CN110867577A - 811NCM ternary cathode material with three-dimensional nanowire array structure and preparation method thereof - Google Patents
811NCM ternary cathode material with three-dimensional nanowire array structure and preparation method thereof Download PDFInfo
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Abstract
A811 NCM ternary anode material with a three-dimensional nanowire array structure and a preparation method thereof are disclosed, wherein the microstructure of the ternary anode material is that the nanowire is self-assembled by spherical single crystal particles once and then is self-assembled into a strip array structure, the particle size is 10-50 mu m long, and the width is 1-3 mu m; the preparation method comprises the following steps: dissolving nickel salt, cobalt salt and manganese salt in a solvent by adopting a solvothermal method, adding ammonia water or sodium hydroxide to adjust the pH value, carrying out solvothermal reaction for 10-24h at a certain temperature, synthesizing oxalate precipitate containing nickel, cobalt and manganese, uniformly mixing the oxalate precipitate with a lithium source, and calcining at a high temperature to obtain the 811NCM ternary cathode material. The preparation process is simple to operate and low in cost; in the synthesis process, the glycol or the glycerol is used as a solvent and a dispersing agent, so that compared with a coprecipitation method, the problem of particle agglomeration is solved; and the obtained final product has a layered structure and a larger specific surface area, and is beneficial to further soaking the material with electrolyte, so that the electrochemical performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical application, and particularly relates to a 811NCM ternary cathode material with a three-dimensional nanowire array structure and a method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure by utilizing solvothermal.
Background
Nowadays, for the continuous promotion of the demand of energy storage, the research and development of high energy density lithium ion batteries play a key role. The lithium ion battery has the advantages of high working voltage, less self-discharge, large energy density, small memory effect, long cycle life, environmental protection and the like. Compared with the negative electrode material of the lithium ion battery, the positive electrode material has more defects in the aspects of capacity and safety, and the positive electrode material becomes the key for determining the overall performance of the battery, so further research and improvement of related performance are needed.
At present, a nickel-cobalt-manganese (NCM) ternary cathode material is a research hotspot, Ni, Co and Mn are adjacent elements in the same period, and the production cost of the material can be reduced by replacing Co with partial Ni and Mn. In the NCM ternary positive electrode material, Ni is +2 valence, Co is +3 valence, Mn is +4 valence, and Mn is4+Acting to stabilize the structure, Co3+Is favorable for improving the electronic conductivity, Ni2+The material capacity can be increased by redox. 811NCM ternary cathode Material (LiNi)0.8Co0.1Mn0.1O2) And the increase of the nickel content can improve the capacity of the material, and has wider development prospect. In the prior art, the 811NCM ternary cathode material is mainly prepared by using a coprecipitation method to control the pH value of a solution to synthesize a hydroxide precursor containing nickel, cobalt and manganese, mixing the hydroxide precursor with a lithium source, and then calcining the mixture at high temperature to obtain a final product, wherein the size and the length of particles of the material are basically more than 5 mu m. During the precipitation process, dissolveThe change of the pH value of the solution has direct influence on the precipitation of three elements of nickel, cobalt and manganese, and incomplete precipitation is easily caused by overhigh and overlow values; in addition, the rotating speed of the solution has great influence on the appearance of the material, particle agglomeration is easily caused by too low rotating speed, and particle breakage is easily caused by too high rotating speed. The shape and the size of the material are important factors influencing the electrochemical performance of the high-nickel 811NCM ternary cathode material, so that the synthesized high-nickel 811NCM ternary cathode material with good shape and uniform size has important significance for improving the electrochemical performance of the battery.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a 811NCM ternary cathode material with a three-dimensional nanowire array structure and a preparation method thereof.
A811 NCM ternary cathode material with a three-dimensional nanowire array structure has a layered structure, and has a microscopic appearance that a nanowire is self-assembled by spherical single crystal particles once and then is self-assembled into a strip-shaped array structure, wherein the particle size is 10-50 mu m long and 1-3 mu m wide.
