CN115072798A - Preparation method and application of high-compaction-density nickel cobalt lithium manganate positive electrode material - Google Patents
Preparation method and application of high-compaction-density nickel cobalt lithium manganate positive electrode material Download PDFInfo
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Abstract
The invention relates to the field of lithium ion secondary battery anode materials, in particular to a preparation method and application of a nickel cobalt lithium manganate anode material, wherein the preparation method of the nickel cobalt lithium manganate anode material comprises the following steps: mixing 2 nickel cobalt lithium manganate precursors with different particle sizes and lithium salt, performing primary sintering to obtain a semi-finished product of the mixed nickel cobalt lithium manganate positive electrode material, coating nano oxide, performing secondary sintering, and sieving to obtain the lithium nickel cobalt lithium manganate positive electrode material. According to the preparation method, the precursor is prepared by an intermittent method, two times of sintering are sequentially adopted, and by controlling the size, sintering temperature and sintering time of a sintering forming body, on the premise of not specifically treating the precursor, the sintered crystal form of the precursor with a smaller particle size after sintering is stable, polycrystalline agglomeration is avoided, meanwhile, the anode material with a larger compaction density can be obtained, the size of the battery can be effectively reduced, excellent electrical property is guaranteed, and the preparation method is very beneficial to further development of the battery.
Description
Technical Field
The invention relates to the field of lithium ion secondary battery positive electrode materials, in particular to a preparation method of a nickel cobalt lithium manganate positive electrode material.
Background
The lithium ion battery has the advantages of high voltage, high energy density, long cycle life, environmental friendliness and the like, and through more than ten years of development, the lithium ion battery is an important novel energy storage form. The ternary cathode material is a main material of the lithium ion battery, and is the highest in cost of single material in the lithium ion battery. In order to meet the national requirements for the continuous development of new energy industries and the continuous development of electric automobiles, a new generation of lithium ion battery is required to have higher volume energy density, better rate capability and safety performance. Meanwhile, for 3C consumer mobile electronic products, the battery is required to have the smallest volume and be portable, and the anode material is the most limiting factor of the volume energy density.
The compacted density of the anode material greatly depends on the components, the structure and the particle size distribution of the material, for the same component and the structural material, the wider the particle size distribution is, the higher the compacted density of the material is, the particle size distribution of the anode material mainly depends on the particle size distribution of the precursor, and the best mode for widening the particle size distribution of the precursor is precursor blending of large and small particles. Compared with a precursor prepared by a continuous coprecipitation method (hereinafter referred to as a continuous method for short), the precursor prepared by the batch method has the advantage of more uniform particle size distribution, the batch method overcomes the defect that the particle size distribution of the precursor prepared by the continuous method is difficult to control strictly, and the compacted density of the mixture, namely the compacted density of the mixture is greater than that of the pure large particles and that of the pure small particles can be realized by mixing the precursor prepared by the batch method of the large particles and the small particles in a proper ratio.
Disclosure of Invention
In view of some problems in the prior art, a first aspect of the present invention provides a method for preparing a lithium nickel cobalt manganese oxide positive electrode material, including: mixing 2 nickel cobalt lithium manganate precursors with different particle sizes and lithium salt, performing primary sintering to obtain a semi-finished product of the mixed nickel cobalt lithium manganate positive electrode material, coating nano oxide, performing secondary sintering, and sieving to obtain the lithium nickel cobalt lithium manganate positive electrode material.
In one embodiment, the lithium salt is lithium carbonate.
In one embodiment, the difference between the particle sizes of the 2 nickel cobalt lithium manganate precursors with different particle sizes is 6-8 μm, and the particle sizes are 10 μm and 3 μm respectively.
In one embodiment, the conditions of the primary sintering are set as that the furnace temperature is increased from room temperature to 850- 3 h/Kg, the gas amount in the constant temperature stage is set to be 0.8-1.5m 3 /h/Kg。
In one embodiment, the nano-oxide comprises at least one of an oxide of iridium, an oxide of zirconium, and an oxide of aluminum.
In one embodiment, 2 lithium nickel cobalt manganese oxide precursors with different particle sizes and lithium salt are loaded into a pot by 3-5 kg.
