CN112028064A - Preparation method of micro hollow sphere graphite negative electrode material - Google Patents

Preparation method of micro hollow sphere graphite negative electrode material Download PDF

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CN112028064A
CN112028064A CN202010830208.1A CN202010830208A CN112028064A CN 112028064 A CN112028064 A CN 112028064A CN 202010830208 A CN202010830208 A CN 202010830208A CN 112028064 A CN112028064 A CN 112028064A
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CN112028064B (en
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彭渊敏
韩峰
韩少峰
杨栋梁
郭峰
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Ganzhou Rui Fute Technology Co ltd
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Abstract

The invention discloses a preparation method of a micro hollow sphere graphite cathode material, which aims to solve the technical problems that the cycle life and the rapid charge and discharge performance of the conventional graphite cathode material cannot be improved while the high energy density cannot be considered. The method comprises the following steps: firstly, selecting and pre-treating a proper core material, then selecting and treating a proper shell material, then coating the core material with an asphalt binder to manufacture a sphere, and finally graphitizing the spherical coated particles at high temperature to obtain the graphite cathode material of the micro hollow sphere. According to the method, the graphite negative electrode material is made into a hollow sphere structure, so that the graphite negative electrode material not only has high capacity characteristic, but also has good multiplying power cycling performance, and thus the specific capacity, the charging and discharging multiplying power and the cycling performance of the graphite negative electrode material are improved; meanwhile, the method belongs to waste material recycling and has high economic and environmental values.