A preparation method of 811NCM ternary cathode material with a three-dimensional nanowire array structure comprises the following steps:
dissolving a nickel source, a cobalt source and a manganese source in a prepared solvent, and uniformly stirring until the nickel source, the cobalt source and the manganese source are completely dissolved; then adding oxalic acid, and stirring uniformly until the oxalic acid is completely dissolved to obtain a mixed solution; adding ammonia water and/or NaOH to adjust the pH value to 7-14; the concentration of the solution obtained by dissolving the nickel source, the cobalt source and the manganese source in the solvent is 0.1-0.4 mol.L-1(ii) a The addition amount of the oxalic acid is 2-10 times of the total amount of the metal ions; the concentration of the ammonia water is 0.01 mol.L-1(ii) a The concentration of NaOH is 1-4 mol.L-1(ii) a The solvent is one or a mixture of more than one of deionized water, glycol or glycerol in any proportion.
Pouring 80mL of the mixed solution prepared in the step (1) into a 100mL reaction kettle, carrying out solvothermal reaction at 160-200 ℃ for 10-24h to obtain green precipitate, carrying out suction filtration and washing on the green precipitate with water and alcohol, carrying out suction filtration, and drying filter residues in an oven at 60-80 ℃ for 12-24 h to obtain an intermediate product;
completely dissolving a lithium source in 10-20 mL of absolute ethyl alcohol, uniformly stirring, adding the intermediate product obtained in the step (2), continuously stirring, heating in a water bath at 60-80 ℃ for drying by distillation to obtain mixed solid powder, and drying in an oven at 60-80 ℃ for 12-24 hours;
and (4) grinding the mixed solid powder obtained in the step (3) for 30-60 min, then placing the ground mixed solid powder into a muffle furnace for calcining, setting the temperature rise rate of the muffle furnace to be 2-5 ℃/min, pre-sintering the mixed solid powder at 400-600 ℃ for 3-6 h, calcining the mixed solid powder at 750-850 ℃ for 10-15 h, and cooling the calcined mixed solid powder to obtain the 811NCM ternary cathode material with the three-dimensional nanowire array structure.
The cobalt source is one or a mixture of more than one of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride in any proportion.
The nickel source is one or a mixture of more than one of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride in any proportion.
The manganese source is one or a mixture of more than one of manganese nitrate, manganese sulfate, manganese acetate and manganese chloride in any proportion.
The adding amount of the nickel source, the cobalt source and the manganese source in the step (1) and the step (3) in the reaction with the lithium source is according to the following atomic molar ratio, namely Ni: co: mn: li is 0.8:0.1:0.1: 1.05-1.15.
The lithium source is one or a mixture of more than one of lithium nitrate, lithium hydroxide and lithium carbonate in any proportion.
The invention has the beneficial effects that:
the 811NCM ternary cathode material with the three-dimensional nanowire array structure is prepared by a solvothermal method, ethylene glycol or glycerol is used as a solvent and a dispersing agent in the synthesis process, compared with a co-precipitation method, the problem of particle agglomeration is solved, and the obtained carbonate precipitate has good appearance, good dispersibility and uniform size.
2, the 811NCM ternary positive electrode material with the three-dimensional nanowire array structure prepared by the solvothermal method has the length of 10-50 microns and large specific surface area, and is beneficial to further soaking the material with electrolyte, so that the electrochemical performance of the battery is improved, and the cycle performance is greatly improved.
Drawings
Fig. 1 is an X-ray diffraction diagram of a 811NCM ternary cathode material with a three-dimensional nanowire array structure prepared by a solvothermal method in the first embodiment of the present invention.
Fig. 2 is a scanning electron microscope image of 811NCM ternary cathode material with a three-dimensional nanowire array structure prepared by a solvothermal method in the first embodiment of the present invention.