In one embodiment, after primary sintering, the mixed lithium nickel cobalt manganese oxide cathode material semi-finished product is obtained through double-roller crushing, grading and sieving.
In one embodiment, the conditions of the secondary sintering are set as that the furnace temperature is increased from room temperature to 550-650 ℃ at the speed of 2-5 ℃/min, the temperature is kept for 6-11h, and then the crystal is naturally cooled.
In one embodiment, the second sintering is performed by sieving with a 350-mesh sieve in 300 meshes to obtain the product.
In one embodiment, a method for preparing a 10 μm lithium nickel cobalt manganese oxide precursor comprises: introducing nitrogen into a reaction kettle, adding dilute ammonia solution, then adding nickel salt solution, cobalt salt solution and manganese salt solution, then adding dilute alkali solution and concentrated ammonia water, continuously stirring at the temperature of 45-60 ℃ for 20-30h, controlling the pH value of a reaction system to be 10.5-11.5, and filtering, washing and drying precipitates after the reaction is finished to obtain the catalyst.
In a preferred embodiment, the preparation method of the lithium nickel cobalt manganese oxide precursor with the thickness of 10 μm comprises the following steps: introducing nitrogen into a reaction kettle, adding dilute ammonia solution, then adding nickel salt solution, cobalt salt solution and manganese salt solution, then adding dilute alkali solution and concentrated ammonia water, continuously stirring at the temperature of 50 ℃ for 25h, controlling the pH value of a reaction system to be 11, and filtering, washing and drying the precipitate after the reaction is finished to obtain the catalyst.
In one embodiment, the preparation method of the 3 μm lithium nickel cobalt manganese oxide precursor comprises the following steps: introducing nitrogen into a reaction kettle, adding dilute ammonia solution, then adding nickel salt solution, cobalt salt solution and manganese salt solution, then adding dilute alkali solution and concentrated ammonia water, continuously stirring for 10-15h at the temperature of 45-60 ℃, controlling the pH value of a reaction system to be 10.5-11.5, and filtering, washing and drying precipitates after the reaction is finished to obtain the catalyst.
In a preferred embodiment, the preparation method of the 3 μm lithium nickel cobalt manganese oxide precursor comprises the following steps: introducing nitrogen into a reaction kettle, adding dilute ammonia solution, then adding nickel salt solution, cobalt salt solution and manganese salt solution, then adding dilute alkali solution and concentrated ammonia water, continuously stirring at the temperature of 50 ℃ for 12h, controlling the pH value of a reaction system to be 11, and filtering, washing and drying the precipitate after the reaction is finished to obtain the catalyst.
In one embodiment, the concentration of the nickel salt solution, the cobalt salt solution and the manganese salt solution is 1.5-2.5 mol/L.
In one embodiment, the nickel salt is selected from one or more of the group consisting of sulfate, nitrate, and hydrochloride.
Preferably, the nickel salt is nickel sulfate.
In one embodiment, the cobalt salt is selected from one or more of the group consisting of sulfate, nitrate, and hydrochloride.
Preferably, the cobalt salt is cobalt sulfate.
In one embodiment, the manganese salt is selected from one or more of the group consisting of sulfate, nitrate, and hydrochloride.
Preferably, the manganese salt is manganese sulfate.
In one embodiment, the dilute ammonia solution has a concentration of 0.5 to 2 mol/L.
Preferably, the concentration of the dilute ammonia liquid is 1 mol/L.
In one embodiment, the concentrated aqueous ammonia has a concentration of 20 to 22 wt%.
In one embodiment, the concentration of the dilute alkali solution is 4-5 mol/L.
Preferably, the concentration of the dilute alkali liquor is 5 mol/L.
In one embodiment, the diluted ammonia solution is added in an amount of 1/4-1/2 of the effective volume in the reaction kettle.
Preferably, the addition amount of the dilute ammonia liquid is 1/2 of the effective volume in the reaction kettle.
In one embodiment, the diluted alkali solution, the metal salt solution and the concentrated ammonia water are used in the following standard: solute alkali: solute metal salt: NH (NH) 3 ·H 2 The molar ratio of O is (1.4-2.5): (1-1.5): 1.
preferably, the solute metal salt: NH (NH) 3 ·H 2 The molar ratio of O is 2.5:1.5: 1.
