in the step (4), the powder C is subjected to jet milling under the condition of 0.5-0.7 MPa to obtain the ultra-small grain size single crystal nickel cobalt manganese ternary cathode material with the grain size D50 being less than 1 mu m.
The single crystal nickel-cobalt-manganese ternary cathode material with the ultra-small grain size is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through the steps of calcination modification, water washing coating modification, crushing and the like, the ternary (nickel-cobalt-manganese) single crystal type anode material with D50 being less than 2 mu m and good dispersibility is prepared, namely the advantage of single crystal safety is kept, and meanwhile, the ternary (nickel-cobalt-manganese) single crystal type anode material is applied to a lithium ion battery, the intercalation and deintercalation of lithium ions can be effectively improved, and the gram capacity and the rate capability of the material are finally improved, the first discharge capacity (0.2C charge and discharge) of the material can exceed 215mAh/g, the first efficiency is more than 88%, and under the same test condition, the capacity retention rate fluctuation between five continuous cycles is very small and is basically less than 1.3 per thousand; charging and discharging under the high-rate condition of 16c, and still keeping the discharge capacitance at 162mAh/g after circulating for 36 times; the material has wide application range, and can be used for high-precision products with strict limitation on volume, such as a micro unmanned aerial vehicle, a micro notebook computer and partial batteries for military use, on one hand, because the gram capacity of the ultra-small single crystal particles is high; on the other hand, the composite material can be blended with other anode materials to be used for products of different scenes. The invention not only keeps the safety of single crystal, but also improves the electrochemical performance of the single crystal, and reaches or even exceeds the level of polycrystal.
Furthermore, the crushing adopted in the invention can be matched with other steps, so that the particle size of the obtained material is effectively reduced, and the electrochemical performance is improved.
Drawings
FIG. 1 is a micro-topography of a ternary cathode material made in accordance with a first embodiment of the present invention;
FIG. 2 is a graph of the first charge-discharge capacity of the ternary cathode material prepared in the first embodiment of the present invention;
fig. 3 shows the capacity retention efficiency of the ternary cathode material prepared in the first embodiment of the present invention, tested at different rate capabilities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method comprises the following steps:
1) high nickel ternary precursor Ni0.83Co0.12Mn0.05(OH)2Uniformly mixing a lithium source and a modification auxiliary agent, and calcining, wherein the sintering temperature is 230-780 ℃ in a temperature rise section, the sintering time is 4-8 h, the temperature is 800-920 ℃ in a constant temperature section, and the sintering time is 7-15 h to obtain an oxidation-modified high-nickel ternary cathode material;
wherein the molar ratio of the precursor to the lithium source is 100: (103-110), wherein D50 of PSD of the precursor is 2-5 um; the lithium source is lithium hydroxide, and D50 of PSD is 2-5 um; the modification auxiliary agent is at least one oxide, hydroxide or fluoride containing Zr, Mg, Ti, Ce, Mo, Al, W, Nb, B or Sr elements, the D50 of the particle size PSD is 10-100 nm, and the addition amount of the modification auxiliary agent is 100-5000 ppm of the total mass of the high-nickel ternary precursor and the lithium source;
2) crushing the ternary cathode material subjected to oxidation modification after primary calcination to obtain powder A with the particle size D50 being less than 1 mu m; the crushing method comprises the following specific steps: firstly, carrying out rotary wheel milling to obtain a particle size D50 of below 10 mu m, then carrying out roller milling to obtain a particle size D50 of below 5 mu m, and finally carrying out jet mill milling under the pressure of 1-1.5 MPa to obtain ternary single crystal material powder A with the D50 of less than 1 mu m.
