CN107887581A - Porous graphene coated graphite, preparation and the application on lithium ion battery - Google Patents

Porous graphene coated graphite, preparation and the application on lithium ion battery Download PDF

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Publication number
CN107887581A
CN107887581A CN201711038173.2A CN201711038173A CN107887581A CN 107887581 A CN107887581 A CN 107887581A CN 201711038173 A CN201711038173 A CN 201711038173A CN 107887581 A CN107887581 A CN 107887581A
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porous graphene
graphene
composite material
preparation
nano composite
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Inventor
张小廷
刘程程
马贺然
曹炬
马锐
商北雁
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BEIJING WANYUAN INDUSTRY CO LTD
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BEIJING WANYUAN INDUSTRY 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
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • 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
    • H01M4/58Selection 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
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Abstract

The present invention relates to field of nanocomposite materials, discloses a kind of porous graphene coated graphite nano composite material, preparation method and its application as lithium ion battery negative material.Porous graphene is coated on the surface of graphite in the composite.When for lithium ion battery negative material, high capacity, good high rate performance and cyclical stability are shown.The composite material and preparation method thereof is simple, and raw material resources used is abundant, cost is relatively low, and preparation technology is simple, is easy to mass produce.

Description

Porous graphene coated graphite, preparation and the application on lithium ion battery
Technical field
The invention belongs to nano composite material technical field, and in particular to a kind of porous graphene coated graphite composite wood Material, preparation method and its application as lithium ion battery negative material.
Background technology
At present, commercialized negative material is mainly graphite material, but because its Capacity Ratio is relatively low, and be not suitable for Fast charging and discharging, become the main reason for restricting lithium ion battery development.Therefore, development is with higher capacity, more preferable multiplying power Performance, low cost, long-life and safe and reliable novel anode material are very urgent.
The method of modifying of traditional negative material mainly includes coating modification, oxidation modification, doping vario-property and surface deposition Metal or metal oxide.Oxidizing process advantage is can to use the air of low cost, but it has the shortcomings that one very big Exactly oxidation can only occur in the particle surface that air contact arrives, therefore prepared material is it is difficult to ensure that its homogeneity.Doping Some hetero atoms that modification can be introduced outside carbon atom, coulombic efficiency reduction first can be caused.Surface deposited metal or gold Although category oxide can improve the cycle performance of electrode, metal ion can greatly be broken in the test process of full battery The overall performance of bad battery.Coating modification is the unformed charcoal " shell " of one layer of Surface coating in graphite, forms " core-shell structure copolymer " knot Structure, the shortcomings that can effectively avoiding graphite carbon material.It is possible, firstly, to reduce the irreversible capacity of graphite material;Secondly, can To improve the electrolyte adaptability of graphite material so that it can be used in the electrolyte that PC is solvent;Finally, can improve The cyclical stability of graphite material.Therefore, compared with other method of modifying, coating modification is considered as a kind of simple and had The method of effect.
Traditional cladding presoma mainly includes macromolecule and pitch, Jiao such as phenolic resin, epoxy resin, polyvinyl alcohol The byproduct of the coals such as charcoal or oil.But the clad formed is generally thicker, it is difficult to strict control.Graphene is due to tool There are high electrical conductivity, big ratio surface and excellent mechanical performance, be expected to the negative material as lithium ion battery.Porous stone On the one hand black alkene has the intrinsic very good mechanical properties of common graphite alkene and electric conductivity, on the other hand lacked containing many extra Fall into, therefore receive much concern.Special loose structure promotes electrolyte when alloing it as lithium ion battery negative material Infiltration, shorten the diffusion length of lithium ion, so as to improve chemical property.But graphene can not individually be used as lithium ion again The negative material of battery, this does not have obvious platform mainly due to it, it is impossible to have a stable voltage output, and cost compared with It is high.Accordingly, it is desirable to provide porous graphene coated graphite composite, preparation method and its conduct of a kind of advantages with reference to both The application of lithium ion battery negative material.