Fig. 3 is a cycle performance diagram of a battery assembled by 811NCM ternary cathode materials with a three-dimensional nanowire array structure prepared by a solvothermal method according to the first embodiment of the present invention at a magnification of 0.1C.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example one
The 811NCM ternary cathode material of the present embodiment has a layered crystal structure and a microscopic morphology: after the primary spherical single crystal particles are self-assembled into a nanowire, the nanowire is self-assembled into a strip array structure, and the particle size is basically between 10 mu m in length and 2 mu m in width.
The preparation method of this example includes the following steps:
dissolving 0.08mol of nickel acetate, 0.01mol of manganese acetate and 0.01mol of cobalt acetate in 100mL of deionized water, and uniformly stirring until the nickel acetate, the manganese acetate and the cobalt acetate are completely dissolved; then adding 0.2mol of oxalic acid powder, stirring uniformly until the oxalic acid is completely dissolved to obtain a mixed solution, measuring the pH value to be 5, and then adding 0.01 mol.L-1Adjusting the pH value of the ammonia water solution to 7;
step (2), pouring 80mL of the mixed solution prepared in the step (1) into a 100mL reaction kettle, carrying out solvothermal reaction for 10h at 200 ℃ to obtain green precipitate, washing the obtained green precipitate with water and alcohol for 3 times respectively, carrying out suction filtration, and drying filter residues in an oven at 80 ℃ for 12h to obtain an intermediate product;
step (3), dissolving 0.105mol of lithium carbonate in 20mL of absolute ethyl alcohol, uniformly stirring, adding the intermediate product obtained in the step (2), continuously stirring, heating in a water bath at 60 ℃ and evaporating to dryness to obtain mixed solid powder, and then drying in an oven at 80 ℃ for 12 hours;
and (4) grinding the mixed solid obtained in the step (3) for 60min, then placing the ground mixed solid in a muffle furnace for calcining, setting the temperature rise rate of the muffle furnace to be 2 ℃/min, pre-sintering the mixed solid at 500 ℃ for 5h, and calcining the mixed solid at 800 ℃ for 12h to obtain the 811NCM ternary cathode material LiNi with the three-dimensional nanowire array structure0.8Co0.1Mn0.1O2。
The 811NCM ternary positive electrode material prepared in example one was used for battery assembly and performance testing as follows:
assembling the battery: mixing the 811NCM ternary cathode material prepared in the first embodiment with acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), grinding into uniform slurry, coating the slurry on an aluminum foil, drying for 24 hours at 80 ℃, cutting into pieces, rolling and using the pieces as working electrodes, using a lithium piece as a counter electrode and using 1M LiPF as electrolyte6The solvent is a mixed solution of dimethyl carbonate (DMC), Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1: 1. A half cell model 2032 was assembled in a glove box under argon atmosphere.
(1) X-ray diffraction (XRD) test by analyzing the crystal structure of a sample using an X-ray diffractometer (XRD; Rigaku Ultima IV-185), the X-ray diffraction (XRD) result of the final product is shown in FIG. 1 to conform to the diffraction peak of 811NCM ternary cathode material having good α -NaFeO2A hexagonal layered structure.
(2) Scanning Electron Microscope (SEM) testing: the microscopic morphology of the material was characterized using a field emission scanning electron microscope (FESEM, FEI, Quanta200f), and the Scanning Electron Microscope (SEM) results of the 811NCM ternary cathode material are shown in fig. 2, indicating that the 811NCM ternary cathode material product has a good nanowire array morphology with good dispersibility, and the particle size is substantially between 10 μm long and 2 μm wide.
(3) And (3) testing the electrochemical performance of the battery: constant current charge and discharge test is carried out on a blue battery tester (LAND-CT2001A), the charge and discharge voltage range is 2.8-4.3V, and 1C is 200 mAh.g-1The assembled battery has a charging and discharging test result as shown in FIG. 3, and the specific discharge capacity is 175mAh g after the material is cycled for 100 weeks in a charging and discharging voltage range of 2.8-4.3V and under a multiplying power of 0.1C-1Changed to 165mAh g-1The capacity retention rate was 94.2%.