3) Washing, coating and modifying the crushed high-nickel ternary cathode material powder A, and then performing filter pressing and drying to obtain powder B, wherein the drying is performed at 120-160 ℃ under vacuum, and the vacuum degree is more than or equal to 0.06 MPa; carrying out secondary calcination on the powder B to obtain powder C; the secondary sintering temperature is 200-400 ℃ in a temperature rising section, and the sintering time is 3-7 h; the constant temperature section is 500-700 ℃, and the sintering time is 5-10 h;
the water washing process comprises the following steps: the solid-liquid ratio is 1 g: (1-2) mL, washing for 20-60 min, washing at 0-50 ℃, stirring at 500r/min, adding a coating agent while washing, wherein the coating agent is at least one sulfate of Co, Al, W, Ce, Nb, B, Ti, Mg and Zr, and the adding amount of the coating agent is 500-5000 ppm of the mass of the powder A;
4) and (3) carrying out jet milling on the ternary cathode material powder C after secondary calcination, wherein the milling pressure is 0.5-0.7 MPa, and obtaining the coated modified ultra-small-particle-size high-nickel single crystal ternary cathode material with the particle size D50 being less than 1 mu m.
The present invention is further illustrated by the following specific examples.
Example one
1) Uniformly mixing a high-nickel ternary precursor, lithium source lithium hydroxide and a modification auxiliary agent, and calcining, wherein the temperature is raised to 500 ℃ in a sintering temperature raising section of 6 hours, the temperature in a constant temperature section is 850 ℃, and the time is 10 hours to obtain an oxidation-modified high-nickel ternary cathode material;
wherein the total mass part of the high-nickel ternary precursor and the lithium hydroxide is 205 parts, and the modification auxiliary agent is 0.00205 parts of Mg (OH) by mass2That is, the amount added was 2050 ppm. The molar ratio of the high-nickel ternary precursor to the lithium hydroxide is 100: 105; ni is adopted as the ternary precursor of Ni, Co and Mn0.83Co0.12Mn0.05(OH)2。
2) Crushing the ternary cathode material subjected to primary calcination to obtain powder A with the particle size D50 being less than 1 mu m; the crushing method comprises the following specific steps: firstly, wheel-selecting grinding is carried out, the granularity D50 is below 10 mu m, then the granularity D50 is below 5 mu m through roller pair grinding, and finally the ternary single crystal material powder A with the D50 being less than 1 mu m is obtained through a jet mill under the grinding pressure of 1.5 MPa;
3) washing, coating and modifying the crushed high-nickel ternary cathode material powder A, filtering and drying to obtain powder B, wherein the drying is carried out at 140 ℃ under vacuum with the vacuum degree of 0.06 MPa; carrying out secondary calcination on the powder B to obtain powder C; the secondary sintering temperature is as follows: the temperature rising section is 300 ℃, and the sintering time is 5 h; the constant temperature section is 600 ℃, and the sintering time is 8 hours;
the water washing process comprises the following steps: the solid-liquid ratio of the powder A to water is 1 g: 1mL, washing time of 40min, washing temperature of 25 ℃, stirring speed of 500r/min, adding a coating agent while washing, wherein the coating agent is CoSO, and the addition amount of the coating agent is 2000ppm of the mass of the powder A;
4) and (3) crushing the ternary cathode material powder C subjected to secondary calcination under the crushing pressure of 0.6MPa to obtain the coated and modified ultra-small-particle-size single crystal nickel-cobalt-manganese ternary cathode material.
The particle size range is 0.35-0.90 μm as shown in figure 1.
As shown in FIG. 2, the first discharge capacity (0.2C charge-discharge) of the obtained material is more than 215mAh/g, and the first efficiency is more than 88%.
