CN103545521A - Graphite-based carbon negative composite material in special shell structure and preparation method thereof - Google Patents
Graphite-based carbon negative composite material in special shell structure and preparation method thereof Download PDFInfo
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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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- 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 belongs to the technical field of chemical power source materials and in particular relates to a graphite-based carbon negative composite material in a special shell structure and a preparation method and application thereof. The graphite-based carbon negative composite material is prepared by carrying out microporous treatment, impregnation, vapor deposition and pyrolytic carbon coating on graphite, and particularly is in a graphite/carbon nanotube or carbon fiber/metal/pyrolytic carbon core/shell structure. The material has the advantages that carbon nanotubes or carbon fibers grow in situ and are pinned between graphite and amorphous pyrolytic carbon shell layers; meanwhile, the coating rate of carbon on the surface of the graphite can reach 100% by virtue of a special pyrolytic carbon source, so that the electrical conductivity and the stability of a composite material core-shell structure are increased, and then the high-ratio charge and discharge properties and the cycling performance of the material are increased. The modified graphite material in the special shell structure is stable in structure, high in capacity and good in multiplying power and cycling performance and can be used as a negative material of small lithium ion batteries and large-current charging and discharging lithium ion power batteries.
Description
Technical field
The invention belongs to chemical power source material technology field, relate to a kind of phosphorus/carbon composite negative electrode material of lithium ion battery and preparation method thereof, a shell structurre natural graphite base negative material particularly, is specially preparation and the application thereof of carbon composite of the core // shell structure of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON.
Background technology
At present, along with global non-renewable energy resources resource is petered out, energy supply and demand contradiction is becoming increasingly acute, and countries in the world ubiquity multi-form energy crisis,, thus the exploitation of new forms of energy are become to one of focus of people's concern.Meanwhile, the problems such as the environmental pollution causing in particularly exploitation of fossil energy resources process of the energy and ecological disruption are increasingly outstanding, and the Global climate change that energy source emission causes has proposed challenge to the mankind's existence and Economic Development Mode.For this reason, encouragement taps a new source of energy becomes the energy strategy emphasis of numerous countries with new-energy automobile.Electrokinetic cell is new-energy automobile " heart ", and battery material is the core of supporting motive force battery.Therefore, the key technology of new-energy automobile is still the exploitation of new energy materials.In all kinds of electrokinetic cells, power lithium-ion battery is to become most potential new-energy automobile power source with its excellent performance and resource.Active development cheapness and high performance power lithium ion battery electrode material have important social and economic significance.Negative material is the critical material of power lithium-ion battery.Find new technique, produce high power capacity, high power, long circulation life and negative material is of far-reaching significance cheaply.
What current commercial lithium ion battery negative material mainly adopted is native graphite and Delanium.Wherein, Delanium production cost is high, capacity is on the low side.The large high rate performance of native graphite is not good enough, but aboundresources, cheap, degree of crystallinity is high, after deep processing, discharge platform is more steady, and structural stability is good, can meet its requirement.Present stage, generally by graphite negative electrodes material being carried out to the modified methods such as surface oxidation, carbon coated and surface deposition layer of metal or metal oxide, improve its capacity and high rate performance.Wherein, graphite type material is carried out to the reversible capacity that surface oxidation treatment has improved graphite to a certain extent, but the high-rate performance of graphite after modification is not done to further research; The fragmentation after being coated of traditional organic resin class or Polymer-pyrolysis carbon source coated graphite based composites, is difficult to prepare coated intact core-shell material, thereby causes material surface stability not good; And due to the Volumetric expansion of metal alloy, after graphite surface plated metal or metal oxide, the charge/discharge capacity under large electric current is still lower.This project is by designing and prepare a kind of special shell structurre, core // shell carbon compound cathode materials of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON, by multicomponent coordinating effect, have complementary advantages, can access high structural stability and high power modified graphite base carbon anode material for power lithium-ion battery, thereby actively push forward further developing of new-energy automobile industry.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of special shell structurre graphite-based carbon composite material.Graphite, by processes such as microporous, dipping, vapour deposition and RESEARCH OF PYROCARBON are coated, is made to the graphite-based carbon composite material with special shell structurre, be specially the core // shell structure of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON.Advantage applies of the present invention exists: by growth in situ CNT (carbon nano-tube) or carbon fiber, be pinned between graphite and amorphous RESEARCH OF PYROCARBON shell, utilize its good electric conductivity and mechanical performance, improve composite material core-shell structural conductive and stability, and then improve material high rate charge-discharge performance and cycle performance; Meanwhile, utilize unique pyrolysis carbon source, make Graphite Coating rate reach 100%.The modified graphite class material of this special shell structurre has high structural stability, high electrochemistry capacitance, high magnification and high cycle performance, can meet the application of small lithium ion secondary batteries and high current charge-discharge lithium ion power cell cathode.
