CN109935792B - Composite surface modification method for lithium ion battery cathode material - Google Patents
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Abstract
The invention discloses a composite surface modification method of a lithium ion battery cathode material, which comprises the steps of crushing three raw materials of oil-based asphalt, a modifier and a graphitization catalyst, mixing, heating in a grading manner, crushing, introducing a carbon source for graphitization, passivating to obtain graphene micro-sheets, performing polyurethane oligomer modification and SBS modification on the graphene micro-sheets to obtain composite modified graphite, and covering the surface of natural graphene with the composite modified graphite to form the battery cathode material which takes the natural graphene as an inner core and is coated with the composite modified graphite at the outer layer. The surface modification method has low cost, overcomes the defects of high cost and uneven coating modification of the surface of the conventional cathode material, and can effectively improve the surface modification efficiency and uniformity of the material.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to a composite surface modification method of a lithium ion battery cathode material.
Background
The artificial graphite is a main negative electrode material used in the production of lithium ion batteries in China at present, has high theoretical lithium intercalation capacity and stable performance, and is an ideal negative electrode material of the lithium ion batteries. However, due to the high orientation of graphite crystals, the dynamic resistance of rapid charge and discharge is large, and the van der waals force between graphite layers is weak, so that the cycle performance of graphite is not ideal enough due to expansion and contraction during charge and discharge, and therefore, graphite can be used after being subjected to surface modification.
Disclosure of Invention
In view of the above, the present invention provides a method for modifying a composite surface of a negative electrode material of a lithium ion battery, which solves the problems of high cost and uneven coating modification on the surface of the negative electrode material, and effectively improves the surface modification efficiency and uniformity of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite surface modification method for a lithium ion battery cathode material comprises the following steps
Step (1), respectively crushing the oil-based asphalt, the modifier and the graphitization catalyst to crush the particles to 150-240 meshes;
step (2), the weight portions are as follows: 80-100 parts of oil-series asphalt, 10-30 parts of modifier and 1-5 parts of graphitization catalyst are put into a mixing machine, the rotating speed of the mixing machine is adjusted to be 10-100r/s, and the mixing time is 2-10 hours, so that the modifier is uniformly adhered to the surface of the oil-series asphalt;
step (3), putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to 10-100r/s, heating in a furnace, carrying out primary roasting treatment at normal temperature to 200 ℃ for 0.5-10 hours, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 300-500 meshes; continuously heating the reaction kettle in the furnace at the temperature of 200-; continuously heating the reaction kettle furnace to 500 ℃ and keeping the temperature for 1-5 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to ensure that the particle size of the material is 300-500 meshes; continuously heating the reaction kettle in the furnace at the temperature of 500-650 ℃ for 0.5-10 hours, carrying out fourth roasting treatment, and carrying out fourth crushing treatment on the material subjected to the fourth roasting treatment to ensure that the particle size of the material is 500 meshes at 300-650 ℃;
step (4), under the protective gas atmosphere, passing a carbon source into the reaction kettle, wherein the flow rate of the carbon source is 50-300sccm, continuously heating from 650-800 ℃, and keeping the temperature for 10-30min to obtain graphene;
step (5), collecting the graphene, removing the nano catalyst on the surface by adopting an acid solution with the mass concentration of 5-50%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain a passivated graphene microchip;
and (6), according to the weight ratio of 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, ultrasonically oscillating for 5-10min in an ultrasonic disperser, then adding the polyurethane oligomer, reacting in water at 50-80 ℃ for 3-5h, then adding hydrazine hydrate, placing the solution in an oil bath at 100-200 ℃ for 12-24h, then filtering, and drying filter residues to obtain the polyurethane oligomer modified graphene nanoplatelets;
step (7), according to the weight ratio of 3-15: 30-150, respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, crushing SBS modified particles, fully mixing the crushed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 1-2 hours at the temperature of 200 ℃ by using a stirrer to obtain composite modified graphite;
and (8) covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
Compared with the prior art, the method has obvious advantages and beneficial effects, and concretely, the technical scheme shows that the oil-based asphalt is modified by the modifier and the graphitization catalyst, the surface modification effect on calcined petroleum coke or needle coke or asphalt coke or coal coke is good, the surface modification technology is used for various raw material cokes, the modifier is low in price and sufficient in supply, the equipment structure is simple, and the production efficiency is high. In addition, the modification equipment adopts a vertical reaction kettle, the circulating water is used for cooling, the special cooling kettle is used for cooling, continuous production is realized, the productivity is improved by more than 40 percent, the cost is reduced by more than 50 percent, simultaneously, a good modification effect can be achieved, and the market competitiveness is strong. And (5) introducing a carbon source in the step (5), and using high-temperature heat treatment to improve a large amount of energy for rearrangement of carbon atoms, in order to improve the graphitization degree of the graphitized carbon material, adding a catalyst to catalyze graphitization, so that the activation energy required by bond breaking rearrangement of the carbon atoms is reduced, and the carbon material is prevented from reaching the graphitization degree standard due to the influence of temperature in industrial graphitization, so that the graphitization yield is improved, and the electrical property of the graphite material can be improved by improving the graphitization degree. And finally, covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material which takes the natural graphene as an inner core and is coated with the composite modified graphite on the outer layer, so that the graphite capacity can be improved, and the problems of poor graphite rate performance and high-current charge-discharge performance are solved.
