CN107342411B - Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material - Google Patents

Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material Download PDF

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CN107342411B
CN107342411B CN201710544133.9A CN201710544133A CN107342411B CN 107342411 B CN107342411 B CN 107342411B CN 201710544133 A CN201710544133 A CN 201710544133A CN 107342411 B CN107342411 B CN 107342411B
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CN107342411A (en
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付健
梅海龙
朱亚锋
刘双双
冷九够
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Anhui Keda New Materials Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
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    • H01M4/366Composites as layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the technical field of electrode material preparation, in particular to a preparation method of a graphene-silicon carbon lithium ion battery cathode material; the method comprises the following steps: graphene coating of nano silicon particles, carbon coating of the primary composite material, carbonization and mixing; according to the invention, the nano silicon is dispersed among graphene sheet layers or on the surface of the graphene sheet layers to form a sphere-like graphene/nano silicon composite material, the graphene has good mechanical properties and flexibility, the deformation stress of silicon can be relieved, and the excellent electrical conductivity and thermal conductivity provide rapid electronic conduction and heat evacuation; the carbon-coated primary composite material is prepared by growing the carbon microspheres after heat treatment, and the formed carbon-coated layer avoids direct contact between silicon and electrolyte caused by the island effect of silicon particles, so that the structural stability and the cycle performance of the material are further improved; the silicon-carbon cathode material prepared by the method has the advantages of high initial coulombic efficiency, stable cycle performance, high compaction density and stable electrode structure.

Description

Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a preparation method of a graphene-silicon carbon lithium ion battery cathode material.
Background
With the continuous acceleration of the industrialization process of new economic bodies in the world, the global energy consumption is continuously increased, and the global fossil energy is being exhausted at an accelerated speed. Meanwhile, the problems of environmental pollution and carbon dioxide emission are becoming more serious, and the attention of countries around the world on energy conservation and environmental protection is increasing. From the trend of energy conservation and emission reduction in the automobile industry, the development of electric automobiles is a necessary choice for the technical progress and the industrial upgrading of automobiles. In recent years, major automobile production countries in the world are increasingly deployed, new energy automobiles are developed as national strategies, development and industrialization of technologies are accelerated, and automobile energy-saving technologies are vigorously developed, popularized and applied. From the emerging industrial development strategy continuously introduced by the major developed countries in the world, new energy and electric vehicles become the consensus of global development and are the key high points for seizing future economic development.
The cathode material is one of four main constituent materials of the lithium battery, is in the core link of lithium battery industry, and plays an important role in improving the capacity and the cycle performance of the battery. In the field of negative electrode materials, graphite has firmly occupied a dominating position since the last 90 th century, and the market share is about 80% at present. The graphite negative electrode has obvious price advantage and perfect matching foundation with positive electrode materials, electrolyte and other lithium battery materials. However, the reversible specific capacity of the current commercial graphite negative electrode material is already close to the theoretical specific capacity of 372mA · h/g, and the improvement space is limited, so that the development and application of other high-capacity negative electrode materials are urgent.
According to the planning of 'energy-saving and new energy automobile technical route map' in China, the single energy density target of the pure electric automobile power battery in China is 350Wh/kg by 2020. Currently, the main approach to achieve this goal is the development of high energy density electrode materials. Under the background, it is necessary and important to actively research and produce a novel negative electrode material to improve the energy density of the lithium ion battery.
The silicon carbon material is a high-capacity anode material which is researched more and is closest to industrialization. Although the capacity of the silicon negative electrode is as high as 4200mAh/g, the silicon negative electrode material is accompanied by volume expansion of 300% during lithium intercalation and cannot be applied to a lithium ion battery alone. At present, the excessive volume expansion is relieved by forming a nano silicon-carbon composite material with carbon through silicon nano-crystallization (<150nm), and the performances of the material such as cycle, multiplying power and the like are improved. However, the rate capability and cycle performance of the current silicon-carbon cathode can not meet the requirement.
Graphene, as a novel nanomaterial, was successfully isolated in 2004 by England scientists Andeli, Haim and Constantine, NovoShoulov, using mechanical exfoliation, and received the Nobel prize in 2010. Graphene is the hardest and most flexible material in the world, and is the only two-dimensional free-state atomic crystal discovered at present, and is called as a wonder material. In addition, the graphene also has a very large specific surface area, is almost completely transparent, and has excellent electric and thermal conductivity.
