CN104934603A - Preparation method of graphene-dopedand carbon-coated modified graphite anode material - Google Patents
Preparation method of graphene-dopedand carbon-coated modified graphite anode material Download PDFInfo
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- CN104934603A CN104934603A CN201510266358.3A CN201510266358A CN104934603A CN 104934603 A CN104934603 A CN 104934603A CN 201510266358 A CN201510266358 A CN 201510266358A CN 104934603 A CN104934603 A CN 104934603A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of graphene-doped and carbon-coated modified graphite anode material. The doping and modification of the graphene to graphite could solve the problem that high-rate performance of the graphite is relative bad. Because the graphene is used as an electronic transmission buffer layer in a graphite composite material, the cycle performance of the graphite composite material is improved. In addition, the introduction of the graphene could effectively restrain the gather of graphite particles in a heat treatment process, and simultaneously, the Li-ion diffusion coefficient in the graphene-doped graphite composite material is increased. The graphene prepared according to the invention has higher specific surface area, and therefore, the high-rate performance of the graphite could be further improved.
Description
Technical field
The present invention relates to lithium ion battery negative material, be specifically related to the preparation method of the doping of a kind of Graphene and coated modified carbon graphite cathode material.
Background technology
Along with the development of automobile industry, the exhaustion of the non-renewable fossil fuel such as oil, natural gas receives publicity day by day, and air pollution and room temperature effect also become global problem.For solving energy problem, realize low-carbon environment-friendly, based on the development level of current energy technology, electric vehicle engineering becomes the emphasis direction of global economic development gradually, the countries such as the U.S., Japan, Germany, China in succession limit fuel vehicle and use, and greatly develop electric motor car.As the core component of electric automobile---electrokinetic cell has also welcome large good opportunity to develop.Electrokinetic cell refers to the battery being applied to electric motor car, comprise lithium ion battery, lead-acid battery, fuel cell etc., wherein, specific energy is high, specific power is large, self discharge is few because having for lithium ion battery, long service life and the advantage such as fail safe is good, has become the emphasis of current various countries development.
And as the graphite type material of lithium ion battery negative material, there is lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, be more satisfactory lithium ion battery negative material.But it also exists first, and discharging efficiency is low, cycle performance is poor, to shortcomings such as electrolyte selectivity are high, make graphite material application be restricted.In order to solve the above-mentioned shortcoming of graphite material, people carry out modification by various method to graphite, and the method usually adopted at present is carbon cladding process.Yang Ruizhi etc. are at " resin carbon coated graphite is as the research of lithium ion battery negative electrode " (" Journal of Inorganic Materials ", 2000,15(4): 712-718) with liquid-phase impregnation process at natural flake graphite Surface coating phenolic resins, use constant current charge and discharge, powder microelectrode cyclic voltammetry has investigated charging-discharging performances.Experimental result shows, through heat treated phenolic resins carbon coated graphite material to put a capacity higher, cycle life is longer, can be used as the negative material of high performance lithium ion battery.He Ming etc. are at " preparation of resin carbon-coated graphite and chemical property thereof " (" battery ", 2003, at natural micro crystal graphite particle surface coated one deck resin carbon 3(5): 281-284), coated process can reduce the irreversible capacity first of natural micro crystal graphite, adopt and first mix the method coated graphite then disperseed, inside is natural micro crystal graphite, and outside is the phenolic resins pyrolysis carbon-coating of 1 ~ 2 μm.The irreversible capacity that lithium ion experimental cell records natural micro crystal graphite is 14%, and the irreversible capacity of coated graphite is 7%.Coated process can reduce the irreversible capacity of natural micro crystal graphite to a great extent.Chen Meng etc. are at " the preparation and property research of pitch-coating native graphite " (" battery industry ", 2007,12(5): 298-302) adopt liquid phase coating method, be coated on natural spherical plumbago, to improve its cycle performance by pitch cracking carbon.Experimental result shows, native graphite is after pitch-coating, irreversible capacity loss has reduced to 32.5mAh/g from 125.5mAh/g, specific capacity has brought up to 365.3mAh/g from 290.8mAh/g, capability retention after 50 circulations has brought up to 93.66% from 55.4%, effectively improves the cycle performance of native graphite.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the doping of a kind of Graphene and coated modified carbon graphite cathode material, be intended to solve the problems such as graphite high-rate charge-discharge capability difference and anti-electrolyte organic solvent poor compatibility, improve the cycle performance of battery charging and discharging.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of Graphene doping and the preparation method of coated modified carbon graphite cathode material, is characterized in that comprising the following steps:
(1) Graphene is dissolved in solvent, is made into the graphene solution that concentration is 1 ~ 12 mg/mL;
(2) under agitation, graphite is mixed in graphene solution, simultaneously in graphite weight 5 ~ 20% ratio add a certain amount of carbon matrix precursor, obtain the collosol and gel of Graphene and graphite and carbon matrix precursor, after mixing, dry except desolventizing under 60 ~ 80 DEG C of conditions, obtain powder;
(3) under inert gas shielding; step (2) gained powder is heated to 700 ~ 950 DEG C; continue 1 ~ 5 hour, namely obtain Graphene doping and coated modified carbon graphite cathode material, Graphene doping is 1 ~ 5 wt.% with the mass percent of Graphene in coated graphite composite material.