The present invention will be described in detail with reference to specific embodiments in order to more clearly illustrate the structural features and effects of the present invention.
Detailed Description
The invention discloses a composite surface modification method of a lithium ion battery cathode material, which comprises the following steps.
In the step (1), the oil-based asphalt, the modifier and the graphitization catalyst are respectively crushed to obtain particles of 150-240 meshes. Wherein the oil-based asphalt is at least one of calcined petroleum coke, needle coke, asphalt coke or coal coke. The modifier is an organic molecule having a conjugated structure with a large pi bond. The organic molecule having a conjugated structure with a large pi bond is at least one of pyrenes and derivatives thereof. The graphitizing catalyst is at least one of borax, urea, silicon powder and silicon oxide.
The step (2) comprises the following steps in parts by weight: 80-100 parts of oil-series asphalt, 10-30 parts of modifier and 1-5 parts of graphitization catalyst are put into a mixing machine, the rotating speed of the mixing machine is adjusted to be 10-100r/s, and the mixing time is 2-10 hours, so that the modifier is uniformly adhered to the surface of the oil-series asphalt.
Step (3) putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to 10-100r/s, heating in a furnace, carrying out primary roasting treatment at normal temperature to 200 ℃ for 0.5-10 hours, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 300-500 meshes; continuously heating the reaction kettle in the furnace at the temperature of 200-; continuously heating the reaction kettle furnace to 500 ℃ and keeping the temperature for 1-5 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to ensure that the particle size of the material is 300-500 meshes; the reaction kettle is heated for 0.5 to 10 hours at the temperature of 650 ℃ for 500-.
And (4) under the protective gas atmosphere, passing a carbon source into the reaction kettle, wherein the flow rate of the carbon source is 50-300sccm, continuously heating at the temperature of 650-800 ℃, and keeping the temperature for 10-30min to obtain the graphene. Wherein the carbon source is at least one of methanol, ethanol, propanol, ethylene, propylene, acetylene and propyne.
And (5) collecting the graphene, removing the nano catalyst on the surface by adopting an acid solution with the mass concentration of 5-50%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain the passivated graphene microchip. Wherein the acid solution is at least one of nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid.
Step (6) is that the weight ratio is 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, ultrasonically oscillating for 5-10min in an ultrasonic disperser, then adding the polyurethane oligomer, reacting in water at 50-80 ℃ for 3-5h, then adding hydrazine hydrate, reacting the solution in an oil bath at 100-200 ℃ for 12-24h, then filtering, and drying filter residues to obtain the polyurethane oligomer modified graphene nanoplatelets. Wherein, the filtering is to wash the filter residue with clean water, methanol and ethanol alternately.
The step (7) is carried out according to the weight ratio of 3-15: 30-150, respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, crushing SBS modified particles, fully mixing the crushed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 1-2 hours at the temperature of 150-200 ℃ by using a stirrer to obtain the composite modified graphite. Wherein the composite modified graphite is in a hollow mesh bag shape, the sheet size of the graphite is 0.5-50 μm, and the thickness of the graphite is 0.3-0.5 nm.
