CN106169582A - A kind of natural pin Jiao's composite graphite negative electrode material production method - Google Patents

A kind of natural pin Jiao's composite graphite negative electrode material production method Download PDF

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CN106169582A
CN106169582A CN201610707852.3A CN201610707852A CN106169582A CN 106169582 A CN106169582 A CN 106169582A CN 201610707852 A CN201610707852 A CN 201610707852A CN 106169582 A CN106169582 A CN 106169582A
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raw material
carry out
weigh
production method
negative electrode
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CN106169582B (en
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王丽琼
叶涛
韩团辉
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Dalian Hongguang Lithium Industry Co.,Ltd.
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Dalian Hongguan Liye 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
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention provides a kind of natural pin Jiao's composite graphite negative electrode material production method, with needle coke as raw material A, with native graphite for raw material B, with Colophonium micropowder for raw material C, with graphene conductive agent for raw material D, with CNT for raw material E, above-mentioned raw materials is through a series of machinings, surface modification, the methods such as Chemical deep modification and doping, prepare one to have extended cycle life, charge-discharge velocity is fast, high temperature performance is good, good processability, the negative material of applicable electrokinetic cell, its production technology is simple, production efficiency is high, low cost, course of processing safety, can be used for industrialized production.It is an advantage of the current invention that: add graphene conductive agent and CNT mixing material, improve the electric conductivity of material;Carry out graphitization under coarse powder state, it is possible to reduce particle surface oxidation activity point, degree of oxidation and materials loss rate, improve capacity and the yield of material.