Description

Preparation method of micro hollow sphere graphite negative electrode material
Technical Field
The invention belongs to the field of preparation of graphite cathode materials of lithium batteries, and particularly belongs to a preparation method of a micro hollow sphere graphite cathode material.
Background
Compared with the common battery, the lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect and the like, so the lithium ion battery is rapidly popularized in the aspects of mobile phones, notebook computers and the like; and with the increasing requirements of various electronic products on small-size, light-weight, multifunction and long-time driving, the requirements on the capacity of the lithium ion battery are also increasing day by day. At present, the improvement of the capacity of the lithium ion battery mainly depends on the development and the perfection of a negative electrode material, so that the specific capacity of the negative electrode material of the lithium ion battery is improved, the first irreversible capacity is reduced, and the rate characteristic is improved for a long time, and the improvement is always a key point for the research and the development of the lithium ion battery.
At present, most researches on negative electrode materials of lithium ion batteries are carbon materials, silicon-based materials, tin-based materials, lithium titanate, transition metal oxides and the like, wherein graphite carbon materials have mature technology, good performances in the aspects of safety, cycle life and the like, and are cheap and non-toxic, so that graphite becomes the most common negative electrode material of the lithium ion batteries at present.
For lithium ion batteries with graphite negative electrodes, during the charging process, the graphite negative electrode material can react with Li+Reaction to produce LiC6The theoretical specific capacity of the compound is 372mAh/g, while the actual specific capacity of the graphite cathode material with the highest capacity at present can reach 360mAh/g, which is very close to the theoretical capacity, so that the space which can be theoretically improved for the actual specific capacity is smaller; therefore, in the prior art, in order to obtain higher energy density, when a graphite negative electrode lithium ion battery is produced, the compacted density of the graphite negative electrode material can only be increased, so that the actual specific capacity of the graphite negative electrode material is increased. However, at present, the graphite negative electrode material has discharge rate property under the high compaction density stateThe problem of poor energy and short cycle life greatly facilitates the performance improvement of the graphite cathode lithium ion battery, so that breakthrough improvement is urgently needed on the premise that the current lithium ion battery is more and more widely applied, so that the cycle life and the rapid charge and discharge performance of the graphite cathode material can be further improved while high energy density is considered.
Disclosure of Invention
(1) Technical problem to be solved
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a micro hollow sphere graphite cathode material, which aims to solve the technical problems that the cycle life and the rapid charge and discharge performance of the conventional graphite cathode material cannot be improved while the conventional graphite cathode material cannot give consideration to high energy density. According to the method, the graphite negative electrode material is made into a hollow sphere structure, so that the graphite negative electrode material not only has high capacity characteristic, but also has good multiplying power cycling performance, and thus the specific capacity, the charging and discharging multiplying power and the cycling performance of the graphite negative electrode material are improved; meanwhile, the method belongs to waste material recycling and has high economic and environmental values.
(2) Technical scheme
In order to solve the technical problems, the invention provides a preparation method of a micro hollow sphere graphite cathode material, which comprises the following specific steps:
taking barium sulfate powder as a core material of a micro hollow sphere graphite negative electrode material, dispersing and preheating the barium sulfate powder by using a high-speed coating kettle, and adding stearic acid serving as a surfactant into the high-speed coating kettle to coat barium sulfate particles;
preferably, in the step one, the median particle size of the barium sulfate is controlled to be 15-20 μm, the purity is more than or equal to 98 percent, the Fe content is less than or equal to 0.004 percent, and the specific gravity of the barium sulfate is 4.0-4.5g/cm3The water content is less than or equal to 0.15 percent.
Preferably, in the step one, the dispersion rotation speed of the dispersion preheating is controlled to be 30-80r/min, the preheating temperature is controlled to be 150-.
Further, in the first step, the dispersion rotation speed of the dispersion preheating is controlled to be 50r/min, the preheating temperature is controlled to be 250 ℃, the temperature is increased at the heating rate of 3 ℃ per minute, and the temperature is kept for 45min after the preheating temperature is reached.
Preferably, in the first step, the stearic acid is 1801 type, and the coating rotating speed of the coated barium sulfate particles is controlled to be 105rpm, and the coating time is controlled to be 30-60 minutes.
Wherein, the first step is the selection and pretreatment of the core material.