And (8) covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
The invention modifies the oil asphalt by adopting the modifier and the graphitizing catalyst, has good surface modification effect on calcined petroleum coke or needle coke or asphalt coke or coal coke, and the surface modification technology is used for various raw material cokes, and has the advantages of low price of the modifier, sufficient supply, simple equipment structure and high production efficiency. In addition, the modification equipment adopts a vertical reaction kettle, the circulating water is used for cooling, the special cooling kettle is used for cooling, continuous production is realized, the productivity is improved by more than 40 percent, the cost is reduced by more than 50 percent, simultaneously, a good modification effect can be achieved, and the market competitiveness is strong. And (5) introducing a carbon source in the step (5), and using high-temperature heat treatment to improve a large amount of energy for rearrangement of carbon atoms, in order to improve the graphitization degree of the graphitized carbon material, adding a catalyst to catalyze graphitization, so that the activation energy required by bond breaking rearrangement of the carbon atoms is reduced, and the carbon material is prevented from reaching the graphitization degree standard due to the influence of temperature in industrial graphitization, so that the graphitization yield is improved, and the electrical property of the graphite material can be improved by improving the graphitization degree. And finally, covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material which takes the natural graphene as an inner core and is coated with the composite modified graphite on the outer layer, so that the graphite capacity can be improved, and the problems of poor graphite rate performance and high-current charge-discharge performance are solved.
Example 1
In step 1, calcined petroleum coke, an organic molecule with a conjugated structure at pi bond and silicon powder are respectively crushed to crush the particles to 150 meshes. Step 2, the weight portions are as follows: 100 parts of calcined petroleum coke, 30 parts of organic molecules with a large pi bond conjugated structure and 5 parts of silicon powder are put into a mixing machine, the rotating speed of the mixing machine is adjusted to be 80r/s, and the mixing time is adjusted to be 3 hours, so that the organic molecules with the large pi bond conjugated structure are uniformly adhered to the surface of the calcined petroleum coke. Step 3, putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to 80r/s, heating the reaction kettle in a furnace, carrying out primary roasting treatment at the normal temperature of 200 ℃ for 0.5 hour, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 300 meshes; continuously heating the inside of the reaction kettle at 300 ℃ for 0.5 hour, carrying out secondary roasting treatment, and carrying out secondary crushing treatment on the material subjected to the secondary roasting treatment to enable the particle size of the material to be 300 meshes; continuously heating the reaction kettle to 500 ℃ in the furnace, keeping the temperature for 1-5 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to enable the particle size of the material to be 300 meshes; and (3) continuously heating the inside of the reaction kettle at 650 ℃ for 0.5 hour, performing fourth roasting treatment, and performing fourth crushing treatment on the material subjected to the fourth roasting treatment to enable the particle size of the material to be 300 meshes. And 4, under the protective gas atmosphere, passing methanol into the reaction kettle, wherein the flow of the methanol is 100sccm, continuously heating to 800 ℃, and keeping the temperature constant for 10min to obtain the graphene. And 5, collecting the graphene, removing the nano catalyst on the surface by using nitric acid with the mass concentration of 35%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain the passivated graphene microchip. Step 6, according to the weight ratio of 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, carrying out ultrasonic oscillation for 5min in an ultrasonic disperser, then adding the polyurethane oligomer, putting the polyurethane oligomer in water with the temperature of 50 ℃ for reaction for 3h, then adding hydrazine hydrate, putting the solution in an oil bath for reaction for 18h at the temperature of 150 ℃, then filtering, and drying filter residues to obtain the graphene nanoplatelets modified by the polyurethane oligomer. And 7, preparing the raw materials in a weight ratio of 3: 70 respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, smashing SBS modified particles, fully mixing the smashed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 2 hours at the temperature of 150 ℃ by using a stirrer to obtain the composite modified graphite. And 8, covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
Example 2