Description

A kind of natural pin Jiao's composite graphite negative electrode material production method
Technical field
The present invention relates to a kind of natural pin Jiao's composite graphite negative electrode material production method, belong to lithium ion battery negative material Technical field.
Background technology
The important sources as automobile power of lithium ion battery, has the saving energy, the effect of protection environment.And lithium from The negative material of sub-battery is the main contents of current scientific research personnel research, the most preferably makes battery play maximum usefulness, Energy-saving and emission-reduction, optimize the environment, and have vital effect for socioeconomic development.At present, the lithium in research range from Sub-cell negative electrode material remains based on graphite etc., in daily life, using graphite as lithium ion battery negative material Battery operated principle be, battery in charging process, on positive pole abjection lithium ion embed rapidly negative pole, when embed lithium from Son is the most, and the when of embedding the fastest, the capacity of charging is the highest, and discharge capacity is the biggest, and charge-discharge velocity is the fastest.Currently, The lithium ion battery negative material of commercialization mostly is single Carbon Materials, but Carbon Materials is as the negative material of lithium ion itself There is also certain defect, Carbon anode current potential with the current potential of lithium metal close to when, easily there is separating out Li dendrite, thus Cause short circuit, form the potential safety hazard of lithium ion battery.The performance of lithium ion battery negative material is also electrokinetic cell development One of bottleneck, it is possible to constantly improve research and development Novel cathode material for lithium ion battery, is the important process of development lithium electric power industry.
China's lithium-ion-power cell development starts from twentieth century, starts late.But since 2000, along with China More than 10 hundred million funds of input are used for supporting to develop electric motor car and associated batteries technology, and the reality of " 863 " electric automobile key special subjects Executing, strong state-run, private enterprise have carried out developmental research to lithium-ion-power cell, the performance of lithium ion battery of production with External product is suitable, and some aspect is even better than external product, and export abroad amount constantly rises.China's lithium ion power electricity at present Pond mainly includes power tool battery, battery of electric bicycle, extraordinary Vehicular battery and battery for electric automobile etc., also has future Being probably the ideal source replacing existing submarine electrokinetic cell, various lithium-ion-power cells are in the industrialization starting stage.
In general, a kind of good negative material is selected should to follow following principle: specific energy is high, discharge and recharge reaction reversibility Good good with the compatibility of electrolyte and binding agent, high temperature performance is good, and charge-discharge velocity is fast.The present invention is directed to different carbonaceous material The performance of material carries out Improvement, reaches to adapt to the performance requirement that electrokinetic cell uses.
Summary of the invention
It is an object of the invention to provide a kind of natural pin Jiao's composite graphite negative electrode material production method, single artificial to solve The problem that graphite degree of graphitization is low and in heat treatment process, capacity caused by degree of oxidation height is low, overcome native graphite Cycle Difference, The defects such as high temperature performance and flexibility (adaptability) of operation difference, improve the electric conductivity of material, high rate performance etc. simultaneously.
Technical scheme: a kind of natural pin Jiao's composite graphite negative electrode material production method, concrete production technology is: A () is with needle coke as raw material A;
B () is with native graphite for raw material B;
(c) with Colophonium micropowder for raw material C, particle diameter D50≤5 m;
D () is with graphene conductive agent for raw material D;
E () is with CNT for raw material E;
F raw material A is ground into the granule that particle diameter is 0.5-3mm by (), carry out graphitization at 2800 ~ 3200 DEG C, then carries out thin Pulverizing, grinding particle size D50 is 8 ~ 12 m;
G raw material A fine powder that (f) step is obtained by () and raw material B, by weight A/B=100/(30 ~ 100) ratio carry out uniformly Mixing, fusion;
H material and raw material C, the by weight ratio of (A+B)/C=100/2 ~ 10 that (g) step is obtained by () mix, mixing After at 1200 ~ 1500 DEG C, carry out carbonization;
(i) by raw material D and raw material E by weight D/E=100/(50 ~ 200) ratio carry out air-flow mixing;
J material that (h) step is obtained by () and the material that (i) step obtains, by weight (A+B+C)/(D+E)=100/(1 ~ 3) Ratio uniformly mix, screening, finally obtain product.
Preferably, described raw material A is petroleum needle coke or coal-based needle Jiao.
Preferably, described raw material B is asphalt or coal tar pitch.
Preferably, described in step (g), (h), (j), mixing uses double-cone mixer.
Preferably, employing jet mill is pulverized described in step (f).
Beneficial effects of the present invention:
1, needle coke is the excellent raw material for developing power graphite cathode material, and the present invention uses high-quality needle coke to be main Raw material, the performance advantage utilizing needle coke the high power capacity combining native graphite and the good advantage of isotropism, compound preparation is negative Pole material, is product pattern, processing characteristics, and the application performance such as capacity, efficiency, circulation is significantly improved;
2, it is processed into coarse powder owing to the present invention carries out mechanical activation comminution to needle coke, under coarse powder state, carries out graphitization, can subtract The surface oxidation degree of few material, reduces active site, and effectively reduces graphited material loss;After fine powder, material is thin Particle surface is not oxidized, can improve effective charge-discharge velocity, and contribute to pitch-coating layer cladding solid closely, no Easy to fall off;
3, needle coke carries out graphitization under coarse powder state, is possible not only to reduce material oxidation degree, after bonding after continuous process More can reduce the specific surface area of material, improve drawing abillity, i.e. pole piece compacting bounce-back is little, pole piece compaction density is high;
4, use needle coke to add a certain proportion of native graphite and carry out surface modification, improve the appearance of needle coke, improve jolt ramming Density, reduces specific surface area, improves the isotropism of needle coke, thus improves charge-discharge velocity, concurrently facilitates and make material list Face is evenly coated, and forms firm pitch-coating layer;
5, carry out asphalt carbon cladding after graphitization, form one layer of fine and close soft charcoal layer at graphite surface, be favorably improved surface Electric conductivity, adds a small amount of graphene conductive agent and CNT, can increase substantially the electric conductivity of material, improves charge and discharge Electricity speed;
6, in sum, the present invention, by utilizing needle coke and native graphite, through a series of machinings, surface modification, changes The degree of depth is modified, and the method such as doping, and preparing one has extended cycle life, and charge-discharge velocity is fast, and high temperature performance is good, processability Can be good, the negative material of applicable electrokinetic cell, its production technology is simple, and production efficiency is high, low cost, and the course of processing is pacified Entirely, can be used for industrialized production.
Detailed description of the invention:
Embodiment 1
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3000 DEG C, carry out graphitization, so After carry out finely divided, grinding particle size D50 is 10 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 15kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 1.5 kg, at 1300 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 2kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.2kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 348.6mAh/g, and discharging efficiency is 93.0%, through 50 circulations Rear capability retention is 98.4%, and after 100 circulations, capability retention is 96.5%, as shown in table 1.
Embodiment 2
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3000 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 8 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 20kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 2.5 kg, at 1300 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 1kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 349.2mAh/g, and discharging efficiency is 93.2%, through 50 circulations Rear capability retention is 98.8%, and after 100 circulations, capability retention is 96.3%, as shown in table 1.
Embodiment 3
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 2800 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 11 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 25kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 3.0 kg, at 1200 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 1.2kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.6kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 347.3mAh/g, and discharging efficiency is 92.9%, through 50 circulations Rear capability retention is 97.5%, and after 100 circulations, capability retention is 96.4%, as shown in table 1.
Embodiment 4
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 2900 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 12 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 25kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 2.0 kg, at 1400 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 1.6kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 350.0mAh/g, and discharging efficiency is 93.5%, through 50 circulations Rear capability retention is 98.7%, and after 100 circulations, capability retention is 96.6%, as shown in table 1.
Embodiment 5
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3100 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 10 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 30kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 4.0 kg, at 1500 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 2.4kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 348.6mAh/g, and discharging efficiency is 92.5%, through 50 circulations Rear capability retention is 98.2%, and after 100 circulations, capability retention is 96.3%, as shown in table 1.
Embodiment 6
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3200 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 8 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 40kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 1.5 kg, at 1300 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 3kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.2kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 352.4mAh/g, and discharging efficiency is 93.4%, through 50 circulations Rear capability retention is 97.3%, and after 100 circulations, capability retention is 95.6%, as shown in table 1.
Embodiment 7
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3100 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 11 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 50kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 2.0 kg, at 1400 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 4kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 358.8mAh/g, and discharging efficiency is 94.2%, through 50 circulations Rear capability retention is 98.4%, and after 100 circulations, capability retention is 96.7%, as shown in table 1.
Embodiment 8
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3000 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 10 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 25kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 2.5 kg, at 1300 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 3kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.2kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 354.7mAh/g, and discharging efficiency is 93.7%, through 50 circulations Rear capability retention is 98.6%, and after 100 circulations, capability retention is 96.8%, as shown in table 1.
Embodiment 9
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3100 DEG C, carry out graphitization, Then carrying out finely divided, grinding particle size D50 is 12 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 15kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 1.5 kg, at 1400 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 2kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 349.6mAh/g, and discharging efficiency is 94.5%, through 50 circulations Rear capability retention is 98.4%, and after 100 circulations, capability retention is 96.6%, as shown in table 1.
Embodiment 10
Weigh needle-shape coke raw material A 200kg, be ground into the granule that particle diameter is about 0.5 ~ 3mm, at 3000 DEG C, carry out graphitization, so After carry out finely divided, grinding particle size D50 is 10 m.
Weigh the needle-shape coke raw material A 50kg after graphitization, add natural graphite starting material B 15kg, mix, then enter Row merges shaping.
Weigh the raw material after fusion (A+B) 50kg and add Colophonium powder material C 1.5 kg, at 1300 DEG C, carry out carbonization.
Weigh graphene conductive agent raw material D 2kg and add carbon nanometer tube material E 3.6kg, carry out air-flow mixing.
Weigh the raw material after carbonization (A+B+C) 20kg and add compound (D+E) 0.4kg, uniformly mix, sieve, remove Miscellaneous, obtain product.
Carry out product of the present invention pulling an oar, after the series of process such as coating, then make LIR2430 type button cell, warp Test, gained composite graphite negative electrode material discharge capacity first is 349.4mAh/g, and discharging efficiency is 94.4%, through 50 circulations Rear capability retention is 97.6%, and after 100 circulations, capability retention is 95.7%, as shown in table 1.