The high capacity maintaining efficiency is still maintained after testing under different multiplying power performances, as shown in figure 3, when the capacitor is charged and discharged at 0.2c, the first discharge capacitance of 218mAh/g basically does not change after five continuous cycles; when the capacitor is charged and discharged at 0.5c, the capacity retention rate is basically unchanged after six to ten times of circulation, and the discharge capacitance is 212.2 mAh/g; 1c, charging down, wherein the discharge capacitance after ten times of circulation is 206mAh/g, the discharge capacitance after fifteen times of circulation is 205.8mAh/g, the discharge capacitance after 36 times of circulation is 205.1mAh/g, the discharge capacitance after 40 times of circulation is 204.9mAh/g, and the capacity retention rate after 40 times of circulation is relatively eleven times (which can be considered to be basically equal to the first discharge capacitance) is 99.47%; even when 16c is charged and discharged, the discharge capacity is still kept at 162mAh/g after 36 times of circulation.
As can be further seen from fig. 3, under the same test condition, the material obtained by the present invention has a small fluctuation of the capacity retention rate between five consecutive cycles, which is substantially less than 1.3%, and when the material is charged and discharged below 1c, the fluctuation of the capacity retention rate between five consecutive cycles is less than 1%.
Example two
1) Uniformly mixing the high-nickel ternary precursor, a lithium source and a modification auxiliary agent, and calcining, wherein the temperature is raised to 230 ℃ in 8h in a sintering temperature raising section, the temperature is 800 ℃ in a constant temperature section, and the time is 15h to obtain an oxidation-modified high-nickel ternary cathode material;
wherein the total mass part of the high-nickel ternary precursor and the lithium hydroxide is 203 parts, and the mass part of the modification auxiliary agent is 0.005 part of TiO2I.e., the amount added was 5000 ppm. The molar ratio of the high-nickel ternary precursor to the lithium hydroxide is 100: 103.
2) Crushing the ternary cathode material subjected to primary calcination to obtain powder A with the particle size D50 being less than 1 mu m; the crushing method comprises the following specific steps: firstly, wheel selection grinding is carried out, the grain size D50 is below 10 mu m, then the grain size D50 is below 5 mu m through roller pair grinding, and finally the ternary single crystal material powder A with the D50 being less than 1 mu m is obtained through a jet mill under the grinding pressure of 1.2 MPa.
3) Washing, coating and modifying the crushed high-nickel ternary cathode material powder A, filtering and drying to obtain powder B, and calcining the powder B for the second time to obtain powder C; the secondary sintering temperature is 200 ℃ in a temperature rising section, and the sintering time is 7 hours; the constant temperature section is 500 ℃, and the sintering time is 10 hours;
the water washing process comprises the following steps: the solid-liquid ratio of the powder A to water is 1 g: 1.5mL of the powder A, wherein the washing time is 20min, the washing temperature is 2 ℃, the stirring speed is 500r/min, the coating agent is added while washing, the coating agent is MgSO, and the addition amount of the coating agent is 5000ppm of the mass of the powder A;
4) and (3) crushing the ternary cathode material powder C subjected to secondary calcination, wherein the crushing pressure is 0.5MPa, so as to obtain the coated and modified ultra-small-particle-size single crystal nickel-cobalt-manganese ternary cathode material, the particle size range is 0.50-1.65 mu m through testing, and the first discharge capacity (0.2C charge and discharge) after the battery is assembled is 214 mAh/g.
EXAMPLE III
1) Uniformly mixing the high-nickel ternary precursor, a lithium source and a modification auxiliary agent, and calcining, wherein the temperature is raised to 780 ℃ in 4 hours in a sintering temperature raising section, the temperature is 920 ℃ in a constant temperature section, and the time is 7 hours to obtain an oxidation-modified high-nickel ternary cathode material;
wherein the total mass part of the high-nickel ternary precursor and the lithium hydroxide is 210 parts, and the modification auxiliary agent is MgF with the mass part of 0.0001 each2And WO3I.e. the addition amount is 200 ppm; high nickel ternary precursor and lithium hydroxideIs 100: 110.