Example two
The 811NCM ternary cathode material of the present embodiment has a layered crystal structure and a microscopic morphology: the micro-morphology is as follows: after the primary spherical single crystal particles are self-assembled into a nanowire, the nanowire is self-assembled into a strip array structure, and the particle size is basically between 50 μm in length and 3 μm in width.
The preparation method of this example includes the following steps:
dissolving 0.04mol of nickel chloride and 0.04mol of nickel acetate in 20mL of glycol solution, and uniformly stirring until the nickel chloride and the nickel acetate are completely dissolved to obtain a solution A; dissolving 0.005mol of cobalt chloride and 0.005mol of cobalt acetate in 20mL of glycol solution, and uniformly stirring until the cobalt chloride and the cobalt acetate are completely dissolved to obtain a solution B; dissolving 0.005mol of manganese chloride and 0.005mol of manganese acetate in 20mL of glycol solution, and uniformly stirring until the manganese chloride and the manganese acetate are completely dissolved to obtain a solution C; mixing and stirring the solution A, B, C for 0.5h, then adding 5mol of oxalic acid, and uniformly stirring until the oxalic acid is completely dissolved to obtain a mixed solution; sequentially adding 0.01 mol.L-1Ammonia water and concentration of 4 mol. L-1Adjusting the pH value to 14 by NaOH;
pouring 80mL of the mixed solution prepared in the step (1) into a 100mL reaction kettle, carrying out solvothermal reaction for 24h at 160 ℃ to obtain green precipitate, carrying out suction filtration and washing on the green precipitate with water and alcohol, carrying out suction filtration, and drying filter residues in an oven at 80 ℃ for 12h to obtain an intermediate product;
step (3), dissolving 0.575mol of lithium nitrate and 0.575mol of lithium carbonate in 10mL of absolute ethyl alcohol, uniformly stirring, adding the intermediate product obtained in the step (2), continuously stirring, heating in a water bath at 80 ℃, evaporating to dryness to obtain mixed solid powder, and drying in an oven at 60 ℃ for 24 hours;
and (4) grinding the mixed solid powder obtained in the step (3) for 60min, then placing the ground mixed solid powder into a muffle furnace for calcination, setting the temperature rise rate of the muffle furnace to be 5 ℃/min, pre-sintering the mixed solid powder at 600 ℃ for 3h, and calcining the mixed solid powder at 750 ℃ for 15h to obtain the 811NCM ternary cathode material LiNi with the three-dimensional nanowire array structure0.8Co0.1Mn0.1O2。
The 811NCM ternary positive electrode material prepared in example two was used for battery assembly and performance testing as follows:
assembling the battery: mixing the 811NCM ternary cathode material prepared in the second embodiment with acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), grinding into uniform slurry, coating the slurry on an aluminum foil, drying for 24 hours at 80 ℃, cutting into pieces, rolling and using the pieces as working electrodes, using a lithium piece as a counter electrode and using 1M LiPF as electrolyte6The solvent is a mixed solution of dimethyl carbonate (DMC), Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1: 1. A half cell model 2032 was assembled in a glove box under argon atmosphere.
(1) X-ray diffraction (XRD) test by analyzing the crystal structure of a sample using an X-ray diffractometer (XRD; Rigaku Ultima IV-185), the X-ray diffraction (XRD) result of the final product showed that the diffraction peak of 811NCM ternary cathode material having good α -NaFeO was satisfied2A hexagonal layered structure.
(2) Scanning Electron Microscope (SEM) testing: the microscopic morphology of the material is characterized by using a field emission scanning electron microscope (FESEM, FEI, Quanta200f), and the Scanning Electron Microscope (SEM) result of the 811NCM ternary cathode material shows that the 811NCM ternary cathode material is in a strip shape, which indicates that the product has good array morphology and good dispersibility, and the particle size is basically between 50 μm in length and 3 μm in width.