The preparation process of described Graphene is as follows: the graphene oxide water solution of preparation 0.5 ~ 6 mg/mL, graphene oxide water solution is poured in stainless steel cauldron, stainless steel cauldron sealing is placed in air dry oven, react 10 ~ 24 hours under 100 ~ 200 DEG C of conditions, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution to dry, it is fully dry that the powder obtained is placed in vacuum drying chamber, namely obtain Graphene, the specific surface of grapheme material is at 1800 ~ 2400m
2/ g.
Described graphite is Delanium or native graphite, particle diameter D50 between 5 ~ 25 μm, specific area≤6m
2/ g, tap density>=0.7g/cm
3.
Described Graphene: the mass ratio of graphite is (0.02 ~ 0.1): 1.
Described solvent is water, methyl alcohol or ethanol.
Described carbon matrix precursor is one or more the mixture in sodium cellulose glycolate, polyvinyl alcohol, phenolic resins, epoxy resin, glucose, starch, pitch.
Described inert gas is nitrogen or argon gas.
Compared with prior art, the invention has the advantages that the doping of the Graphene of super large surface area and the coated conductivity that improve graphite, obtained Graphene doping is high with coated graphite composite negative pole material specific capacity, and good cycle, can be widely used in various lithium ion battery.Meanwhile, preparation method of the present invention is with low cost, and technique is simple, is suitable for large-scale industrial production.
Graphene can solve the poor problem of the high rate capability of graphite to the doping vario-property of graphite.Because Graphene serves the effect of electric transmission resilient coating in graphite composite material, therefore improve the cycle performance of graphite composite material, the introducing of Graphene effectively can suppress the gathering of graphite granule in heat treatment process in addition, and in Graphene doped graphite composite material, lithium ion diffusion coefficient increases simultaneously.Graphene prepared by the present invention has higher specific area, and therefore the high rate capability of graphite will improve further.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
Graphene doping and a preparation method for coated graphite composite negative pole material, comprise the following steps:
(1) graphene oxide water solution of 5mg/mL is prepared, the graphene oxide water solution of 40mL 5mg/mL being poured into 50mL polytetrafluoroethylene is in the stainless steel cauldron of inner bag, stainless steel cauldron sealing is placed in air dry oven, react 20 hours under 180 DEG C of conditions, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution to dry, it is fully dry that the powder obtained is placed in vacuum drying chamber, obtains grapheme material.The specific surface of grapheme material is at 2000m
2/ g;
(2) under agitation, by Graphene: native graphite (D50:10.82 μm, specific area: 6.1m
2/ g, tap density: 0.96g/cm
3) mass ratio be the ratio of 0.05:1, graphite is mixed in graphene solution, add carbon matrix precursor-polyvinyl alcohol in the ratio of graphite weight 5% simultaneously, obtain the collosol and gel of Graphene and graphite and carbon matrix precursor, after mixing, dry except desolventizing under 80 DEG C of conditions, obtain powder;
(3) under inert gas shielding, step (2) gained powder is heated to 950 DEG C, continues 3 hours, namely obtain Graphene doping and coated modified carbon graphite cathode material.