The content of the invention
It is an object of the invention to for existing graphite electrode specific capacity it is relatively low the problem of, there is provided a kind of porous graphene Coated graphite, preparation method and its application as lithium ion battery negative material.
Technical scheme is as follows:
A kind of porous graphene coated graphite nano composite material, including porous graphene and graphite, described porous stone Black alkene is coated on the surface of graphite.
A kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 1, its feature It is in turn include the following steps:
Step 1. prepares graphene dispersing solution, is 1 by the mass ratio of graphene and metal salt:100~1:0.01 to graphite Metal salt is added in alkene dispersion liquid and obtains mixed solution;
Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, be ultrasonically treated 0 minute to 1 hour, Then through magnetic stirrer 1-24 hours, then graphene metal salt mixture is obtained after freezing;By obtained graphene gold Category salt mixture is placed in inert atmosphere, is in 100-1000 DEG C of progress charing process, the sample after being carbonized, reaction time 0 minute to 10 hours;Then the sample after charing being handled with acid solution again, the concentration of hydrochloric acid is 0.01-10mol/L, Processing time is 30 minutes to 8 hours;It is lyophilized to obtain porous graphene powder after neutrality is washed with deionized again;
Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01 Solid phase mixing;Mixed material is placed in inert atmosphere again, charing process, reaction time 0 are carried out at 100-1000 DEG C Minute was by 10 hours, you can obtains porous graphene coated graphite nano composite material.
The mass ratio of graphene and metal salt is 1 in step 1:10~1:0.1.
Graphene oxide, redox graphene or the machinery stripping that graphene described in step 1 is prepared for chemical method The graphene prepared from method.
Metal salt described in step 1 is transition metal sulfate, transition metal nitrate, transition metal chloride or mistake Cross metal acetate.
The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal Nitrate is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride is iron chloride, chlorination Cobalt, nickel chloride, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or second Sour manganese.
The methods of solid phase mixing method described in step 3 can use grinding or ball milling.
Porous graphene powder and graphite quality ratio are 1 in step 3:10~1:0.1.
The porous graphene coated graphite nano composite material being prepared is as lithium ion battery negative material.
A kind of lithium ion battery, the porous graphene coated graphite nanometer that negative material employs described in claim 1 are answered Condensation material.
The beneficial effects of the present invention are:
1. the porous graphene coated graphite nano composite material prepared by the present invention mainly has following characteristics:(1) it is porous The loose structure of graphene can shorten the diffusion path of lithium ion, there is provided more storage lithium avtive spots;(2) porous graphene Graphite surface is coated on, therefore can effectively improve the cycle performance of graphite.
2. preparation technology provided by the invention, which need to only pass through simple mixing and carbonization process, can obtain porous graphene Coated graphite electrode material.Raw material resources used in the present invention enriches, cost is relatively low, and preparation technology is simple, is easy to advise greatly The production of mould.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the porous graphene coated graphite nano composite material of the present invention;
Fig. 2 is the cycle performance curve of the porous graphene coated graphite nano composite material of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to the present invention.
Embodiment 1
Present embodiments provide a kind of porous graphene coated graphite nano composite material, including porous graphene and stone Ink, described porous graphene are coated on the surface of graphite.Described graphite can be native graphite or Delanium.
The present embodiment additionally provides a kind of preparation method of above-mentioned porous graphene coated graphite nano composite material, successively Comprise the following steps:
Graphene powder is added to the water by step 1. is prepared into graphene dispersing solution, by graphene and the mass ratio of metal salt For 1:100~1:0.01 adds metal salt into graphene dispersing solution obtains mixed solution.The mass ratio of graphene and metal salt Preferably 1:10~1:0.1.
Described graphene is prepared by graphene oxide, redox graphene or mechanical stripping method prepared by chemical method Graphene.
