CN110697799A - Preparation method of porous lithium ion battery anode material - Google Patents
Preparation method of porous lithium ion battery anode material Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a porous lithium ion battery anode material, belonging to the technical field of preparation of lithium ion battery anode materials0.5CO0.2Mn0.3O2The primary particles are mutually stacked together to form a sphere of secondary particles, a carbon source is gradually sintered in an oxygen environment in the air along with the gradual rise of the sintering temperature in the sintering process, and finally the carbon source is completely escaped by the formation of carbon dioxide, water vapor or other gases, and the remaining secondary particle small spheres have more holes and pores due to the disappearance of the carbon source mixed with the particlesThe porous structure of the lithium ion battery anode material provides a smooth passage for lithium ion deintercalation in the charge and discharge processes of the lithium ion battery, and shortens a lithium ion diffusion path.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery anode materials, and particularly relates to a preparation method of a porous lithium ion battery anode material.
Background
The lithium ion battery is a secondary battery having the strongest versatility and the widest usability. The lithium ion battery as a novel green power supply has many excellent performances, such as high energy density, high open circuit voltage, no memory effect, safety, no pollution and the like. The lithium ion battery is mainly assembled by a positive electrode material, a negative electrode material, a diaphragm and electrolyte, and the positive electrode material is an indispensable part and has important influence on the performance of the lithium ion battery.
The types of the lithium ion battery anode materials are many, and the ternary materials are pursued by more and more researchers due to the advantages of high energy density, high specific capacity, excellent cycle performance, small influence of temperature change and the like. However, the ternary materials prepared by the conventional methods have the following disadvantages: the obtained secondary particles have small specific surface area and small contact area with the electrolyte, so that a lithium ion diffusion channel is too long, the diffusion rate is small, and the performance of the lithium ion battery anode material is influenced to a certain extent.
Disclosure of Invention
The invention solves the technical problem of providing the preparation method of the porous lithium ion battery anode material which has simple process and low cost and is suitable for industrial production.
The invention adopts the following technical scheme for solving the technical problems:
a preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: respectively weighing nickel sources, cobalt sources, manganese sources and lithium sources according to a molar ratio of 5:2:3:10.8, ball-milling and mixing the materials, keeping the volume ratio of the ball materials to be 10:1, and ball-milling for 2-7h, wherein the nickel sources, the cobalt sources, the manganese sources and the lithium sources are carbonates corresponding to corresponding elements;
step S2: adding an organic polymer carbon source into deionized water at 60-80 ℃ and stirring until the carbon source is uniformly dissolved, wherein the organic polymer carbon source is one or two of hydroxypropyl methyl cellulose or starch;
step S3: adding the mixture prepared in the step S1 into a high-speed mixer, uniformly dropwise adding the organic polymer carbon source solution prepared in the step S2 when the mixing speed is 100-;
step S4: drying the mixture obtained in the step S3 at 60 ℃, heating the dried material to 500 ℃./min at a heating rate of 5 ℃/min in a nitrogen environment, keeping the temperature for 5-9h at 650 ℃, used for synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 900 ℃./min at a heating rate of 5 ℃/min in an aerobic environment, keeping the temperature for 6-8h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system by gas, and finally preparing the porous lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2。
Further preferably, the mass ratio of the organic polymer carbon source to the deionized water in the step S2 is 1-10:100, and the mass ratio of the mixture to the organic polymer carbon source solution in the step S3 is 100: 5-10.
A preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: respectively weighing 200g of materials of nickel carbonate, cobalt carbonate, manganese carbonate and lithium carbonate according to a molar ratio of 5:2:3:10.8, carrying out ball milling and mixing on the materials, keeping the volume ratio of ball materials at 10:1, and carrying out ball milling for 5 hours;
step S2: adding 0.5g of hydroxypropyl methyl cellulose into 10mL of deionized water at 70 ℃, and stirring until the hydroxypropyl methyl cellulose is uniformly dissolved;
step S3: adding the mixture prepared in the step S1 into a high-speed mixer, uniformly dropwise adding the solution prepared in the step S2 when the mixing speed is 200rpm, and adjusting the rotating speed of the mixer to 1000rpm and maintaining for 15min after dropwise adding;
step S4: drying the mixture obtained in the step S3 at 60 ℃ for 5h, heating the dried material to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 7h, synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 950 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 8h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system with gas, and finally preparing the porous lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2The specific surface area of the porous lithium ion battery anode material is 2.168m2(ii)/g, first discharge specific capacity of 155.7mAh/g, and ionic conductivity at 35 ℃ of 7.13 x 10-7S/cm。
A preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: grinding graphite in an eccentric spherical tank at the rotating speed of 500 plus 700rpm for 4-7h, and filtering with a 800-mesh screen to obtain graphite powder;
step S2: adding the graphite powder obtained in the step S1 into an ethanol-water mixed solution, and simultaneously carrying out mechanical stirring and ultrasonic dispersion to prepare a suspension;
step S3: respectively weighing a soluble nickel source, a soluble cobalt source and a soluble manganese source according to a molar ratio of 5:2:3, dissolving the soluble nickel source, the soluble cobalt source and the soluble manganese source in deionized water to prepare a 2mol/L salt solution, adding a 4mol/L sodium hydroxide solution, ammonia water and the step S2 to obtain a suspension, wherein the temperature of a reaction solution is 50-55 ℃, the stirring speed of a reactor is 1000rpm, the reaction time is 8h, the pH of the reaction solution is maintained to be 10.5-11, and introducing nitrogen for protection in the whole process;
step S4: filtering and drying the product obtained in the step S3, and mixing the product with a lithium source;
step S5: drying the mixture obtained in the step S4, and firstly drying the dried material in a nitrogen environment at the temperature of 5 ℃/minRaising the temperature to 700-plus 900 ℃ at a temperature rate for 8-12h for synthesizing secondary particles mixed with the organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, raising the temperature to 1000-plus 1200 ℃ at a temperature rate of 5 ℃/min in an aerobic environment for 1-2h for further optimizing the secondary particle structure so that the organic polymer carbon source is fully oxidized and forms a separation system by gas, and finally obtaining the anode material LiNi of the porous lithium ion battery0.5Co0.2Mn0.3O2。
More preferably, in step S2, the mass ratio of the graphite powder to the ethanol-water mixture is 3-8:100, and the volume ratio of ethanol to water in the ethanol-water mixture is 1-10: 1.
Further preferably, in step S3, the soluble nickel source, the soluble cobalt source and the soluble manganese source are sulfates, nitrates or chlorides of corresponding elements, and NH in the aqueous ammonia solution3·H2The molar ratio of O to the total metal amount of the soluble nickel source, the soluble cobalt source and the soluble manganese source is 0.5-1:1, and the volume ratio of the suspension obtained in the step S2 to the salt solution is 8-12:100.
More preferably, in step S4, the lithium source is Li (OH)2Or LiCO3The molar ratio of the lithium source to the total metal content of the soluble nickel source, the soluble cobalt source and the soluble manganese source was 1.08: 1.
A preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: grinding 5g of graphite in an eccentric spherical tank at the rotating speed of 700rpm for 5h, and filtering by using a 800-mesh screen to obtain graphite powder;
step S2: adding the graphite powder obtained in the step S1 into an ethanol-water mixed solution consisting of 75mL of ethanol and 25mL of water, and simultaneously carrying out mechanical stirring and ultrasonic dispersion to prepare a suspension;
step S3: 262.86g of NiSO4、62g CoSO4、90.6g MnSO4Adding 1L of deionized water into the reactor to prepare 2mol/L salt solution, adding 4mol/L sodium hydroxide solution containing 1.6mol of NH3·H2Ammonia water of O and step S2 to obtain suspension, wherein the temperature of the reaction liquid is 55 ℃, and the temperature of the reaction liquid is in a reactorThe stirring speed of the reaction kettle is 1000rpm, the reaction time is 8 hours, the pH of the reaction solution is maintained to be 11, and nitrogen is introduced for protection in the whole process;
step S4: carrying out suction filtration and drying on the product obtained in the step S3, and mixing the product with lithium source lithium carbonate;
step S5: drying the mixture obtained in the step S4 at 60 ℃, heating the dried material to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 10h, synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 1100 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 1h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system by gas, and finally preparing the positive electrode material LiNi of the porous lithium ion battery0.5Co0.2Mn0.3O2The specific surface area of the porous lithium ion battery anode material is 2.324m2(ii)/g, first discharge specific capacity of 162.4mAh/g, and ionic conductivity of 8.36 x 10 at 35 ℃-7S/cm。
The invention has the following beneficial effects:
1. the invention adopts the three-element anode material of the porous lithium ion battery obtained by the two methods, wherein the porous framework is made of micron-sized LiNi0.5CO0.2Mn0.3O2And (4) forming. The organic carbon source acts as a pore-forming agent in the formation process of the porous material, and the organic carbon source and LiNi0.5CO0.2Mn0.3O2The primary particles are stacked together to form a sphere of secondary particles, in the sintering process, along with the gradual rise of the sintering temperature, the carbon source is gradually sintered in the oxygen environment in the air, and finally the carbon source is completely escaped by the formation of carbon dioxide, water vapor or other gases, and the residual secondary particle small sphere has more holes due to the disappearance of the carbon source mixed in the particles.
2. The porous lithium ion battery anode material prepared by the invention increases the specific surface area of the secondary particles due to the increase of the holes. The porous structure of the porous lithium ion battery anode material is lithium ions in the process of charging and discharging the lithium ion batteryDe-intercalation provides an open channel, shortening the lithium ion diffusion path. Compared with the anode material synthesized by the traditional method, the anode material synthesized by the invention has the advantages that the ionic conductivity and the first discharge specific capacity are both improved to a certain extent. The preparation method has wide applicability and can be used for various ternary materials LiNi1-x-yCoxMnyO2The (x is more than 0 and less than 1, and y is more than 0 and less than 1) has stronger applicability.
Drawings
FIG. 1 is a graph showing the comparison of specific discharge capacity of 20 previous cycles of the NCM523 of the positive electrode material of the lithium ion battery prepared in example 1 and comparative example 1 (voltage 2.75-4.3V 1C);
FIG. 2 is a graph showing the comparison of the discharge specific capacities of 20 previous cycles of the NCM523 positive electrode material of the lithium ion battery obtained in example 4 and the comparative example 1 (voltage 2.75-4.3V 1C);
FIG. 3 is an SEM image of the positive electrode material of the lithium ion battery prepared in example 1;
FIG. 4 is an SEM image of the positive electrode material of the lithium ion battery prepared in example 4;
fig. 5 is an SEM image of the positive electrode material for the lithium ion battery prepared in comparative example 1.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: respectively weighing 200g of materials of nickel carbonate, cobalt carbonate, manganese carbonate and lithium carbonate according to a molar ratio of 5:2:3:10.8, carrying out ball milling and mixing on the materials, keeping the volume ratio of ball materials at 10:1, and carrying out ball milling for 5 hours;
step S2: adding 0.5g of hydroxypropyl methyl cellulose into 10mL of deionized water at 70 ℃, and stirring until the hydroxypropyl methyl cellulose is uniformly dissolved;
step S3: adding the mixture prepared in the step S1 into a high-speed mixer, uniformly dropwise adding the solution prepared in the step S2 when the mixing speed is 200rpm, and adjusting the rotating speed of the mixer to 1000rpm and maintaining for 15min after dropwise adding;
step S4: drying the mixture obtained in the step S3 at 60 ℃ for 5h, heating the dried material to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 7h, synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 950 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 8h, further optimizing the structure of the secondary particles, fully oxidizing the organic polymer carbon source, forming a separation system by gas, and finally preparing the porous lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2。
Example 2
The same parts as those in embodiment 1 are not described again, and the differences from embodiment 1 are: in step S2, a mixture of hydroxypropyl methylcellulose and starch is weighed in a mass ratio of 1:1 to prepare a solution.