The invention provides a kind of method of preparing the silicon/carbon/graphite in lithium ion batteries base carbon anode material with special shell structurre, material has the core // shell structure of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON.
The method comprises that following step is poly-:
(1) microporous: graphite is slowly added in liquid solution and fully stirred, by liquid-solid reaction, graphite surface is formed after uniform micro-nano micropore, washing, Separation of Solid and Liquid, obtain microporous graphite.
(2) dipping: by early stage graphite after surface micropore be immersed in the salting liquid of metallic catalyst, fully stir and infiltrate, by strict control concentration of salt solution, dipping temperature and time, metallic catalyst ion is fully entered in the middle of the nanometer micropore of graphite, centrifugation is liquid-solid rear dry, obtains the modified graphite of metallic catalyst ion dipping.
(3) vapour deposition: first carry out hydrogen reducing reaction, then micropore graphite surface growth in situ CNT (carbon nano-tube) or the carbon fiber after dipping by vapour deposition process.
(4) surface is coated: the graphite of vapour deposition modification is immersed in the aqueous solution or organic solution of organic carbon source, the modified graphite stir, evaporating solvent obtaining coated with uniform one deck organic carbon, drying, high temperature pyrolysis are at the graphite surface amorphous carbon layer that evenly coated one deck is obtained by organic carbon source pyrolysis.
The present invention's graphite used comprises one or more in natural flake graphite, micro crystal graphite, Delanium and high temperature graphitization material with carbon element (MCMB and CMS).
The present invention's liquid solution used is oxidizing solution, comprises one or more in sulfuric acid and sulfate, persulfate, hydrogen peroxide, nitric acid and nitrate.
One or more in the solution of the soluble-salt that the present invention's metallic catalyst salting liquid used is Fe, Co, Ni.
In the present invention, the needed carbon-source gas of carbon nano-tube or carbon fibre growth is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas.
It is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile that the present invention selects organic carbon source; Selecting solvent is one or more in water, ethanol, acetone, carbon disulfide, oxolane.
Special shell structurre graphite-based carbon anode material prepared by the present invention has good electrochemistry capacitance and high rate charge-discharge performance, the battery core made from this material, under 0.2C multiplying power, discharge and recharge, reversible capacity is higher than 360 mAh/g, coulombic efficiency is higher than 93% first, and the capability retention that circulates after 100 times is higher than 92%; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 340 and 320 mAh/g, and coulombic efficiency is higher than 85% first, and the capability retention after 100 times that circulates, higher than 85%, is the high performance lithium ionic cell cathode material that has very much application prospect.