Described metal salt is transition metal sulfate, transition metal nitrate, transition metal chloride or transition metal Acetate.The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal nitre Hydrochlorate is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride be iron chloride, cobalt chloride, Nickel chloride, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or acetic acid Manganese.
Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, be ultrasonically treated 0 minute to 1 hour, Then through magnetic stirrer 1-24 hours, reuse after freeze dryer freezes and obtain graphene metal salt mixture;
Obtained graphene metal salt mixture is placed in inert atmosphere, charing process is carried out at 100-1000 DEG C, obtains Sample after to charing, reaction time are 0 minute to 10 hours;
Then the sample after charing is handled with hydrochloric acid again, the concentration of hydrochloric acid is 0.01-10M, processing time 30 Minute was by 8 hours;
After neutrality is washed with deionized again, porous graphene powder is obtained after lyophilized;
Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01 Solid phase mixing;Mixed material is placed in inert atmosphere again, charing process, reaction time 0 are carried out at 100-1000 DEG C Minute was by 10 hours, you can obtains porous graphene coated graphite nano composite material.Described solid phase mixing method can adopt The methods of with grinding or ball milling.Porous graphene powder and graphite quality ratio preferably 1:10~1:0.1.
The present embodiment additionally provides a kind of lithium ion battery, and its negative material employs above-mentioned porous graphene coated graphite Nano composite material.
Compared with prior art, the technical scheme of the present embodiment has advantages below:
1. the porous graphene coated graphite nano composite material prepared by the present invention mainly has following characteristics:(1) it is porous The loose structure of graphene can shorten the diffusion path of lithium ion, there is provided more storage lithium avtive spots;(2) porous graphene Graphite surface is coated on, therefore can effectively improve the cycle performance of graphite.
2. preparation technology provided by the invention, which need to only pass through simple mixing and carbonization process, can obtain porous graphene Coated graphite electrode material.Raw material resources used in the present invention enriches, cost is relatively low, and preparation technology is simple, is easy to advise greatly The production of mould.
Embodiment 2
It is 1 in mass ratio:1 adds 1g ferric nitrates into 1g graphene oxide solutions forms mixed solution.Then put Ultrasound 30 minutes in ultrasonic machine, stirred on magnetic stirring apparatus 10 hours, graphene is obtained after then being freezed using freeze dryer Metal salt mixture, the graphene metal salt mixture after freezing are placed in inert atmosphere, and charing process are carried out at 800 DEG C, Reaction time is 3 hours, processing 2 hours is then carried out to the sample after charing with 0.1M hydrochloric acid again, then be washed with deionized water It is lyophilized to can obtain porous graphene powder after washing neutrality.Then it is according to mass ratio with graphite by porous graphene powder 1:10 solid phase mixings, mixed material is placed in inert atmosphere, carries out charing process 1h at 1000 DEG C, you can obtain porous Graphene coated graphite nanometer composite material.As the scanning electron microscope analysis of accompanying drawing 1 show prepared porous graphene bag Cover the surface that porous graphene in graphite nanometer composite material is coated on graphite.As the electrochemical property test result of accompanying drawing 2 shows, The composite material is under 0.5C current densities after 90 circulations, and capacity is still up to 353mAh/g.
Embodiment 3
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:5, maintain it Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations Afterwards, capacity is still up to 362mAh/g.
Embodiment 4
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:4, maintain it Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations Afterwards, capacity is still up to 367mAh/g.
Embodiment 5
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:3, maintain it Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations Afterwards, capacity is still up to 373mAh/g.
Embodiment 6
Porous graphene preparation method is changed to 1 with embodiment 2, porous graphene powder with graphite quality ratio:2, maintain it Its condition is constant.Electrochemical property test result shows that the composite material is under 0.5C current densities by 100 circulations Afterwards, capacity is still up to 381mAh/g.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention God and scope.It is if these modifications and variations belong within the scope of the claims in the present invention and its equivalent technologies, then of the invention It is also intended to comprising including these changes and modification.