Step two, taking fine particles generated in the process of crushing the needle-shaped calcined coke, and carrying out sphericity on the fine particles by a sphericizing machine to obtain spherical particles;
preferably, in the second step, the median particle size of the spherical particles is controlled to be 4-6 μm, the tap density is controlled to be 0.55-0.6, and the carbon content is more than or equal to 99%.
And the second step is to select and treat a shell material on the surface of the core material, the needle-shaped calcined coke is a common carburant and graphite electrode material at present, fine particles generated in the process of crushing the needle-shaped calcined coke are taken and are subjected to sphericity by a sphericizing machine to obtain spherical particles with higher sphericity and uniform particle size distribution, and the fine particles obtained after crushing the needle-shaped calcined coke are recycled.
Step three, adding asphalt into the high-speed coating kettle, and bonding and coating the spherical particles on the surfaces of the barium sulfate particles by using the bonding and high-speed coating effects of the asphalt to obtain spherical coated particles;
preferably, in the third step, the bonding and the high-speed coating are controlled by the high-speed coating kettle and are carried out in two stages, and in the first stage, the target temperature of the high-speed coating kettle is controlled to be 400 ℃, the temperature rise time is controlled to be 200min, the heat preservation time is controlled to be 30min, and the rotating speed is controlled to be 105 rpm; in the second stage, the target temperature of the high-speed coating kettle is controlled to be 600 ℃, the temperature rise time is 120min, the heat preservation time is 120min, and the rotating speed is 80 rpm.
The method comprises the steps of adopting a solid-phase coating mode, utilizing the bonding and high-speed coating effects of asphalt, taking the asphalt as an organic carbon source, utilizing a high-speed coating kettle to bond and coat small-granularity spherical particles on the surfaces of barium sulfate particles, and controlling the granulation effect through the rotating speed and the temperature of the high-speed coating kettle.
And step four, carrying out high-temperature graphitization on the spherical coating particles to ensure that barium sulfate particles at the core part are decomposed at high temperature, thereby obtaining the graphite cathode material of the micro hollow sphere.
Preferably, in the fourth step, the temperature for high-temperature graphitization is controlled to be more than or equal to 3000 ℃.
Wherein, in the high-temperature graphitization process of the spherical coating particles, barium sulfate particles at the core part are heated and decomposed, so that the micro hollow sphere graphite cathode material is finally obtained.
In addition, in the preparation process of the micro hollow sphere graphite cathode material, the type of the applied core substance, the physicochemical index of the core substance, the coating material of the core substance, the selection of the binder, the coating process and other conditions can greatly influence the particle size, the structure and the morphology of the prepared material, and the particle size, the structure and the morphology of the material can further influence the specific capacity, the primary efficiency, the compaction density, the rate capability and the cycle life of the cathode material.
(3) Advantageous effects
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the invention takes fine particles generated in the process of crushing the needle-shaped calcined coke as the main raw material, namely, the tailing generated in the process of crushing the graphite cathode material is utilized, and belongs to waste recycling, so the preparation method has high economic and environmental values; meanwhile, the graphite cathode material is made into a hollow sphere structure by utilizing the integral structure of the core material and the surface shell material thereof and combining the high-temperature graphitization and other processes of the structure, and the material not only has high capacity characteristic, but also has good multiplying power cycling performance, thereby improving the specific capacity, the charging and discharging multiplying power and the cycling performance of the graphite cathode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the technical solutions in the prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM image of barium sulfate particles in step one of example 1 of the present invention.
FIG. 2 is a diagram of carbon particles as spherical particles of shell material in step two of example 1 of the present invention.
Fig. 3 is a negative electrode diagram of the fine hollow sphere graphite negative electrode material obtained in example 1 of the present invention.
Fig. 4 shows the specific capacity of the graphite negative electrode material of the micro hollow sphere obtained in example 1 of the present invention.
Fig. 5 is a test curve of 20C-rate discharge cycle performance of the graphite negative electrode material of a hollow microsphere obtained in example 1 of the present invention.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood and obvious, the technical solutions in the embodiments of the present invention are clearly and completely described below to further illustrate the invention, and obviously, the described embodiments are only a part of the embodiments of the present invention, but not all the embodiments.
Example 1
The specific embodiment is to prepare a micro hollow sphere graphite cathode material, which comprises the following steps:
step one, selecting and pretreating a core substance; taking barium sulfate powder as a core material of a micro hollow sphere graphite negative electrode material, dispersing and preheating the barium sulfate powder by using a high-speed coating kettle, and adding 1801 type stearic acid as a surfactant into the high-speed coating kettle to coat barium sulfate particles;
wherein the median particle size of barium sulfate is controlled to be 15-20 μm, the purity is more than or equal to 98%, the Fe content is less than or equal to 0.004%, and the specific gravity of barium sulfate is 4.0-4.5g/cm3The water content is less than or equal to 0.15 percent;
controlling the dispersion rotation speed of the dispersion preheating to be 50r/min and the preheating temperature to be 250 ℃, heating at the heating rate of 3 ℃ per minute, and keeping the temperature for 45min after the temperature reaches the preheating temperature;
the coating speed of the coated barium sulfate particles was controlled to be 105rpm, and the coating time was controlled to be 45 minutes.
Selecting and treating a shell material on the surface of the core substance; taking oil needle-shaped calcined coke as a raw material, crushing the raw material by a mechanical crusher to generate cyclone collecting materials, and carrying out sphericity by a sphericizing machine to obtain spherical particles;
wherein the median particle size of the spherical particles is controlled to be 4-6 μm, the tap density is controlled to be 0.55-0.6, and the carbon content is more than or equal to 99%.
Step three, adding asphalt into the high-speed coating kettle, adopting a solid-phase coating mode, utilizing the bonding and high-speed coating effects of the asphalt, taking the asphalt as an organic carbon source, utilizing the high-speed coating kettle to bond and coat the small-granularity spherical particles on the surfaces of the barium sulfate particles, controlling the carbon content of the organic carbon source asphalt to be 5-10 wt% of the core material and the shell material, and obtaining the spherical coated particles through the bonding and high-speed coating effects of the asphalt by the spherical particles;
the bonding and the high-speed coating are controlled by a high-speed coating kettle to be carried out in two stages, in the first stage, the target temperature of the high-speed coating kettle is controlled to be 400 ℃, the temperature rise time is controlled to be 200min, the heat preservation time is controlled to be 30min, and the rotating speed is controlled to be 105 rpm; in the second stage, the target temperature of the high-speed coating kettle is controlled to be 600 ℃, the temperature rise time is 120min, the heat preservation time is 120min, and the rotating speed is 80 rpm.
And step four, cooling the spherical coating particles, and then graphitizing the spherical coating particles at a high temperature by an Acheson graphitizing furnace, wherein the graphitizing temperature is controlled to be more than or equal to 3000 ℃, and in the graphitizing process, the barium sulfate particles at the core part are decomposed by heating, so that the graphite cathode material of the micro hollow sphere is finally obtained.
Example 2
The specific embodiment is to prepare a micro hollow sphere graphite cathode material, which comprises the following steps:
step one, selecting and pretreating a core substance; taking barium sulfate powder as a core material of a micro hollow sphere graphite negative electrode material, dispersing and preheating the barium sulfate powder by using a high-speed coating kettle, and adding 1801 type stearic acid as a surfactant into the high-speed coating kettle to coat barium sulfate particles;
wherein the median particle size of barium sulfate is controlled to be 15-20 μm, the purity is more than or equal to 98%, the Fe content is less than or equal to 0.004%, and the specific gravity of barium sulfate is 4.0-4.5g/cm3The water content is less than or equal to 0.15 percent;
controlling the dispersion rotation speed of the dispersion preheating to be 30r/min and the preheating temperature to be 300 ℃, heating at the heating rate of 2 ℃ per minute, and keeping the temperature for 30min after the temperature reaches the preheating temperature;
the coating speed of the coated barium sulfate particles was controlled to be 105rpm, and the coating time was controlled to be 30 minutes.
Selecting and treating a shell material on the surface of the core substance; taking oil needle-shaped calcined coke as a raw material, crushing the raw material by a mechanical crusher to generate cyclone collecting materials, and carrying out sphericity by a sphericizing machine to obtain spherical particles;
wherein the median particle size of the spherical particles is controlled to be 4-6 μm, the tap density is controlled to be 0.55-0.6, and the carbon content is more than or equal to 99%.
Step three, adding asphalt into the high-speed coating kettle, adopting a solid-phase coating mode, utilizing the bonding and high-speed coating effects of the asphalt, taking the asphalt as an organic carbon source, utilizing the high-speed coating kettle to bond and coat the small-granularity spherical particles on the surfaces of the barium sulfate particles, controlling the carbon content of the organic carbon source asphalt to be 5-10 wt% of the core material and the shell material, and obtaining the spherical coated particles through the bonding and high-speed coating effects of the asphalt by the spherical particles;