Example 3
The same parts as those in embodiment 1 are not described in detail, and the differences from embodiment 1 are: in step S4, the two stages of sintering are: the first stage is carried out in a nitrogen protection environment, the temperature is 500 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 9 hours; the second stage is carried out in an aerobic environment, the temperature is 950 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 6 h.
Example 4
Step S1: grinding 5g of graphite in an eccentric ball milling tank at the rotating speed of 700rpm for 5h, and filtering with a 800-mesh screen to obtain graphite powder;
step S2: adding the graphite powder obtained in the step S1 into an ethanol-water mixed solution consisting of 75mL of ethanol and 25mL of water, and simultaneously carrying out mechanical stirring and ultrasonic dispersion to prepare a suspension;
step S3: 262.86g of NiSO4、62g CoSO4、90.6g MnSO4Adding 1L of deionized water into the reactor to prepare 2mol/L salt solution, and then adding 4mol/L sodium hydroxide solution and ammonia water (1.6 mol NH)3·H2O) and step S2 to obtain a suspension wherein the temperature of the reaction solution is 55 ℃ and the stirring of the reactor is carried outThe speed is 1000rpm, the reaction time is 8 hours, the pH of the reaction solution is maintained to be 11, and nitrogen is introduced for protection in the whole process;
step S4: carrying out suction filtration and drying on the product obtained in the step S3, and mixing the product with lithium source lithium carbonate;
step S5: drying the mixture obtained in the step S4 at 60 ℃ for 8h, heating the dried material to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 10h, synthesizing secondary particles mixed with an organic polymer carbon source without oxidizing the organic polymer carbon source, heating to 1100 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 1h, further optimizing the structure of the secondary particles, fully oxidizing the organic polymer carbon source and forming a separation system by gas, and finally preparing the positive electrode material LiNi of the porous lithium ion battery0.5Co0.2Mn0.3O2。
Example 5
The same parts of this embodiment as embodiment 4 are not described again, except that: the sintering process is carried out in two stages in an air atmosphere: in the first stage, the temperature is maintained at 700 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 12 h; in the second stage, the temperature is kept at 1000 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h.
Comparative example 1
Step S1: 262.86g of NiSO4、62g CoSO4、90.6g MnSO4Adding 1L of deionized water into the reactor to prepare 2mol/L salt solution, and then adding 4mol/L sodium hydroxide solution and ammonia water (1.6 mol NH)3·H2O), wherein the temperature of the reaction liquid is 55 ℃, the stirring speed of the reactor is 1000rpm, the reaction time is 8 hours, the pH of the reaction liquid is maintained at 11, and nitrogen is introduced for protection in the whole process;
step S2: filtering and drying the product obtained in the step S1, and mixing the product with a lithium source;
step S3: drying the mixture obtained in the step S2 at 60 ℃, heating the dried material to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 10 hours, heating to 1100 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 1 hour, and finally obtaining the lithium ion battery positive electrodeLiNi as a polar material0.5Co0.2Mn0.3O2。
LiNi positive electrode material for lithium ion batteries prepared in examples 1 to 5 and comparative example 10.5Co0.2Mn0.3O2The specific surface area, the specific first discharge capacity and the ionic conductivity of (A) are shown in tables 1 to 2, respectively.