The graphene and the nano silicon are compounded to form the graphene/nano silicon composite material, the excellent performances of the graphene, such as high strength, high toughness, high electric and heat conductivity and the like, are well applied, the volume expansion of the nano silicon in the charging and discharging process is further relieved, the conductivity of the material is improved, and the method is a good method for improving the performances of the silicon-carbon cathode material, such as high-rate charging and discharging, circulation and the like.
Patent CN201610205702 obtains graphene coated silicon composite negative electrode material by ultrasonically mixing graphene oxide and silicon powder, freeze-drying, and then passing through, although the material has a first discharge capacity as high as 3215mAh/g, the first coulombic efficiency is as low as 74%, which indicates that silicon particles are not well coated, and are in contact with and pulverized with electrolyte.
In patent CN201510294379, the composite material of graphene and nano-silicon is obtained by performing ultrasonic treatment on graphite powder and nano-silicon powder dispersion, then performing suction filtration and centrifugation to obtain supernatant, and calcining. Although the method has simple process, because a plurality of nano-silicon are exposed outside, the capacity is low and the cycle is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a graphene-silicon carbon lithium ion battery cathode material, and the silicon carbon cathode material prepared by the method has the advantages of high initial coulombic efficiency, stable cycle performance, high compaction density and stable electrode structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphene-silicon carbon lithium ion battery cathode material comprises the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
Preferably, the conditions required for spray drying in step 1) are inlet temperature of 110-.
Preferably, the heat treatment process in step 2) is as follows: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving the heat for 0.5-3h at the temperature of 600-800 ℃.
Preferably, in the step 1), the particle size of the silicon powder is 2-8 μm, and the concentration of the graphene solution is 0.1-0.5 g/mL.
Preferably, the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 1-10.
Preferably, the growing method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 200-.
Preferably, the asphalt used in step 2) is medium-temperature coal-based asphalt.
Preferably, the other carbon materials in step 3) are selected from any one, two, three or four of artificial graphite, natural graphite, hard carbon and soft carbon.
Preferably, the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 1-10.
By adopting the technical scheme, the invention has the beneficial effects that:
1. in the patent, nano silicon is dispersed among graphene sheet layers or on the surface of the graphene sheet layers to form a sphere-like graphene/nano silicon composite material, the good mechanical property and flexibility of graphene can relieve the deformation stress of silicon, and the excellent electrical conductivity and thermal conductivity provide rapid electronic conduction and heat evacuation.
2. The carbon-coated primary composite material is prepared by growing the carbon microspheres after heat treatment, and the formed carbon-coated layer prevents silicon from being in direct contact with electrolyte due to the island effect of silicon particles, so that the structural stability and the cycle performance of the material are further improved. And finally, uniformly fusing the carbon-coated primary composite material and artificial graphite to prepare the graphene/nano silicon-carbon composite negative electrode material.
3. The silicon-carbon cathode material prepared by the method has the advantages of high initial coulombic efficiency, stable cycle performance, high compaction density and stable electrode structure.
Drawings
FIG. 1 is a schematic view of a carbon microsphere comprising graphene-nano-silicon particles according to the present invention;
FIG. 2 is a scanning electron microscope image of a carbon microsphere in accordance with the present invention;
fig. 3 is a charge-discharge curve of the graphene-silicon-carbon negative electrode material prepared by the invention at a test current of 0.1C;
fig. 4 is a cycle curve of the graphene-silicon carbon anode material prepared by the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
a preparation method of a graphene-silicon carbon lithium ion battery cathode material comprises the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
Preferably, the conditions required for spray drying in step 1) are an inlet temperature of 110 ℃ and an outlet temperature of 80 ℃.
Preferably, the heat treatment process in step 2) is as follows: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving heat for 0.5h at the temperature of 600 ℃.
Preferably, in the step 1), the particle size of the silicon powder is 2 μm, and the concentration of the graphene solution is 0.1 g/mL.
Preferably, the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 1.
preferably, the growing method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 100 ℃, adding graphene-nano silicon spherical particles, stirring uniformly, heating to 200 ℃, keeping the temperature for 0.5h, naturally cooling, adding a certain amount of washing oil when the temperature is reduced to 80 ℃, performing heat filtration when the temperature is reduced to 70 ℃, and then drying for 0.5h at 60 ℃ in a forced air drying oven.
Preferably, the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 1.
the first charging specific capacity of the graphene-silicon carbon negative electrode material prepared by the invention is 660mAh/g under the test current of 0.1C. The capacity was also maintained at 618mAh/g after 300 weeks of cycling.
Example 2:
a preparation method of a graphene-silicon carbon lithium ion battery cathode material comprises the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
Preferably, the conditions required for spray drying in step 1) are an inlet temperature of 160 ℃ and an outlet temperature of 90 ℃.