(3) And (3) testing the electrochemical performance of the battery: constant current charge and discharge test is carried out on a blue battery tester (LAND-CT2001A), the charge and discharge voltage range is 2.8-4.3V, and 1C is 200 mAh.g-1The assembled battery has a charging and discharging voltage range of 2.7-4.3V and a discharge specific capacity of 185.6mAh g after the material is cycled for 100 weeks under a multiplying power of 0.1C-1It became 178.7mAh · g-1The capacity retention rate was 96.3%.
EXAMPLE III
A811 NCM ternary cathode material with a three-dimensional nanowire array structure has a layered structure, and has a microscopic appearance that a strip-shaped array structure is formed by self-assembling a nanowire from primary spherical single crystal particles, wherein the particle size is basically 10 mu m in length and 1 mu m in width.
A preparation method of 811NCM ternary cathode material with a three-dimensional nanowire array structure comprises the following steps:
step (1), dissolving 0.004mol of nickel acetate and 0.004mol of nickel sulfate in 20mL of mixed solution of deionized water and glycerol (wherein the ratio of the deionized water to the glycerol is 2: 1), and uniformly stirring until the nickel acetate and the nickel sulfate are completely dissolved to obtain solution A; dissolving 0.004mol of cobalt acetate and 0.004mol of cobalt sulfate in 20mL of a mixed solution of deionized water and glycerol (wherein the ratio of the deionized water to the glycerol is 2: 1), and uniformly stirring until the cobalt acetate and the cobalt sulfate are completely dissolved to obtain a solution B; dissolving 0.004mol of manganese acetate and 0.004mol of manganese sulfate in 20mL of mixed solution of deionized water and glycerol (wherein the ratio of the deionized water to the glycerol is 2: 1), and uniformly stirring until the manganese acetate and the manganese sulfate are completely dissolved to obtain solution C; mixing and stirring the solution A, B, C for 0.5h, then adding 0.4mol of oxalic acid, and uniformly stirring until the oxalic acid is completely dissolved to obtain a mixed solution; adding 0.01 mol/L-1Ammonia water and 1 mol.L-1Adjusting the pH value to 11 by NaOH;
pouring 80mL of the mixed solution prepared in the step (1) into a 100mL reaction kettle, carrying out solvothermal reaction for 24h at 180 ℃ to obtain green precipitate, carrying out suction filtration and washing on the green precipitate with water and alcohol, carrying out suction filtration, and drying filter residues in a 70 ℃ drying oven for 20h to obtain an intermediate product;
step (3), dissolving 0.6mol of lithium hydroxide and 0.7mol of lithium carbonate in 15mL of absolute ethyl alcohol together, stirring uniformly, adding the intermediate product obtained in the step (2), continuously stirring, heating in a water bath at 70 ℃ and evaporating to dryness to obtain mixed solid powder, and drying in an oven at 70 ℃ for 20 hours;
and (4) grinding the mixed solid powder obtained in the step (3) for 50min, then placing the ground mixed solid powder into a muffle furnace for calcination, setting the temperature rise rate of the muffle furnace to be 3 ℃/min, pre-sintering the mixed solid powder at 400 ℃ for 6h, and calcining the mixed solid powder at 850 ℃ for 10h to obtain the 811NCM ternary cathode material LiNi with the three-dimensional nanowire array structure0.8Co0.1Mn0.1O2。
The 811NCM ternary positive electrode material prepared in example three was used for battery assembly and performance testing as follows:
assembling the battery: mixing the 811NCM ternary cathode material prepared in the third embodiment with acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), grinding into uniform slurry, coating the slurry on an aluminum foil, drying for 24 hours at 80 ℃, cutting into pieces, rolling and using the pieces as working electrodes, using a lithium piece as a counter electrode and using 1M LiPF as electrolyte6The solvent is a mixed solution of dimethyl carbonate (DMC), Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1: 1. A half cell model 2032 was assembled in a glove box under argon atmosphere.
(1) X-ray diffraction (XRD) test A sample was subjected to crystal structure analysis using an X-ray diffractometer (XRD; Rigaku Ultima IV-185), and the X-ray diffraction (XRD) result of the final product showed that the diffraction peaks of a 811NCM ternary cathode material having a good hexagonal layered structure of α -NaFeO2 were satisfied.