the bonding and the high-speed coating are controlled by a high-speed coating kettle to be carried out in two stages, in the first stage, the target temperature of the high-speed coating kettle is controlled to be 400 ℃, the temperature rise time is controlled to be 200min, the heat preservation time is controlled to be 30min, and the rotating speed is controlled to be 105 rpm; in the second stage, the target temperature of the high-speed coating kettle is controlled to be 600 ℃, the temperature rise time is 120min, the heat preservation time is 120min, and the rotating speed is 80 rpm.
And step four, cooling the spherical coating particles, and then graphitizing the spherical coating particles at a high temperature by an Acheson graphitizing furnace, wherein the graphitizing temperature is controlled to be more than or equal to 3000 ℃, and in the graphitizing process, the barium sulfate particles at the core part are decomposed by heating, so that the graphite cathode material of the micro hollow sphere is finally obtained.
Example 3
The specific embodiment is to prepare a micro hollow sphere graphite cathode material, which comprises the following steps:
step one, selecting and pretreating a core substance; taking barium sulfate powder as a core material of a micro hollow sphere graphite negative electrode material, dispersing and preheating the barium sulfate powder by using a high-speed coating kettle, and adding 1801 type stearic acid as a surfactant into the high-speed coating kettle to coat barium sulfate particles;
wherein the median particle size of barium sulfate is controlled to be 15-20 μm, the purity is more than or equal to 98%, the Fe content is less than or equal to 0.004%, and the specific gravity of barium sulfate is 4.0-4.5g/cm3The water content is less than or equal to 0.15 percent;
controlling the dispersion rotation speed of the dispersion preheating to be 80r/min and the preheating temperature to be 150 ℃, heating at the heating rate of 5 ℃ per minute, and keeping the temperature for 60min (45min) after the temperature reaches the preheating temperature;
the coating speed of the coated barium sulfate particles was controlled to be 105rpm, and the coating time was controlled to be 60 minutes.
Selecting and treating a shell material on the surface of the core substance; taking oil needle-shaped calcined coke as a raw material, crushing the raw material by a mechanical crusher to generate cyclone collecting materials, and carrying out sphericity by a sphericizing machine to obtain spherical particles;
wherein the median particle size of the spherical particles is controlled to be 4-6 μm, the tap density is controlled to be 0.55-0.6, and the carbon content is more than or equal to 99%.
Step three, adding asphalt into the high-speed coating kettle, adopting a solid-phase coating mode, utilizing the bonding and high-speed coating effects of the asphalt, taking the asphalt as an organic carbon source, utilizing the high-speed coating kettle to bond and coat the small-granularity spherical particles on the surfaces of the barium sulfate particles, controlling the carbon content of the organic carbon source asphalt to be 5-10 wt% of the core material and the shell material, and obtaining the spherical coated particles through the bonding and high-speed coating effects of the asphalt by the spherical particles;
the bonding and the high-speed coating are controlled by a high-speed coating kettle to be carried out in two stages, in the first stage, the target temperature of the high-speed coating kettle is controlled to be 400 ℃, the temperature rise time is controlled to be 200min, the heat preservation time is controlled to be 30min, and the rotating speed is controlled to be 105 rpm; in the second stage, the target temperature of the high-speed coating kettle is controlled to be 600 ℃, the temperature rise time is 120min, the heat preservation time is 120min, and the rotating speed is 80 rpm.
And step four, cooling the spherical coating particles, and then graphitizing the spherical coating particles at a high temperature by an Acheson graphitizing furnace, wherein the graphitizing temperature is controlled to be more than or equal to 3000 ℃, and in the graphitizing process, the barium sulfate particles at the core part are decomposed by heating, so that the graphite cathode material of the micro hollow sphere is finally obtained.
Analysis of results
The process of the embodiment obviously shows that the fine particles generated in the process of crushing the needle-shaped calcined coke are used as the main raw material, namely, the tailings generated in the process of crushing the graphite cathode material are utilized, and the method belongs to waste recycling, so that the method has high economic and environmental values; meanwhile, the graphite cathode material is made into a hollow sphere structure by utilizing the integral structure of the core material and the surface shell material thereof and combining the high-temperature graphitization and other processes of the structure, and the material not only has high capacity characteristic, but also has good multiplying power cycling performance, thereby improving the specific capacity, the charging and discharging multiplying power and the cycling performance of the graphite cathode material.
Having thus described the principal technical features and basic principles of the invention, and the advantages associated therewith, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description is described in terms of various embodiments, not every embodiment includes only a single embodiment, and such descriptions are provided for clarity only, and those skilled in the art will recognize that the embodiments described herein can be combined as a whole to form other embodiments as would be understood by those skilled in the art.