TABLE 1
| Specific capacity of first discharge/mAh/g | Ion conductivity/S/cm (35 ℃ C.) | |
| Example 1 | 155.7 | 7.13*10-7 |
| Example 2 | 153.3 | 6.96*10-7 |
| Example 3 | 150.4 | 6.32*10-7 |
| Example 4 | 162.4 | 8.36*10-7 |
| Example 5 | 158.9 | 7.42*10-7 |
| Comparative example 1 | 148.4 | 3.18*10-7 |
TABLE 2
| Specific surface area (m)2/g） | |
| Example 1 | 2.168 |
| Example 2 | 1.987 |
| Example 3 | 2.047 |
| Example 4 | 2.324 |
| Example 5 | 1.894 |
| Comparative example 1 | 0.5819 |
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (8)
1. A preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: respectively weighing nickel sources, cobalt sources, manganese sources and lithium sources according to a molar ratio of 5:2:3:10.8, ball-milling and mixing the materials, keeping the volume ratio of the ball materials to be 10:1, and ball-milling for 2-7h, wherein the nickel sources, the cobalt sources, the manganese sources and the lithium sources are carbonates corresponding to corresponding elements;
step S2: adding an organic polymer carbon source into deionized water at 60-80 ℃ and stirring until the carbon source is uniformly dissolved, wherein the organic polymer carbon source is one or two of hydroxypropyl methyl cellulose or starch;
step S3: adding the mixture prepared in the step S1 into a high-speed mixer, uniformly dropwise adding the organic polymer carbon source solution prepared in the step S2 when the mixing speed is 100-;
step S4: drying the mixture obtained in the step S3 at 60 ℃, heating the dried material to 500 ℃./min at a heating rate of 5 ℃/min in a nitrogen environment, keeping the temperature for 5-9h at 650 ℃, used for synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 900 ℃./min at a heating rate of 5 ℃/min in an aerobic environment, keeping the temperature for 6-8h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system by gas, and finally preparing the porous lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2。
2. The preparation method of the porous lithium ion battery cathode material according to claim 1, characterized in that: the mass ratio of the organic polymer carbon source to the deionized water in the step S2 is 1-10:100, and the mass ratio of the mixture to the organic polymer carbon source solution in the step S3 is 100: 5-10.
3. The preparation method of the porous lithium ion battery anode material according to claim 1, which is characterized by comprising the following specific steps:
step S1: respectively weighing 200g of materials of nickel carbonate, cobalt carbonate, manganese carbonate and lithium carbonate according to a molar ratio of 5:2:3:10.8, carrying out ball milling and mixing on the materials, keeping the volume ratio of ball materials at 10:1, and carrying out ball milling for 5 hours;
step S2: adding 0.5g of hydroxypropyl methyl cellulose into 10mL of deionized water at 70 ℃, and stirring until the hydroxypropyl methyl cellulose is uniformly dissolved;
step S3: adding the mixture prepared in the step S1 into a high-speed mixer, uniformly dropwise adding the solution prepared in the step S2 when the mixing speed is 200rpm, and adjusting the rotating speed of the mixer to 1000rpm and maintaining for 15min after dropwise adding;
step S4: drying the mixture obtained in the step S3 at 60 ℃ for 5h, heating the dried material to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 7h, synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 950 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 8h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system with gas, and finally preparing the porous lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2The specific surface area of the porous lithium ion battery anode material is 2.168m2(ii)/g, first discharge specific capacity of 155.7mAh/g, and ionic conductivity at 35 ℃ of 7.13 x 10-7S/cm。
4. A preparation method of a porous lithium ion battery anode material is characterized by comprising the following specific steps:
step S1: grinding graphite in an eccentric spherical tank at the rotating speed of 500 plus 700rpm for 4-7h, and filtering with a 800-mesh screen to obtain graphite powder;
step S2: adding the graphite powder obtained in the step S1 into an ethanol-water mixed solution, and simultaneously carrying out mechanical stirring and ultrasonic dispersion to prepare a suspension;
step S3: respectively weighing a soluble nickel source, a soluble cobalt source and a soluble manganese source according to a molar ratio of 5:2:3, dissolving the soluble nickel source, the soluble cobalt source and the soluble manganese source in deionized water to prepare a 2mol/L salt solution, adding a 4mol/L sodium hydroxide solution, ammonia water and the step S2 to obtain a suspension, wherein the temperature of a reaction solution is 50-55 ℃, the stirring speed of a reactor is 1000rpm, the reaction time is 8h, the pH of the reaction solution is maintained to be 10.5-11, and introducing nitrogen for protection in the whole process;
step S4: filtering and drying the product obtained in the step S3, and mixing the product with a lithium source;
step S5: drying the mixture obtained in the step S4, heating the dried material to 700-0.5Co0.2Mn0.3O2。
5. The preparation method of the porous lithium ion battery cathode material according to claim 4, characterized in that: in the step S2, the mass ratio of the graphite powder to the ethanol-water mixed solution is 3-8:100, and the volume ratio of ethanol to water in the ethanol-water mixed solution is 1-10: 1.