2) Crushing the ternary cathode material subjected to primary calcination to obtain material powder A with the particle size D50 being less than 1 mu m; the crushing method comprises the following specific steps: firstly, wheel selection grinding is carried out, the grain size D50 is below 10 mu m, then the grain size D50 is below 5 mu m through roller pair grinding, and finally the ternary single crystal material powder A with the D50 being less than 1 mu m is obtained through a jet mill under the grinding pressure of 1.0 MPa.
3) Washing, coating and modifying the crushed high-nickel ternary cathode material powder A, filtering and drying to obtain powder B, and calcining the powder B for the second time to obtain powder C; the secondary sintering temperature is 400 ℃ in a temperature rise section, and the sintering time is 3 h; the constant temperature section is 700 ℃, and the sintering time is 5 h;
the water washing process comprises the following steps: the solid-liquid ratio of the powder A to water is 1 g: 2mL, washing time of 60min, washing temperature of 50 ℃, stirring speed of 500r/min, adding coating agents while washing, wherein the coating agents are Al (SO) and Zr (SO) with the addition amount of 2500ppm of powder A by mass;
4) and (3) crushing the ternary cathode material powder C subjected to secondary calcination, wherein the crushing pressure is 0.7MPa, so that the coated and modified ultra-small-particle-size single crystal nickel-cobalt-manganese ternary cathode material is obtained, the particle size range is 0.48-1.72 mu m through tests, and the first discharge capacity (0.2C charge and discharge) after the battery is assembled is 208 mAh/g.
Comparative example 1
And (3) investigating the influence of different coating agent addition modes on the obtained material.
Adding a sulfate coating agent during secondary calcination, not adding the sulfate coating agent during washing, and preparing a sample 1-1 under the same conditions as in the first embodiment; because the coating agent is not uniformly coated on the powder, after the battery is assembled, the first discharge capacity (0.2C charge and discharge) is 195mAh/g, and the first effect is obviously reduced.
Therefore, the coating agent is added in a mode which has great influence on the final performance of the obtained material, and needs to be added in the water washing process, and the uniform coating and impurity removal process can be completed simultaneously with the water washing.
Comparative example 2
The influence of different preparation processes on the material obtained by the invention is examined.
After washing with water at 0 ℃, 20 ℃, 40 ℃ and 60 ℃ respectively, the obtained materials were tested under the same conditions as in example one:
at 0 ℃, the mass fraction of the content of LiOH is 0.07 percent, Li2CO3The mass fraction of the content of (b) is 0.2%; the first discharge (0.2C) of electricity deduction is 212.6, and the first effect is 88%.
At 20 ℃, the mass fraction of the content of LiOH is 0.065%, Li2CO3The mass fraction of the content of (b) is 0.18%; the first discharge (0.2C) is 213.6, and the first effect is 88.2%.
At 40 ℃, the mass fraction of the content of LiOH is 0.062%, Li2CO3The mass fraction of the content of (b) is 0.17%; the first discharge (0.2C) is 211.2, and the first effect is 87.3%.
At 60 ℃, the mass fraction of the content of LiOH is 0.058%, Li2CO3The mass fraction of the content of (b) is 0.16%; the first discharge (0.2C) is 205.2, and the first effect is 85%.
As can be seen from the above, different residual lithium contents were obtained at different temperatures, and the higher the washing temperature, the lower the residual lithium content. However, the surface structure of the material can be damaged due to the fact that the washing temperature is too high, and the electricity-saving first-release and first-effect are too low, so that the temperature is preferably 0-50 ℃.