In step 1, needle coke, an organic molecule having a conjugated structure at a large pi bond, and silicon oxide were pulverized to obtain particles of 240 mesh. Step 2, the weight portions are as follows: 80 parts of needle coke, 10 parts of organic molecule with large pi bond conjugated structure and 1 part of silicon oxide are put into a mixer, the rotation speed of the mixer is adjusted to 10r/s, and the mixing time is adjusted to 2 hours, so that the organic molecule with large pi bond conjugated structure is uniformly adhered to the surface of the needle coke. Step 3, putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to 10r/s, heating the reaction kettle in a furnace, carrying out primary roasting treatment at normal temperature to 200 ℃ for 10 hours, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 500 meshes; continuously heating the reaction kettle at the temperature of 400 ℃ for 10 hours, carrying out secondary roasting treatment, and carrying out secondary crushing treatment on the material subjected to the secondary roasting treatment to enable the particle size of the material to be 500 meshes; continuously heating the reaction kettle to 500 ℃ in the furnace, keeping the temperature for 5 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to enable the particle size of the material to be 500 meshes; and (3) continuously heating the inside of the reaction kettle at 650 ℃ for 10 hours, carrying out fourth roasting treatment, and carrying out fourth crushing treatment on the material subjected to the fourth roasting treatment to enable the particle size of the material to be 500 meshes. And 4, under the protective gas atmosphere, passing ethanol into the reaction kettle, wherein the flow rate of the ethanol is 50sccm, continuously heating to 750 ℃, and keeping the temperature for 30min to obtain the graphene. And 5, collecting the graphene, removing the nano catalyst on the surface by adopting hydrochloric acid with the mass concentration of 5%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain the passivated graphene microchip. Step 6, according to the weight ratio of 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, carrying out ultrasonic oscillation for 10min in an ultrasonic disperser, then adding the polyurethane oligomer, putting the mixture into water with the temperature of 80 ℃ for reaction for 5h, then adding hydrazine hydrate, putting the solution into an oil bath for reaction for 18h at the temperature of 200 ℃, then filtering, and drying filter residues to obtain the graphene nanoplatelets modified by the polyurethane oligomer. And 7, preparing the raw materials in a weight ratio of 15: 30 respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, smashing SBS modified particles, fully mixing the smashed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 1 hour at the temperature of 200 ℃ by using a stirrer to obtain the composite modified graphite. And 8, covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
Example 3
In step 1, coal char, an organic molecule having a conjugated structure at pi bond, and borax are pulverized to pulverize fine particles to 240 mesh. Step 2, the weight portions are as follows: 85 parts of coal tar, 28 parts of organic molecules with a large pi bond conjugated structure and 3 parts of borax are fed into a mixing machine, the rotating speed of the mixing machine is adjusted to be 100r/s, and the mixing time is adjusted to be 3 hours, so that the organic molecules with the large pi bond conjugated structure are uniformly adhered to the surface of the coal tar. Step 3, putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to be 100r/s, heating the reaction kettle in a furnace, carrying out primary roasting treatment at the normal temperature of 200 ℃ for 6 hours, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 400 meshes; continuously heating the reaction kettle at 370 ℃ for 10 hours, carrying out secondary roasting treatment, and carrying out secondary crushing treatment on the material subjected to the secondary roasting treatment to ensure that the particle size of the material is 400 meshes; continuously heating the reaction kettle to 500 ℃ in the furnace, keeping the temperature for 3 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to enable the particle size of the material to be 400 meshes; and (3) continuously heating the inside of the reaction kettle at the temperature of 650 ℃ for 8 hours, carrying out fourth roasting treatment, and carrying out fourth crushing treatment on the material subjected to the fourth roasting treatment to ensure that the particle size of the material is 400 meshes. And 4, under the protective gas atmosphere, passing acetylene into the reaction kettle, wherein the flow rate of the acetylene is 300sccm, continuously heating to 800 ℃, and keeping the temperature for 10min to obtain the graphene. And 5, collecting the graphene, removing the nano catalyst on the surface by adopting hydrofluoric acid with the mass concentration of 5%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain the passivated graphene microchip. Step 6, according to the weight ratio of 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, carrying out ultrasonic oscillation for 6min in an ultrasonic disperser, then adding the polyurethane oligomer, putting the mixture into water with the temperature of 60 ℃ for reaction for 4h, then adding hydrazine hydrate, putting the solution into an oil bath for reaction for 12h at the temperature of 100 ℃, then filtering, and drying filter residues to obtain the graphene nanoplatelets modified by the polyurethane oligomer. And 7, preparing a mixture by weight ratio of 7: 100, respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, smashing SBS modified particles, fully mixing the smashed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 1.5 hours at the temperature of 180 ℃ by using a stirrer to obtain the composite modified graphite. And 8, covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (7)