6. The preparation method of the porous lithium ion battery cathode material according to claim 4, characterized in that: in step S3, the soluble nickel source, the soluble cobalt source and the soluble manganese source are sulfates, nitrates or chlorides of corresponding elements, NH in the ammonia water solution3·H2The molar ratio of O to the total metal amount of the soluble nickel source, the soluble cobalt source and the soluble manganese source is 0.5-1:1, and the volume ratio of the suspension to the salt solution obtained in the step S2 is 8-12:100。
7. The preparation method of the porous lithium ion battery cathode material according to claim 4, characterized in that: in step S4, the lithium source is Li (OH)2Or LiCO3The molar ratio of the lithium source to the total metal content of the soluble nickel source, the soluble cobalt source and the soluble manganese source was 1.08: 1.
8. The preparation method of the porous lithium ion battery anode material according to claim 4, which is characterized by comprising the following specific steps:
step S1: grinding 5g of graphite in an eccentric ball milling tank at the rotating speed of 700rpm for 5h, and filtering with a 800-mesh screen to obtain graphite powder;
step S2: adding the graphite powder obtained in the step S1 into an ethanol-water mixed solution consisting of 75mL of ethanol and 25mL of water, and simultaneously carrying out mechanical stirring and ultrasonic dispersion to prepare a suspension;
step S3: 262.86g of NiSO4、62g CoSO4、90.6g MnSO4Adding 1L of deionized water into the reactor to prepare 2mol/L salt solution, adding 4mol/L sodium hydroxide solution containing 1.6mol of NH3·H2O, ammonia water and the suspension obtained in the step S2, wherein the temperature of the reaction liquid is 55 ℃, the stirring speed of the reactor is 1000rpm, the reaction time is 8 hours, the pH of the reaction liquid is maintained to be 11, and nitrogen is introduced for protection in the whole process;
step S4: carrying out suction filtration and drying on the product obtained in the step S3, and mixing the product with lithium source lithium carbonate;
step S5: drying the mixture obtained in the step S4 at 60 ℃, heating the dried material to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 10h, synthesizing secondary particles mixed with an organic polymer carbon source, wherein the organic polymer carbon source is not oxidized, heating to 1100 ℃ at a heating rate of 5 ℃/min in an aerobic environment, preserving heat for 1h, further optimizing a secondary particle structure to fully oxidize the organic polymer carbon source and form a separation system by gas, and finally preparing the positive electrode material LiNi of the porous lithium ion battery0.5Co0.2Mn0.3O2The specific surface area of the porous lithium ion battery anode material is 2.324m2(ii)/g, first discharge specific capacity of 162.4mAh/g, and ionic conductivity of 8.36 x 10 at 35 ℃-7S/cm。
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