The metal salt solution in the present application is a mixed solution of a nickel salt solution, a cobalt salt solution, and a manganese salt solution.
In one embodiment, the ratio of the nickel salt solution to the cobalt salt solution to the manganese salt solution is based on the following criteria: the molar ratio of nickel, cobalt and manganese is (60-65): (10-15): 25-30).
Preferably, the molar ratio of nickel, cobalt and manganese is 55:15: 30.
In one embodiment, the weight ratio of the large-particle size lithium nickel cobalt manganese oxide precursor to the small-particle size lithium nickel cobalt manganese oxide precursor in the 2 lithium nickel cobalt manganese oxide precursors with different particle sizes is (7.5-9): (2.5-1).
Preferably, the weight ratio of the large-particle-size nickel cobalt lithium manganate precursor to the small-particle-size nickel cobalt lithium manganate precursor is 8: 2.
in one embodiment, 2 lithium nickel cobalt manganese oxide precursors of different particle sizes are mixed first and then mixed with the lithium salt again.
Preferably, the method for mixing the 2 nickel cobalt lithium manganate precursors with different particle sizes comprises the following steps: premixing 2 nickel cobalt lithium manganate precursors with different particle sizes, and then mixing in a high-speed mixer at 750r/min for 10 min.
In one embodiment, a method for mixing 2 lithium nickel cobalt manganese oxide precursors with different particle sizes and lithium salts comprises the following steps: 2 kinds of nickel cobalt lithium manganate precursors with different particle sizes and lithium salt are mixed in a high-speed mixer for 40min at the speed of 750 r/min.
In one embodiment, the molar ratio of the total amount of lithium ions and nickel cobalt manganese in the lithium salt is (0.9-1.2): 1.
preferably, the molar ratio of the total amount of lithium ions and nickel-cobalt-manganese in the lithium salt is (1.03-1.06): 1.
in one embodiment, the coating is dry coated using a high speed fusion coater.
The second aspect of the invention provides an application of the preparation method of the nickel cobalt lithium manganate positive electrode material in the preparation of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts an intermittent method to prepare the precursor, simultaneously adopts twice sintering, and synthesizes the high-compaction material by controlling the sintering temperature and the sintering time, and the material has the following advantages: 1. the micro effect of the mixed doping of the large particles and the small particles is that the small particles occupy gaps among the large particles, so that the mixed doping of the large particles and the small particles can obviously improve the compaction density of the material, the mixed doping of the 2 large particles and the small particles can also improve the electronic conductivity and the lithium ion conductivity of the material, and 3, the lithium battery has higher and higher requirements on the volume of the battery when being developed, and the mixed material can improve the volume energy density of the battery, thereby being very beneficial to the further development of the battery. Meanwhile, the preparation process is simple, convenient to operate and reliable, secondary crushing is reduced, and energy consumption is reduced.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
Embodiment 1 of the invention provides a preparation method of a mixed nickel cobalt lithium manganate positive electrode material, which comprises the following specific steps:
(1) preparing a nickel cobalt lithium manganate precursor by a batch method with large particles of 10 mu m and small particles of 3 mu m:
1) preparing a metal salt solution: adding water into nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate to respectively prepare 2mol/L salt solutions;
2) preparing a dilute alkali solution: diluting 30 wt% concentrated sodium hydroxide lye (about 11.7M) into dilute lye of 5 mol/L;
3) preparing dilute ammonia liquid: 22 wt% concentrated ammonia (about 12.5M) was diluted with water to prepare a 1mol/L dilute ammonia solution.