(2) Scanning Electron Microscope (SEM) testing: the microscopic morphology of the material was characterized using a field emission scanning electron microscope (FESEM, FEI, Quanta200f), and the Scanning Electron Microscope (SEM) results of the 811NCM ternary cathode material are shown in FIG. 2, which indicates that the 811NCM ternary cathode material product has a good nanowire array morphology with good dispersibility, and the particle size is substantially between 10 μm long and 1 μm wide.
(3) And (3) testing the electrochemical performance of the battery: the constant current charging and discharging test is carried out on a blue battery tester (LAND-CT2001A), the charging and discharging voltage range is 2.8-4.3V, and 1C is 200mAh ·g-1The assembled battery has a charging and discharging voltage range of 2.8-4.3V and a discharge specific capacity of 178.6 mAh.g after the material is cycled for 100 weeks under 0.1C multiplying power-1It became 168.7mAh · g-1The capacity retention rate was 94.5%.
Claims (7)
1. A811 NCM ternary cathode material with a three-dimensional nanowire array structure is characterized in that the crystal structure is a layered structure, the microscopic morphology is that nanowires are self-assembled by primary spherical single crystal particles, and then the nanowires are self-assembled into a strip array structure morphology, the particle size is 10-50 mu m in length, and the width is 1-3 mu m.
2. A preparation method of 811NCM ternary cathode material with a three-dimensional nanowire array structure is characterized by comprising the following steps:
dissolving a nickel source, a cobalt source and a manganese source in a prepared solvent, and uniformly stirring until the nickel source, the cobalt source and the manganese source are completely dissolved; then adding oxalic acid, and stirring uniformly until the oxalic acid is completely dissolved to obtain a mixed solution; adding ammonia water and/or NaOH to adjust the pH value to 7-14; the concentration of the solution obtained by dissolving the nickel source, the cobalt source and the manganese source in the solvent is 0.1-0.4 mol.L-1(ii) a The addition amount of the oxalic acid is 2-10 times of the total amount of the metal ions; the concentration of the ammonia water is 0.01 mol.L-1(ii) a The concentration of NaOH is 1-4 mol.L-1(ii) a The solvent is one or a mixture of more than one of deionized water, glycol or glycerol in any proportion.
Pouring 80mL of the mixed solution prepared in the step (1) into a 100mL reaction kettle, carrying out solvothermal reaction at 160-200 ℃ for 10-24h to obtain green precipitate, carrying out suction filtration and washing on the green precipitate with water and alcohol, carrying out suction filtration, and drying filter residues in an oven at 60-80 ℃ for 12-24 h to obtain an intermediate product;
completely dissolving a lithium source in 10-20 mL of absolute ethyl alcohol, uniformly stirring, adding the intermediate product obtained in the step (2), continuously stirring, heating in a water bath at 60-80 ℃ for drying by distillation to obtain mixed solid powder, and drying in an oven at 60-80 ℃ for 12-24 hours;
and (4) grinding the mixed solid powder obtained in the step (3) for 30-60 min, then placing the ground mixed solid powder into a muffle furnace for calcining, setting the temperature rise rate of the muffle furnace to be 2-5 ℃/min, pre-sintering the mixed solid powder at 400-600 ℃ for 3-6 h, calcining the mixed solid powder at 750-850 ℃ for 10-15 h, and cooling the calcined mixed solid powder to obtain the 811NCM ternary cathode material with the three-dimensional nanowire array structure.
3. The method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure according to claim 2, wherein the cobalt source is one or a mixture of more than one of cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride in any proportion.
4. The method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure according to claim 2, wherein the nickel source is one or a mixture of more than one of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride in any proportion.
5. The method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure according to claim 2, wherein the manganese source is one or a mixture of more than one of manganese nitrate, manganese sulfate, manganese acetate and manganese chloride in any proportion.