Claims (8)

1. A preparation method of a micro hollow sphere graphite cathode material is characterized by comprising the following specific steps:
taking barium sulfate powder as a core material of a micro hollow sphere graphite negative electrode material, dispersing and preheating the barium sulfate powder by using a high-speed coating kettle, and adding stearic acid serving as a surfactant into the high-speed coating kettle to coat barium sulfate particles;
step two, taking fine particles generated in the process of crushing the needle-shaped calcined coke, and carrying out sphericity on the fine particles by a sphericizing machine to obtain spherical particles;
step three, adding asphalt into the high-speed coating kettle, and bonding and coating the spherical particles on the surfaces of the barium sulfate particles by using the bonding and high-speed coating effects of the asphalt to obtain spherical coated particles;
and step four, carrying out high-temperature graphitization on the spherical coating particles to ensure that barium sulfate particles at the core part are decomposed at high temperature, thereby obtaining the graphite cathode material of the micro hollow sphere.
2. The preparation method of the micro hollow sphere graphite cathode material according to claim 1, characterized in that in the step one, the median particle size of barium sulfate is controlled to be 15-20 μm, the purity is more than or equal to 98%, the Fe content is less than or equal to 0.004%, and the specific gravity of barium sulfate is 4.0-4.5g/cm3The water content is less than or equal to 0.15 percent.
3. The method as claimed in claim 1, wherein in the step one, the dispersion rotation speed of the dispersion preheating is controlled to be 30-80r/min, the preheating temperature is controlled to be 150 ℃ and 300 ℃, the temperature is increased at the rate of 2-5 ℃ per minute, and the temperature is maintained for 30-60min after the preheating temperature is reached.
4. The method for preparing a hollow microsphere graphite anode material as claimed in claim 3, wherein in the step one, the dispersion rotation speed of the dispersion preheating is controlled to be 50r/min, the preheating temperature is controlled to be 250 ℃, the temperature is increased at the temperature increase rate of 3 ℃ per minute, and the temperature is maintained for 45min after the preheating temperature is reached.
5. The method for preparing a hollow microsphere graphite anode material as claimed in claim 1, wherein in step one, the stearic acid is 1801 type, and the coating speed of the coated barium sulfate particles is controlled to 105rpm, and the coating time is controlled to 30-60 minutes.
6. The preparation method of the hollow microsphere graphite cathode material as claimed in claim 1, wherein in the second step, the median particle size of the spherical particles is controlled to be 4-6 μm, the tap density is controlled to be 0.55-0.6, and the carbon content is not less than 99%.
7. The preparation method of the micro hollow sphere graphite cathode material according to claim 1, characterized in that in the third step, the bonding and the high speed coating are controlled by a high speed coating kettle in two stages, and in the first stage, the target temperature of the high speed coating kettle is controlled to be 400 ℃, the temperature rise time is controlled to be 200min, the heat preservation time is controlled to be 30min, and the rotation speed is controlled to be 105 rpm; in the second stage, the target temperature of the high-speed coating kettle is controlled to be 600 ℃, the temperature rise time is 120min, the heat preservation time is 120min, and the rotating speed is 80 rpm.
8. The method for preparing a hollow microsphere graphite cathode material as claimed in claim 1, wherein in the fourth step, the temperature for high-temperature graphitization is controlled to be not less than 3000 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004031038A (en) * 2002-06-25 2004-01-29 Nippon Carbon Co Ltd Negative electrode material for high-performance lithium ion secondary battery using natural graphite, its manufacturing method and lithium ion secondary battery using it
CN103482606A (en) * 2013-09-23 2014-01-01 辽宁弘光科技(集团)有限公司 Production method for intermediate phase carbon anode material
CN106025277A (en) * 2016-06-18 2016-10-12 湖南星城石墨科技股份有限公司 Low-resilience and high-energy-density composite graphite negative electrode material and preparation method thereof
CN108328613A (en) * 2017-12-15 2018-07-27 大同新成新材料股份有限公司 A kind of method and negative material producing graphite cathode material using needle coke

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004031038A (en) * 2002-06-25 2004-01-29 Nippon Carbon Co Ltd Negative electrode material for high-performance lithium ion secondary battery using natural graphite, its manufacturing method and lithium ion secondary battery using it
CN103482606A (en) * 2013-09-23 2014-01-01 辽宁弘光科技(集团)有限公司 Production method for intermediate phase carbon anode material
CN106025277A (en) * 2016-06-18 2016-10-12 湖南星城石墨科技股份有限公司 Low-resilience and high-energy-density composite graphite negative electrode material and preparation method thereof
CN108328613A (en) * 2017-12-15 2018-07-27 大同新成新材料股份有限公司 A kind of method and negative material producing graphite cathode material using needle coke

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Inventor after: Han Feng

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Denomination of invention: Preparation method of a small hollow sphere graphite negative electrode material

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