4) Preparing a precursor: introducing nitrogen into a 10L reaction kettle, firstly adding 5L of 2mol/L diluted ammonia water as a base solution through a peristaltic pump, respectively adding the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution into the reaction kettle according to the molar ratio of Ni to Co to Mn of 55 to 15 to 30 through a coprecipitation method, and simultaneously respectively adding the diluted alkali solution (NaOH) and the concentrated ammonia water, wherein the diluted alkali solution (NaOH) and the metal salt solution (MSO) 4 ) Concentrated ammonia (NH) 3 Aq.) in the ratio NaOH to MSO 4 :NH 3 ·H 2 Adding O with the molar ratio of 2.5:1.5: 1; continuously stirring and reacting for 12h at 50 ℃; monitoring pH 11 with an online pH meter; filtering, washing and drying the precipitate generated by the reaction to obtain a 3-micron small-particle batch method nickel cobalt lithium manganate precursor, and continuously stirring and reacting at 50 ℃ for 25 hours by the same method; monitoring pH 11 with an online pH meter; and filtering, washing and drying the precipitate generated by the reaction to obtain a 10-micron large-particle batch method nickel cobalt lithium manganate precursor.
(2) Preparing a mixed nickel cobalt manganese lithium precursor by using a 10 mu m large-particle batch method nickel cobalt lithium manganate precursor and a 3 mu m small-particle batch method nickel cobalt lithium manganate precursor in a mass ratio of 8: 2:
accurately weighing 8Kg of 10 mu m batch-process lithium nickel cobalt manganese oxide precursor and 2Kg of 3 mu m batch-process lithium nickel cobalt manganese oxide precursor, manually premixing, and mixing in a high-speed mixer at the mixing speed of 750r/min for 10min to obtain the final product.
(3) Preparing a mixed lithium nickel cobalt manganese oxide positive electrode material:
is 10 mu m largeIntermittent method for mixing nickel-cobalt-manganese-lithium precursor and industrial grade lithium carbonate Li by using particles and 3 mu m small particles 2 CO 3 Taking the total molar ratio of Li to Ni, Co and Mn as 1.055: 1, manually premixing ingredients, then mixing the ingredients in a high-speed mixer, carrying out primary sintering in a bell-type furnace, setting the primary sintering temperature and time as the furnace temperature, heating the furnace temperature from room temperature to 900 ℃ at the speed of 4 ℃/min, keeping the temperature at 900 ℃ for 6h, heating the furnace temperature from 900 ℃ to 940 ℃ at the speed of 4 ℃/min, keeping the temperature at 940 ℃ for 6h, naturally cooling for crystallization, and setting the air amount in the heating and cooling stages to be 2m 3 h/Kg, constant temperature stage set to 1m 3 h/Kg. Crushing and screening by a pair of rollers in a grading way to obtain a mixed type nickel cobalt lithium manganate mixed type ternary material semi-finished product, coating nano zirconium oxide on the semi-finished product by a dry method, carrying out secondary sintering (the temperature and time of the secondary sintering are set as the furnace temperature is increased from room temperature to 600 ℃ at the speed of 4 ℃/min, carrying out heat preservation for 10 hours at the temperature of 600 ℃, then carrying out natural cooling crystallization), and carrying out screening (the screen aperture of a screening screen is 325 meshes) to remove magnetism to obtain a mixed type ternary material finished product.
Example 2
Embodiment 2 of the invention provides a preparation method of a lithium nickel cobalt manganese oxide positive electrode material, which comprises the following specific steps:
(1) preparing a 10-micron large-particle batch method nickel cobalt lithium manganate precursor:
1) preparing a metal salt solution: adding water into nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate to respectively prepare 2mol/L salt solutions;
2) preparing a dilute alkali solution: diluting 30 wt% concentrated sodium hydroxide lye (about 11.7M) into dilute lye of 5 mol/L;
3) preparing dilute ammonia solution: 22 wt% concentrated ammonia (about 12.5M) was diluted with water to prepare a 1mol/L dilute ammonia solution.
4) Preparing a precursor: introducing nitrogen into a 10L reaction kettle, firstly adding 5L of 2mol/L diluted ammonia water as a base solution through a peristaltic pump, respectively adding the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution into the reaction kettle according to the molar ratio of Ni to Co to Mn of 55 to 15 to 30 through a coprecipitation method, and simultaneously respectively adding the diluted alkali solution (NaOH) and the concentrated ammonia water, wherein the diluted alkali solution (NaOH) and the metal salt solution (MSO) 4 ) Concentrated ammonia (NH) 3 Aq.) in the ratio of NaOH to M SO 4 :NH 3 ·H 2 Adding O with the molar ratio of 2.5:1.5: 1; continuously stirring and reacting for 25 hours at 50 ℃; the online pH meter monitored pH 11; and filtering, washing and drying the precipitate generated by the reaction to obtain a 10-micron large-particle batch method nickel cobalt lithium manganate precursor.