The doping of obtained Graphene and carbon coated graphite negative material and acetylene black and binding agent (PVDF) are added NMP by 96:1.5:2.5 mass ratio mix well, obtained quality is about the electrode slice of 7mg, and dry 24 h at 120 DEG C in a vacuum.Negative pole is made with above-mentioned electrode slice, take metal lithium sheet as positive pole, polypropylene film is barrier film, EC+DEC (the 1:1 of 1 mol/L LiPF6, volume ratio) solution makes electrolyte, in the glove box being full of argon gas, be assembled into button cell, make constant current charge-discharge loop test with 0.2C, testing result is in table 1.
Embodiment 2
Graphene doping and a preparation method for coated graphite composite negative pole material, comprise the following steps:
(1) graphene oxide water solution of 2 mg/mL is prepared, pouring the graphene oxide water solution of 40 mL 2 mg/mL into 50 mL polytetrafluoroethylene is in the stainless steel cauldron of inner bag, sealing is placed in air dry oven and reacts 12 hours under 120 DEG C of conditions, then reactor is naturally cooled to room temperature, with the moisture content in filter paper draw solution to dry, it is fully dry that the powder obtained is placed in vacuum drying chamber, obtains grapheme material.The specific surface of grapheme material is at 2300 m
2/ g;
(2) under agitation, by Graphene: Delanium (D50:17.21 μm, specific area: 5.8m
2/ g, tap density: 0.85g/cm
3) mass ratio be the ratio of 0.1:1, graphite is mixed in graphene solution, add carbon matrix precursor-phenolic resins in the ratio of graphite weight 10% simultaneously, obtain the collosol and gel of Graphene and graphite and carbon matrix precursor, after mixing, dry except desolventizing under 70 DEG C of conditions, obtain powder;
(3) under inert gas shielding, step (2) gained powder is heated to 900 DEG C, continues 3 hours, namely obtain Graphene doping and coated modified carbon graphite cathode material.
Detection method is with embodiment 1, and testing result is in table 1.
Embodiment 3
Graphene doping and a preparation method for coated graphite composite negative pole material, comprise the following steps:
(1) graphene oxide water solution of 8mg/mL is prepared, pouring the graphene oxide water solution of 40 mL 8 mg/mL into 50 mL polytetrafluoroethylene is in the stainless steel cauldron of inner bag, sealing is placed in air dry oven and reacts 16 hours under 150 DEG C of conditions, then reactor is naturally cooled to room temperature, with the moisture content in filter paper draw solution to dry, it is fully dry that the powder obtained is placed in vacuum drying chamber, obtains grapheme material.The specific surface of grapheme material is at 1850 m
2/ g;
(2) under agitation, by Graphene: native graphite (D50:8.14 μm, specific area: 6.9m
2/ g, tap density: 1.04g/cm
3) mass ratio be the ratio of 0.08:1, graphite is mixed in graphene solution, add carbon matrix precursor-polyvinyl alcohol in the ratio of graphite weight 7% simultaneously, obtain the collosol and gel of Graphene and graphite and carbon matrix precursor, after mixing, dry except desolventizing under 75 DEG C of conditions, obtain powder;
(3) under inert gas shielding, step (2) gained powder is heated to 850 DEG C, continues 5 hours, namely obtain Graphene doping and coated modified carbon graphite cathode material.
Detection method is with embodiment 1, and testing result is in table 1.
Comparative example 1
Undressed native graphite in embodiment 1.Detection method is with embodiment 1, and testing result is in table 1
Comparative example 2
Undressed Delanium in embodiment 2.Detection method is with embodiment 1, and testing result is in table 1
Table 1: the testing result in above-mentioned specific embodiment
More than show and describe general principle of the present invention and principal character and advantage of the present invention; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and application claims protection range is defined by appending claims and equivalent thereof.