The invention can be blended with other positive electrode materials for products of different scenes, such as:
1. can be mixed with the product of lithium cobaltate (D50>6 μm) to improve the volume density and gram capacity of the lithium cobaltate;
2. can be mixed with lithium iron phosphate to improve the capacity of the lithium iron phosphate;
3 can be mixed with high nickel polycrystal, thereby improving the safety of the polycrystal.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a single crystal nickel-cobalt-manganese ternary cathode material with ultra-small particle size is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing a nickel-cobalt-manganese ternary precursor, a lithium source and a modification auxiliary agent, and calcining at 800-920 ℃ for at least 5 hours to obtain an oxidation-modified ternary cathode material;
(2) crushing the oxidation-modified ternary cathode material to obtain powder A;
(3) adding the powder A into water containing a sulfate type coating agent, carrying out water washing coating modification, filtering to obtain powder B, and carrying out secondary calcination on the powder B at 500-700 ℃ for at least 3h to obtain powder C;
(4) and crushing the powder C again to obtain the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material with the grain size of less than 2 mu m.
2. The preparation method of the ultra-small particle size single crystal nickel cobalt manganese ternary positive electrode material of claim 1, characterized in that: ni is adopted as the ternary precursor of Ni, Co and Mn0.83Co0.12Mn0.05(OH)2D50 of the nickel-cobalt-manganese ternary precursor is 2-5 um; the lithium source is lithium hydroxide with D50 being 2-5 um; the modifying auxiliary agent is at least one of oxide, hydroxide and fluoride containing Zr, Mg, Ti, Ce, Mo, Al, W, Nb, B or Sr elements, and the D50 of the modifying auxiliary agent is 10-100 nm.
3. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the molar ratio of the nickel-cobalt-manganese ternary precursor to the lithium source is 100: (103-110), wherein the addition amount of the modification auxiliary agent is 100-5000 ppm of the total mass of the nickel-cobalt-manganese ternary precursor and the lithium source.
4. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: and (3) crushing in the step (2) to obtain powder A with the particle size D50 less than 1 mu m.
5. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: in the step (3), the coating agent is at least one of sulfates of Co, Al, W, Ce, Nb, B, Ti, Mg and Zr.
6. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: in the step (3), the solid-to-liquid ratio of the powder A to water is 1 g: (1-2) mL; the adding amount of the coating agent is 500ppm to 5000ppm of the mass of the powder A.
7. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: and (4) washing the water in the step (3) at the temperature of 0-50 ℃ and stirring at the speed of 500 r/min.
8. The method for preparing the ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: uniformly mixing the nickel-cobalt-manganese ternary precursor, the lithium source and the modification auxiliary agent in the step (1), sintering at 230-780 ℃ for 4-8 h, heating to 800-920 ℃ and calcining for 7-15 h;
in the step (3), the powder B is sintered for 3-7 hours at 200-400 ℃, then heated to 500-700 ℃ and sintered for 5-10 hours.
9. The method for preparing the ultra-small grain size single crystal nickel cobalt manganese ternary positive electrode material according to any one of claims 1 to 8, wherein the method comprises the following steps: in the step (4), the powder C is subjected to jet milling under the condition of 0.5-0.7 MPa to obtain the ultra-small grain size single crystal nickel cobalt manganese ternary cathode material with the grain size D50 being less than 1 mu m.
10. The ultra-small grain size single crystal nickel-cobalt-manganese ternary cathode material prepared by the preparation method of any one of claims 1 to 8.
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| CN114540934A (en) * | 2021-12-03 | 2022-05-27 | 宜宾锂宝新材料有限公司 | Preparation method of single crystal type nickel-cobalt-manganese ternary cathode material |
| CN114843502A (en) * | 2022-05-16 | 2022-08-02 | 北京卫蓝新能源科技有限公司 | High-rate single-crystal high-nickel cathode material and preparation method and application thereof |
| CN114927693A (en) * | 2022-05-30 | 2022-08-19 | 远景动力技术(江苏)有限公司 | Positive electrode active material, method for producing same, electrochemical device, and electronic device |
| CN115084507A (en) * | 2022-06-22 | 2022-09-20 | 上海大学 | Preparation method of single crystal high-nickel ternary cathode material |
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| CN115084507B (en) * | 2022-06-22 | 2024-04-19 | 上海大学 | Preparation method of monocrystal high-nickel ternary positive electrode material |
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