Claims (10)

  1. A kind of 1. porous graphene coated graphite nano composite material, it is characterised in that:It is described including porous graphene and graphite Porous graphene be coated on the surface of graphite.
  2. 2. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 1, its feature exist In in turn including the following steps:
    Step 1. prepares graphene dispersing solution, is 1 by the mass ratio of graphene and metal salt:100~1:0.01 divides to graphene Metal salt is added in dispersion liquid and obtains mixed solution;
    Then mixed solution that step 2. obtains step 1, which is placed in ultrasonic machine, carries out supersound process 0 minute to 1 hour, then Through magnetic stirrer 1-24 hours, then graphene metal salt mixture is obtained after freezing;
    Obtained graphene metal salt mixture is placed in inert atmosphere, charing process is carried out at 100-1000 DEG C, obtains charcoal Sample after change, reaction time are 0 minute to 10 hours;
    Then the sample after charing is handled with acid solution again, the concentration of hydrochloric acid is 0.01-10mol/L, and processing time is 30 minutes to 8 hours;
    It is lyophilized to obtain porous graphene powder after neutrality is washed with deionized again;
    Then porous graphene powder that step 3. obtains step 2 is 1 according to mass ratio with graphite:100~1:0.01 solid phase Mixing;Mixed material is placed in inert atmosphere again, charing process is carried out at 100-1000 DEG C, the reaction time is 0 minute By 10 hours, you can obtain porous graphene coated graphite nano composite material.
  3. 3. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2, its feature exist In:The mass ratio of graphene and metal salt is 1 in the step 1:10~1:0.1.
  4. 4. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Graphene described in step 1 is graphene oxide, redox graphene or mechanical stripping method prepared by chemical method The graphene of preparation.
  5. 5. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Metal salt described in step 1 is transition metal sulfate, transition metal nitrate, transition metal chloride or transition Metal acetate.
  6. 6. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 5, its feature exist In:The transition metal sulfate is ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate or manganese sulfate;The transition metal nitrate For ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate or manganese nitrate;The transition metal chloride is iron chloride, cobalt chloride, chlorination Nickel, copper chloride or manganese chloride;The transition metal acetate is ferric acetate, cobalt acetate, nickel acetate, copper acetate or manganese acetate.
  7. 7. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:The methods of solid phase mixing method described in step 3 can use grinding or ball milling.
  8. 8. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:Porous graphene powder and graphite quality ratio are 1 in step 3:10~1:0.1.
  9. 9. a kind of preparation method of porous graphene coated graphite nano composite material as claimed in claim 2 or claim 3, its feature It is:The porous graphene coated graphite nano composite material being prepared is as lithium ion battery negative material.
  10. A kind of 10. lithium ion battery, it is characterised in that:Negative material employs the porous graphene cladding described in claim 1 Graphite nanometer composite material.
CN201711038173.2A 2017-10-30 2017-10-30 Porous graphene coated graphite, preparation and the application on lithium ion battery Pending CN107887581A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109411723A (en) * 2018-10-16 2019-03-01 上海应用技术大学 A kind of preparation method of graphene/graphite lithium ion battery negative electrode material
CN109585821A (en) * 2018-11-23 2019-04-05 四川大学 Graphite composite material, preparation method, application and negative electrode of lithium ion battery
CN110085820A (en) * 2019-04-17 2019-08-02 中国航发北京航空材料研究院 A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary
CN110112384A (en) * 2019-04-17 2019-08-09 中国航发北京航空材料研究院 A kind of preparation method of porous graphene silicium cathode material
CN110627034A (en) * 2019-07-31 2019-12-31 宁波中车新能源科技有限公司 Preparation method of dual-functional energy-storage porous carbon-coated graphite composite material
CN111807353A (en) * 2020-07-17 2020-10-23 北京石墨烯研究院 Porous graphene and preparation method and application thereof
CN113161545A (en) * 2021-05-18 2021-07-23 芜湖天弋能源科技有限公司 Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material
CN113871590A (en) * 2021-09-16 2021-12-31 广东凯金新能源科技股份有限公司 Layered porous graphite negative electrode material and preparation method thereof
CN114373897A (en) * 2020-10-14 2022-04-19 山东欧铂新材料有限公司 Porous graphene/artificial graphite composite material, preparation method thereof and lithium ion battery
CN114477155A (en) * 2020-10-27 2022-05-13 中国科学院大连化学物理研究所 Porous graphene/lamellar graphene composite material and preparation method and application thereof
JP7466677B2 (en) 2020-03-13 2024-04-12 エルジー エナジー ソリューション リミテッド Anode active material, its manufacturing method, and lithium secondary battery including said anode active material

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CN109411723A (en) * 2018-10-16 2019-03-01 上海应用技术大学 A kind of preparation method of graphene/graphite lithium ion battery negative electrode material
CN109411723B (en) * 2018-10-16 2022-07-15 上海应用技术大学 Preparation method of graphene/graphite lithium ion battery negative electrode material
CN109585821A (en) * 2018-11-23 2019-04-05 四川大学 Graphite composite material, preparation method, application and negative electrode of lithium ion battery
CN110085820A (en) * 2019-04-17 2019-08-02 中国航发北京航空材料研究院 A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary
CN110112384A (en) * 2019-04-17 2019-08-09 中国航发北京航空材料研究院 A kind of preparation method of porous graphene silicium cathode material
CN110627034A (en) * 2019-07-31 2019-12-31 宁波中车新能源科技有限公司 Preparation method of dual-functional energy-storage porous carbon-coated graphite composite material
JP7466677B2 (en) 2020-03-13 2024-04-12 エルジー エナジー ソリューション リミテッド Anode active material, its manufacturing method, and lithium secondary battery including said anode active material
CN111807353A (en) * 2020-07-17 2020-10-23 北京石墨烯研究院 Porous graphene and preparation method and application thereof
CN114373897A (en) * 2020-10-14 2022-04-19 山东欧铂新材料有限公司 Porous graphene/artificial graphite composite material, preparation method thereof and lithium ion battery
CN114477155A (en) * 2020-10-27 2022-05-13 中国科学院大连化学物理研究所 Porous graphene/lamellar graphene composite material and preparation method and application thereof
CN114477155B (en) * 2020-10-27 2023-11-10 中国科学院大连化学物理研究所 Porous graphene/lamellar graphene composite material and preparation method and application thereof
CN113161545B (en) * 2021-05-18 2022-06-24 芜湖天弋能源科技有限公司 Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material
CN113161545A (en) * 2021-05-18 2021-07-23 芜湖天弋能源科技有限公司 Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material
CN113871590A (en) * 2021-09-16 2021-12-31 广东凯金新能源科技股份有限公司 Layered porous graphite negative electrode material and preparation method thereof

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