Claims (6)
1. Graphene doping and a preparation method for coated modified carbon graphite cathode material, is characterized in that adopting following steps:
(1) Graphene is dissolved in solvent, is made into the graphene solution that concentration is 1 ~ 12 mg/mL;
(2) under agitation, graphite is mixed in graphene solution, simultaneously in graphite weight 5 ~ 20% ratio add a certain amount of carbon matrix precursor, obtain the collosol and gel of Graphene and graphite and carbon matrix precursor, after mixing, dry except desolventizing under 60 ~ 80 DEG C of conditions, obtain powder;
(3) under inert gas shielding; step (2) gained powder is heated to 700 ~ 950 DEG C; continue 1 ~ 5 hour, namely obtain Graphene doping and coated modified carbon graphite cathode material, Graphene doping is 1 ~ 5 wt.% with the mass percent of Graphene in coated graphite composite material.
2. according to the preparation method of a kind of Graphene doping described in claim 1 with coated modified carbon graphite cathode material, it is characterized in that the preparation process of described Graphene is as follows: the graphene oxide water solution of preparation 0.5-6 mg/mL, graphene oxide water solution is poured in stainless steel cauldron, stainless steel cauldron sealing is placed in air dry oven, 10-24 hour is reacted under 100-200 DEG C of condition, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution to dry, it is fully dry that the powder obtained is placed in vacuum drying chamber, namely Graphene is obtained, the specific surface of Graphene is at 1800-2400 m
2/ g.
3., according to a kind of Graphene doping described in claim 1 and the preparation method of coated modified carbon graphite cathode material, it is characterized in that the graphite described in step (2) is Delanium or native graphite, particle diameter D50 between 5 ~ 25 μm, specific area≤6m
2/ g, tap density>=0.7g/cm
3.
4. according to a kind of Graphene doping described in claim 1 and the preparation method of coated modified carbon graphite cathode material, it is characterized in that the Graphene described in step (2): the mass ratio of graphite is (0.02 ~ 0.1): 1
According to a kind of Graphene doping described in claim 1 and the preparation method of coated modified carbon graphite cathode material, it is characterized in that the solvent described in step (1) is water, methyl alcohol or ethanol.
5., according to the preparation method of a kind of Graphene doping described in claim 1 with coated modified carbon graphite cathode material, the carbon matrix precursor that it is characterized in that described in step (2) is one or more the mixture in sodium cellulose glycolate, polyvinyl alcohol, phenolic resins, epoxy resin, glucose, starch, pitch.
6., according to a kind of Graphene doping described in claim 1 and the preparation method of coated modified carbon graphite cathode material, it is characterized in that the inert gas described in step (3) is nitrogen or argon gas.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185967A (en) * | 2015-10-12 | 2015-12-23 | 南京工业大学 | High-performance carbon-based negative electrode material of lithium ion battery and preparing method thereof |
| CN105914355A (en) * | 2016-05-27 | 2016-08-31 | 雅安乾润锂电池材料有限公司 | Graphite negative electrode material for lithium ion batteries and preparation method thereof |
| CN106469814A (en) * | 2016-04-14 | 2017-03-01 | 济南圣泉集团股份有限公司 | A kind of covering, negative material, lithium ion battery and preparation method thereof |
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN107507963A (en) * | 2016-06-14 | 2017-12-22 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of graphene coated artificial plumbago negative pole material |
| CN108199011A (en) * | 2017-11-20 | 2018-06-22 | 深圳市斯诺实业发展股份有限公司 | A kind of preparation method of lithium titanate anode material |
| CN108565446A (en) * | 2018-06-11 | 2018-09-21 | 清华大学深圳研究生院 | A kind of preparation method of porous nitrogen-doped carbon coated graphite material |
| WO2018202377A1 (en) * | 2017-05-03 | 2018-11-08 | Arcelik Anonim Sirketi | A battery |
| CN109037643A (en) * | 2018-08-07 | 2018-12-18 | 内蒙古三信实业有限公司 | A kind of high capacity high-pressure solid graphite composite material and preparation method thereof |