6. The method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure according to claim 2, wherein the nickel source, the cobalt source, the manganese source and the lithium source in the steps (1) and (3) are added in the following atomic molar ratios, namely Ni: co: mn: li is 0.8:0.1:0.1: 1.05-1.15.
7. The method for preparing the 811NCM ternary cathode material with the three-dimensional nanowire array structure according to claim 2, wherein the lithium source is one or a mixture of more than one of lithium nitrate, lithium hydroxide and lithium carbonate in any proportion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675249A (en) * | 2020-06-11 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
| CN112599764A (en) * | 2020-12-28 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of ternary nanowire array @ carbon fiber |
| CN114497474A (en) * | 2021-12-24 | 2022-05-13 | 江苏华峰超纤材料有限公司 | Preparation method of nickel-rich NCM811 nanoparticles |
| CN116216796A (en) * | 2023-04-25 | 2023-06-06 | 荆门市格林美新材料有限公司 | Modified nickel-manganese binary precursor and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001163700A (en) * | 1999-12-08 | 2001-06-19 | Tohoku Techno Arch Co Ltd | Lithium-based composite metal oxide and method of producing the same |
| CN104868122A (en) * | 2015-05-15 | 2015-08-26 | 北京理工大学 | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material |
| CN106299352A (en) * | 2015-05-26 | 2017-01-04 | 宁德新能源科技有限公司 | The preparation method of positive pole material of secondary lithium battery |
| CN107394164A (en) * | 2017-07-26 | 2017-11-24 | 天津银隆新能源有限公司 | Tertiary cathode material and preparation method thereof |
| CN107658451A (en) * | 2017-09-18 | 2018-02-02 | 北京理工大学 | A kind of 622NCM tertiary cathode materials and preparation method thereof |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN108899539A (en) * | 2018-06-28 | 2018-11-27 | 上海电力学院 | A kind of nickelic ternary lithium ion anode material and preparation method thereof |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| CN109273706A (en) * | 2018-09-20 | 2019-01-25 | 中南大学 | A kind of olive-shaped ternary material precursor and the preparation method and application thereof |
-
2019
- 2019-11-18 CN CN201911126416.7A patent/CN110867577A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001163700A (en) * | 1999-12-08 | 2001-06-19 | Tohoku Techno Arch Co Ltd | Lithium-based composite metal oxide and method of producing the same |
| CN104868122A (en) * | 2015-05-15 | 2015-08-26 | 北京理工大学 | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material |
| CN106299352A (en) * | 2015-05-26 | 2017-01-04 | 宁德新能源科技有限公司 | The preparation method of positive pole material of secondary lithium battery |
| CN107394164A (en) * | 2017-07-26 | 2017-11-24 | 天津银隆新能源有限公司 | Tertiary cathode material and preparation method thereof |
| CN107658451A (en) * | 2017-09-18 | 2018-02-02 | 北京理工大学 | A kind of 622NCM tertiary cathode materials and preparation method thereof |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN108899539A (en) * | 2018-06-28 | 2018-11-27 | 上海电力学院 | A kind of nickelic ternary lithium ion anode material and preparation method thereof |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| CN109273706A (en) * | 2018-09-20 | 2019-01-25 | 中南大学 | A kind of olive-shaped ternary material precursor and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BOZHOU CHEN等: "Surface modification with oxygen vacancy in Li-rich layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 for lithium-ion batteries", 《JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY》 * |
| 黄肖: "单晶纳米片结构镍钴锰三元正极材料的制备、表征与改性研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675249A (en) * | 2020-06-11 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
| CN111675249B (en) * | 2020-06-11 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
| CN112599764A (en) * | 2020-12-28 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of ternary nanowire array @ carbon fiber |
| CN114497474A (en) * | 2021-12-24 | 2022-05-13 | 江苏华峰超纤材料有限公司 | Preparation method of nickel-rich NCM811 nanoparticles |
| CN116216796A (en) * | 2023-04-25 | 2023-06-06 | 荆门市格林美新材料有限公司 | Modified nickel-manganese binary precursor and preparation method and application thereof |
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