(2) Preparing a 10-micron large-particle single nickel cobalt lithium manganate positive electrode material:
preparing a nickel-cobalt-manganese-lithium precursor with large particles of 10 mu m by a batch method and industrial-grade lithium carbonate Li 2 CO 3 Taking the total molar ratio of Li to Ni, Co and Mn as 1.055: 1, manually premixing ingredients, then mixing the ingredients in a high-speed mixer, carrying out primary sintering in a bell-type furnace, setting the temperature and time of the primary sintering to be that the furnace temperature is increased from room temperature to 900 ℃ at the speed of 4 ℃/min, keeping the temperature of 900 ℃ for 6h, then is increased from 900 ℃ to 940 ℃ at the speed of 4 ℃/min, keeping the temperature of 940 ℃ for 6h, then naturally cooling and crystallizing, and setting the air amount in the temperature increasing and reducing stages to be 2m 3 h/Kg, constant temperature stage set to 1m 3 h/Kg. Crushing and grading sieving by using a pair of rollers to obtain a 10 mu m large-particle single type ternary cathode material semi-finished product, coating the semi-finished product with nano zirconium oxide by a dry method, carrying out secondary sintering (the temperature and time of the secondary sintering are set as the furnace temperature is increased from room temperature to 600 ℃ at the speed of 4 ℃/min, carrying out heat preservation for 10 hours at the temperature of 600 ℃, then naturally cooling and crystallizing), and sieving (the mesh diameter of a sieve is 325 meshes) to remove magnetism to obtain a 10 mu m large-particle single type nickel cobalt lithium manganate cathode material finished product.
Example 3
Embodiment 3 of the invention provides a preparation method of a lithium nickel cobalt manganese oxide positive electrode material, which comprises the following specific steps:
(1) preparing a 3-micron small-particle batch method nickel cobalt lithium manganate precursor:
1) preparing a metal salt solution: adding water into nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate to respectively prepare 2mol/L salt solutions;
2) preparing a dilute alkali solution: diluting 30 wt% concentrated sodium hydroxide lye (about 11.7M) into dilute lye of 5 mol/L;
3) preparing dilute ammonia liquid: 22 wt% concentrated ammonia (about 12.5M) was diluted with water to prepare a 1mol/L dilute ammonia solution.
4) Preparing a precursor: introducing nitrogen into a 10L reaction kettle, firstly adding 5L of 2mol/L diluted ammonia water as a base solution through a peristaltic pump, respectively adding the nickel sulfate solution, the cobalt sulfate solution and the manganese sulfate solution into the reaction kettle according to the molar ratio of Ni to Co to Mn of 55 to 15 to 30 through a coprecipitation method, and simultaneously respectively adding the diluted alkali solution (NaOH) and the concentrated ammonia water, wherein the diluted alkali solution (NaOH) and the metal salt solution (MSO) 4 ) Concentrated ammonia (NH) 3 Aq.) in the ratio of NaOH to M SO 4 :NH 3 ·H 2 Adding O at a molar ratio of 2.5:1.5: 1; continuously stirring and reacting for 12h at 50 ℃; the online pH meter monitored pH 11; and filtering, washing and drying the precipitate generated by the reaction to obtain a 3 mu m small-particle batch method nickel cobalt lithium manganate precursor.