Claims (3)

1. natural pin Jiao's composite graphite negative electrode material production method, concrete production technology is:
A () is with needle coke as raw material A;
B () is with native graphite for raw material B;
(c) with Colophonium micropowder for raw material C, particle diameter D50≤5 m;
D () is with graphene conductive agent for raw material D;
E () is with CNT for raw material E;
F raw material A is ground into the granule that particle diameter is 0.5-3mm by (), carry out graphitization at 2800 ~ 3200 DEG C, then carries out thin Pulverizing, grinding particle size D50 is 8 ~ 12 m;
G raw material A fine powder that (f) step is obtained by () and raw material B, by weight A/B=100/(30 ~ 100) ratio carry out uniformly Mixing, fusion;
H material and raw material C, the by weight ratio of (A+B)/C=100/2 ~ 10 that (g) step is obtained by () mix, mixing After at 1200 ~ 1500 DEG C, carry out carbonization;
(i) by raw material D and raw material E by weight D/E=100/(50 ~ 200) ratio carry out air-flow mixing;
J material that (h) step is obtained by () and the material that (i) step obtains, by weight (A+B+C)/(D+E)=100/(1 ~ 3) Ratio uniformly mix, screening, finally obtain product.
2. a kind of high-capacity lithium-ion artificial plumbago negative pole material production method as claimed in claim 1, it is characterised in that: institute Stating raw material A is petroleum needle coke or coal-based needle Jiao.
3. a kind of high-capacity lithium-ion artificial plumbago negative pole material production method as claimed in claim 1, it is characterised in that: institute Stating raw material B is asphalt or coal tar pitch.
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Cited By (8)

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CN106876709A (en) * 2017-02-22 2017-06-20 江西紫宸科技有限公司 A kind of preparation method of high magnification carbon negative pole material
CN107293697A (en) * 2017-07-26 2017-10-24 大连宏光锂业股份有限公司 A kind of power-type lithium ion battery negative material production method
CN108383116A (en) * 2018-02-11 2018-08-10 珠海光宇电池有限公司 Artificial plumbago negative pole material and preparation method thereof and negative electrode of lithium ion battery
CN109860524A (en) * 2017-11-30 2019-06-07 宝武炭材料科技有限公司 A kind of method of solid asphalt low temperature cladding preparation negative electrode material
CN113422025A (en) * 2021-06-25 2021-09-21 洛阳月星新能源科技有限公司 Natural graphite composite material and preparation method thereof
CN113912046A (en) * 2021-09-30 2022-01-11 赣州市康达新能源材料有限公司 Preparation method of artificial graphene super conductive agent
CN114824233A (en) * 2022-05-31 2022-07-29 深圳市翔丰华科技股份有限公司 Preparation method of high-energy-density quick-charging graphite negative electrode material of lithium battery
CN116283292A (en) * 2021-12-21 2023-06-23 湖南中科星城石墨有限公司 Quick-charge graphite negative electrode material, preparation method thereof and lithium ion battery

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