1. A method for modifying the composite surface of a lithium ion battery cathode material is characterized by comprising the following steps: comprises the following steps
Step (1), respectively crushing the oil-based asphalt, the modifier and the graphitization catalyst to crush the particles to 150-240 meshes; the modifier is an organic molecule having a conjugated structure with a large pi bond; the organic molecule having a conjugated structure with a large pi bond is at least one of pyrenes and derivatives thereof;
step (2), the weight portions are as follows: 80-100 parts of oil-series asphalt, 10-30 parts of modifier and 1-5 parts of graphitization catalyst are put into a mixing machine, the rotating speed of the mixing machine is adjusted to be 10-100r/s, and the mixing time is 2-10 hours, so that the modifier is uniformly adhered to the surface of the oil-series asphalt;
step (3), putting the mixed graphite into a vertical reaction kettle, adjusting the rotating speed of the reaction kettle to 10-100r/s, heating in a furnace, carrying out primary roasting treatment at normal temperature to 200 ℃ for 0.5-10 hours, and carrying out primary crushing treatment on the material subjected to the primary roasting treatment to ensure that the particle size of the material is 300-500 meshes; continuously heating the reaction kettle in the furnace at the temperature of 200-; continuously heating the reaction kettle furnace to 500 ℃ and keeping the temperature for 1-5 hours, carrying out third roasting treatment, and carrying out third crushing treatment on the material subjected to the third roasting treatment to ensure that the particle size of the material is 300-500 meshes; continuously heating the reaction kettle in the furnace at the temperature of 500-650 ℃ for 0.5-10 hours, carrying out fourth roasting treatment, and carrying out fourth crushing treatment on the material subjected to the fourth roasting treatment to ensure that the particle size of the material is 500 meshes at 300-650 ℃;
step (4), under the protective gas atmosphere, passing a carbon source into the reaction kettle, wherein the flow rate of the carbon source is 50-300sccm, continuously heating from 650-800 ℃, and keeping the temperature for 10-30min to obtain graphene;
step (5), collecting the graphene, removing the nano catalyst on the surface by adopting an acid solution with the mass concentration of 5-50%, drying, and introducing carbon dioxide to remove amorphous carbon to obtain a passivated graphene microchip;
and (6), according to the weight ratio of 20: 1, respectively weighing graphene nanoplatelets and polyurethane oligomer, firstly dissolving the graphene nanoplatelets in water, ultrasonically oscillating for 5-10min in an ultrasonic disperser, then adding the polyurethane oligomer, reacting in water at 50-80 ℃ for 3-5h, then adding hydrazine hydrate, placing the solution in an oil bath at 100-200 ℃ for 12-24h, then filtering, and drying filter residues to obtain the polyurethane oligomer modified graphene nanoplatelets;
step (7), according to the weight ratio of 3-15: 30-150, respectively weighing the graphene nanoplatelets modified by the polyurethane oligomer and the SBS modifier, crushing SBS modified particles, fully mixing the crushed particles with the graphene nanoplatelets modified by the polyurethane oligomer, and stirring and shearing the mixture for 1-2 hours at the temperature of 200 ℃ by using a stirrer to obtain composite modified graphite;
and (8) covering the surface of the natural graphene with the composite modified graphite to form the battery cathode material with the natural graphene as an inner core and the composite modified graphite coated on the outer layer.
2. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (1), the oil-based asphalt is at least one of calcined petroleum coke, needle coke, asphalt coke or coal coke.
3. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (1), the graphitization catalyst is at least one of borax, urea, silicon powder and silicon oxide.
4. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (4), the carbon source is at least one of methanol, ethanol, propanol, ethylene, propylene, acetylene and propyne.
5. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (5), the acid solution is at least one of nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid.
6. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (6), the filtration is to alternately wash the filter residue with clear water, methanol and ethanol respectively.
7. The composite surface modification method for the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (7), the composite modified graphite is in a hollow mesh bag shape, the sheet size of the graphite is 0.5-50 μm, and the thickness of the graphite is 0.3-0.5 nm.
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| WO2013085509A1 (en) * | 2011-12-07 | 2013-06-13 | CNano Technology Limited | Electrode composition for li ion battery |
| CN103241731A (en) * | 2013-04-01 | 2013-08-14 | 东莞市凯金电池材料有限公司 | Preparation method of compound graphite material for lithium ion secondary battery |
| CN105390673A (en) * | 2015-10-28 | 2016-03-09 | 东莞市凯金新能源科技有限公司 | Preparation method of high-capacity and low-resilience graphite anode material for lithium-ion battery |
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| WO2013085509A1 (en) * | 2011-12-07 | 2013-06-13 | CNano Technology Limited | Electrode composition for li ion battery |
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