Preferably, the heat treatment process in step 2) is as follows: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving heat for 1h at 680 ℃.
Preferably, in the step 1), the particle size of the silicon powder is 4 μm, and the concentration of the graphene solution is 0.3 g/mL.
Preferably, the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 5.
preferably, the growing method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 145 ℃, adding graphene-nano silicon spherical particles, stirring uniformly, heating to 320 ℃, keeping the temperature for 1h, naturally cooling, adding a certain amount of washing oil when the temperature is reduced to 110 ℃, performing heat filtration when the temperature is reduced to 85 ℃, and then drying for 1h at 80 ℃ in a forced air drying oven.
Preferably, the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 4.
example 3:
a preparation method of a graphene-silicon carbon lithium ion battery cathode material comprises the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
Preferably, the conditions required for spray drying in step 1) are an inlet temperature of 190 ℃ and an outlet temperature of 105 ℃.
Preferably, the heat treatment process in step 2) is as follows: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving heat for 2 hours at 760 ℃.
Preferably, in the step 1), the particle size of the silicon powder is 6 μm, and the concentration of the graphene solution is 0.4 g/mL.
Preferably, the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 8.
preferably, the growing method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 186 ℃, adding graphene-nano silicon spherical particles, stirring uniformly, heating to 395 ℃, keeping the temperature for 2 hours, naturally cooling, adding a certain amount of washing oil when the temperature is reduced to 135 ℃, performing heat filtration when the temperature is reduced to 93 ℃, and then drying for 1.5 hours at 90 ℃ in a forced air drying oven.
Preferably, the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 7.
example 4:
a preparation method of a graphene-silicon carbon lithium ion battery cathode material comprises the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
Preferably, the conditions required for spray drying in step 1) are an inlet temperature of 210 ℃ and an outlet temperature of 110 ℃.
Preferably, the heat treatment process in step 2) is as follows: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving heat for 3 hours at the temperature of 800 ℃.
Preferably, in the step 1), the particle size of the silicon powder is 8 μm, and the concentration of the graphene solution is 0.5 g/mL.
Preferably, the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 10.
preferably, the growing method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 200 ℃, adding graphene-nano silicon spherical particles, stirring uniformly, heating to 420 ℃, keeping the temperature for 3 hours, naturally cooling, adding a certain amount of washing oil when the temperature is reduced to 150 ℃, performing heat filtration when the temperature is reduced to 100 ℃, and then drying for 2 hours in a forced air drying oven at 100 ℃.
Preferably, the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 10.
the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A preparation method of a graphene-silicon-carbon lithium ion battery cathode material is characterized by comprising the following steps:
1) and (3) coating the nano silicon particles with graphene: firstly, sanding micron-level silicon powder, adding a graphene solution, continuing sanding to obtain a graphene-nano silicon mixed solution, and then performing spray drying to obtain graphene-nano silicon spherical particles;
2) carbon-coated primary composite material: carrying out heat treatment on the graphene-nano silicon spherical particles obtained in the step 1), uniformly dispersing the graphene-silicon nano particles subjected to heat treatment in asphalt, and carrying out high-temperature reaction to obtain carbon microspheres with uniformly dispersed graphene-silicon nano particles;
3) carbonizing and mixing materials: carbonizing the carbon microspheres obtained in the step 2), and mixing the carbonized carbon microspheres with other carbon materials to obtain the graphene-silicon carbon negative electrode material.
2. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the conditions required by the spray drying in the step 1) are that the inlet temperature is 110-210 ℃, and the outlet temperature is 80-110 ℃.
3. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the heat treatment process in the step 2) comprises the following steps: and (3) putting the dried graphene-nano silicon spherical particles into a high-temperature furnace, and preserving the heat for 0.5-3h at the temperature of 600-800 ℃.
4. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step 1), the particle size of the silicon powder is 2-8 μm, and the concentration of the graphene solution is 0.1-0.5 g/mL.
5. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the mass ratio of the silicon powder to the graphene solution in the step 1) is 1: 1-10.
6. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the growth method of the carbon microspheres in the step 2) comprises the following steps: adding asphalt into a reaction kettle, heating to 200-.
7. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the asphalt used in the step 2) is medium-temperature coal-series asphalt.
8. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: and the other carbon materials in the step 3) are any one, two, three or four of artificial graphite, natural graphite, hard carbon and soft carbon.
9. The preparation method of the graphene-silicon-carbon lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the mass ratio of the carbon microspheres to other carbon materials in the step 3) is 1: 1-10.
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