| CN109065878A (en) * | 2018-08-15 | 2018-12-21 | 南通百川新材料有限公司 | A kind of preparation method of modified graphene composite graphite negative electrode material |
| CN110148753A (en) * | 2019-05-22 | 2019-08-20 | 佛山科学技术学院 | A kind of Magnesium ion battery baseband processing method and Magnesium ion battery |
| CN111252764A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Modified carbon material for lead-carbon battery, and preparation and application thereof |
| CN112886008A (en) * | 2021-01-19 | 2021-06-01 | 青海凯金新能源材料有限公司 | Carbon-coated graphite negative electrode material and preparation method thereof |
| CN114804094A (en) * | 2022-04-15 | 2022-07-29 | 广东凯金新能源科技股份有限公司 | Nitrogen-graphene doped composite graphite negative electrode material and preparation method thereof |
| CN117446800A (en) * | 2023-12-26 | 2024-01-26 | 深圳市华明胜科技有限公司 | Preparation process of natural graphite negative electrode material by using intercalation shearing |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185967A (en) * | 2015-10-12 | 2015-12-23 | 南京工业大学 | High-performance carbon-based negative electrode material of lithium ion battery and preparing method thereof |
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN106941151B (en) * | 2016-01-05 | 2019-07-12 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN106469814A (en) * | 2016-04-14 | 2017-03-01 | 济南圣泉集团股份有限公司 | A kind of covering, negative material, lithium ion battery and preparation method thereof |
| WO2017177970A1 (en) * | 2016-04-14 | 2017-10-19 | 济南圣泉集团股份有限公司 | Coating agent, negative electrode material, lithium ion battery, and preparation method therefor |
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| CN105914355B (en) * | 2016-05-27 | 2019-04-09 | 雅安乾润锂电池材料有限公司 | Lithium ion battery graphite cathode material and preparation method thereof |
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| CN107507963A (en) * | 2016-06-14 | 2017-12-22 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of graphene coated artificial plumbago negative pole material |
| WO2018202377A1 (en) * | 2017-05-03 | 2018-11-08 | Arcelik Anonim Sirketi | A battery |
| CN108199011A (en) * | 2017-11-20 | 2018-06-22 | 深圳市斯诺实业发展股份有限公司 | A kind of preparation method of lithium titanate anode material |
| CN108199011B (en) * | 2017-11-20 | 2021-10-26 | 深圳市斯诺实业发展有限公司 | Preparation method of lithium titanate negative electrode material |
| CN108565446A (en) * | 2018-06-11 | 2018-09-21 | 清华大学深圳研究生院 | A kind of preparation method of porous nitrogen-doped carbon coated graphite material |
| CN109037643A (en) * | 2018-08-07 | 2018-12-18 | 内蒙古三信实业有限公司 | A kind of high capacity high-pressure solid graphite composite material and preparation method thereof |
| CN109037643B (en) * | 2018-08-07 | 2020-10-20 | 内蒙古三信实业有限公司 | High-capacity high-compaction graphite composite material and preparation method thereof |
| CN109065878A (en) * | 2018-08-15 | 2018-12-21 | 南通百川新材料有限公司 | A kind of preparation method of modified graphene composite graphite negative electrode material |
| CN109065878B (en) * | 2018-08-15 | 2021-10-26 | 南通百川新材料有限公司 | Preparation method of modified graphene composite graphite negative electrode material |
| CN111252764B (en) * | 2018-11-30 | 2023-04-07 | 中国科学院大连化学物理研究所 | Modified carbon material for lead-carbon battery, and preparation and application thereof |
| CN111252764A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Modified carbon material for lead-carbon battery, and preparation and application thereof |
| CN110148753A (en) * | 2019-05-22 | 2019-08-20 | 佛山科学技术学院 | A kind of Magnesium ion battery baseband processing method and Magnesium ion battery |
| CN112886008A (en) * | 2021-01-19 | 2021-06-01 | 青海凯金新能源材料有限公司 | Carbon-coated graphite negative electrode material and preparation method thereof |
| CN114804094A (en) * | 2022-04-15 | 2022-07-29 | 广东凯金新能源科技股份有限公司 | Nitrogen-graphene doped composite graphite negative electrode material and preparation method thereof |
| CN117446800A (en) * | 2023-12-26 | 2024-01-26 | 深圳市华明胜科技有限公司 | Preparation process of natural graphite negative electrode material by using intercalation shearing |
| CN117446800B (en) * | 2023-12-26 | 2024-03-12 | 深圳市华明胜科技有限公司 | Preparation process of natural graphite negative electrode material by using intercalation shearing |
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Application publication date: 20150923 |