(2) Preparing a 3-micron small-particle single-type nickel cobalt lithium manganate positive electrode material:
preparing a nickel-cobalt-manganese-lithium precursor of 3 mu m small particles by a batch method and industrial-grade lithium carbonate Li 2 CO 3 Taking the total molar ratio of Li to Ni, Co and Mn as 1.055: 1, manually premixing ingredients, then mixing in a high-speed mixer, loading 4Kg into a bowl, feeding into a bell-type furnace for primary sintering, setting the primary sintering temperature and time as the furnace temperature to rise from room temperature to 900 ℃ at the speed of 4 ℃/min, keeping the temperature at 900 ℃ for 6h, then rising from 900 ℃ to 940 ℃ at the speed of 4 ℃/min, keeping the temperature at 940 ℃ for 6h, then naturally cooling for crystallization, and setting the air amount at the temperature rising and reducing stages as 2m 3 h/Kg, constant temperature stage set to 1m 3 h/Kg. Crushing and grading and sieving by using a pair of rollers to obtain a 3 mu m small-particle single type ternary cathode material semi-finished product, coating the semi-finished product with nano zirconium oxide by a dry method, carrying out secondary sintering (the secondary sintering temperature and time are set as the furnace temperature is increased from room temperature to 600 ℃ at the speed of 4 ℃/min, carrying out heat preservation for 10 hours at the temperature of 600 ℃, and then carrying out natural cooling crystallization) and sieving (the sieve mesh size is 325 meshes) to remove magnetism to obtain a 3 mu m small-particle single type nickel cobalt lithium manganate cathode material finished product.
Performance evaluation
The compaction densities of the lithium nickel cobalt manganese oxide positive electrode materials obtained in the embodiments 1 to 3 were respectively tested by maintaining an energy compaction instrument at 50MPa for 10 seconds, and simultaneously respectively testing the lithium nickel cobalt manganese oxide positive electrode materialsThe material is made into a 2032 type button cell and is tested by using model CT2001A blue electricity equipment, the charge-discharge cut-off voltage is 3.0-4.3V, wherein the method for preparing the 2032 type button cell comprises the following active substances: homogenizing SP (90-95): (3-6): (2-4) in proportion, coating, tabletting and slicing to obtain the battery, wherein the compacted density of the pole piece is 3.2-3.6g/cm 3 The electrochemical performance data obtained are shown in the following table:
the experimental data show that the powder compaction density of the mixed nickel cobalt lithium manganate positive electrode material prepared by the method is larger than that of the pure large-particle ternary nickel cobalt lithium manganate positive electrode material and that of the pure small-particle ternary nickel cobalt lithium manganate positive electrode material, and the first discharge specific capacity of the mixed nickel cobalt lithium manganate positive electrode material is slightly larger than that of the pure nickel cobalt lithium manganate positive electrode material, and meanwhile, the mixed first coulombic efficiency is slightly larger than that of the pure nickel cobalt lithium manganate positive electrode material, so that the mixed nickel cobalt lithium manganate positive electrode material shows good electrochemical performance and subsequent processing performance.
Claims (6)
1. A preparation method of a nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps: mixing 2 nickel cobalt lithium manganate precursors with different particle sizes and lithium salt, performing primary sintering to obtain a semi-finished product of a mixed nickel cobalt lithium manganate positive electrode material, coating a nano oxide, performing secondary sintering, and sieving to obtain the lithium nickel cobalt lithium manganate positive electrode material; the particle size difference of the 2 nickel cobalt lithium manganate precursors with different particle sizes is 6-8 mu m.
2. The method for preparing the nickel cobalt lithium manganate cathode material as defined in claim 1, wherein the conditions of the first sintering are set as furnace temperature rising from room temperature to 850- 3 h/Kg, the gas amount in the constant temperature stage is set to be 0.8-1.5m 3 /h/Kg。
3. The method for preparing the lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the nano oxide comprises at least one of an oxide of iridium, an oxide of zirconium and an oxide of aluminum.
4. The method for preparing the lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the semi-finished product of the mixed lithium nickel cobalt manganese oxide cathode material is obtained by crushing, grading and sieving with a pair of rollers after primary sintering.
5. The method for preparing the nickel cobalt lithium manganate cathode material as set forth in claim 1, wherein the conditions of the secondary sintering are set as that the furnace temperature is raised from room temperature to 550-650 ℃ at a speed of 2-5 ℃/min, the temperature is kept for 6-11h, and then the nickel cobalt lithium manganate is naturally cooled and crystallized.
6. Use of the method of any one of claims 1 to 5 for the preparation of a lithium nickel cobalt manganese oxide positive electrode material for the preparation of a lithium ion battery.
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| CN105161710A (en) * | 2015-08-31 | 2015-12-16 | 宁波金和锂电材料有限公司 | Battery cathode material, preparation method thereof and lithium ion battery |
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