Embodiment
In the method for the special shell structurre graphite-based carbon composite negative pole material the present invention relates to, step (1) relates to the microporous technique of graphite surface, and this step provides sufficient uniform micro-nano hole and passage for follow-up impregnation technology.In this step, graphite used comprises one or more in natural flake graphite, micro crystal graphite, Delanium and high temperature graphitization material with carbon element (MCMB and CMS); The weight ratio of material with carbon element and liquid solution is 0.2-8; Liquid solution is oxidizing solution, comprises one or more in sulfuric acid and sulfate, persulfate, hydrogen peroxide, nitric acid and nitrate, and solution concentration is 0.05-3mol/L.This step reaction temperature and time is respectively 0-80 ℃, 0.5-10hr.Step (2) relates to microporous graphite impregnation technique, and the metal ion that floods infiltration into microporous in this step is the catalyst precursor in follow-up vapour deposition process.One or more in the soluble-salt that in this step, metallic catalyst salting liquid used is Fe, Co, Ni, concentration is 0.05-1mol/L; Dipping temperature and time are respectively 0-80 ℃, 0.5-10hr.Step (3) relates to gas-phase deposition, and micropore graphite surface growth in situ CNT (carbon nano-tube) or carbon fiber after dipping, utilize its pinning effect, and nano-sized carbon is taken root in graphite surface micropore evenly, securely.In this step, first utilize hydrogen reducing reaction to obtain one or more in metallic catalyst Fe, Co, Ni, its flow velocity is 1-1000 ml/min, and the time is 0.5-5 hour; The needed carbon-source gas of carbon nano-tube or carbon fibre growth is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas, and its flow velocity is 1-1000 ml/min; Depositing temperature is 500-1200 ℃, and the time is 0.1-5hr; Diluent gas is all high pure nitrogen.Step (4) relates to surface cladding tech, and the graphite surface after CNT (carbon nano-tube) or carbon fiber pinning is evenly coated one deck pyrolysis amorphous carbon again.In this step, selecting organic carbon source is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile, and mass percent is 3-15%; Selecting solvent is one or more in water, ethanol, acetone, carbon disulfide, oxolane; Soaking and stirring 0.5-6 hour, evaporate to dryness temperature are 50-120 ℃, and pyrolysis temperature is 700-1200 ℃, and the time is 2-10hr.
Embodiment 1:
It is in the hydrogen peroxide solution of 0.5M that natural flake graphite is slowly added to 200ml concentration, the weight ratio of graphite and liquid solution is 4, at 40 ℃, stir 5 hours, through Separation of Solid and Liquid, after cyclic washing, in concentration, be in 0.6M iron nitrate solution, 40 ℃ flood 5 hours, to carry out Separation of Solid and Liquid again, product after vacuumize is placed in tube furnace, the first hydrogen 3 hours of logical 600 ml/min, then in the acetylene air-flow of 600 ml/min, at 800 ℃, be deposited as 3 hours, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, it is in 8% aqueous sucrose solution that the graphite of vapour deposition nano-sized carbon is immersed in to mass percent, stir after 3 hours, at 70 ℃, stir evaporate to dryness, at 800 ℃ of high temperature pyrolysis, after 5 hours, obtain core/shell structure carbon anode material.
Using preparation material as negative pole, then take lithium sheet as to electrode, U.S. Celgard 2400 is barrier film, take 1.0 mol.L-1 LiPF6/EC+DMC[V (EC): V (DMC)=1: 1] be electrolyte, in being full of the stainless steel glove box of argon gas, be assembled into button cell.On Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, carry out constant current constant voltage charge-discharge test, discharge-rate is respectively 0.1-3C, and charging/discharging voltage scope is 0.005～3 V.Under 0.2C multiplying power, discharge and recharge, reversible capacity is 367 mAh/g, and coulombic efficiency is 92% first, and capability retention 94% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 350 and 336 mAh/g, and coulombic efficiency is higher than 89% first, and the capability retention that circulates after 100 times is higher than 86%.
Embodiment 2:
It is in the ammonium persulfate solution of 0.4M that natural micro crystal graphite is slowly added to 200ml concentration, the weight ratio of graphite and liquid solution is 6, at 40 ℃, stir 4 hours, through Separation of Solid and Liquid, after cyclic washing, in concentration, be in 0.4M cobalt nitrate solution, 40 ℃ flood 5 hours, to carry out Separation of Solid and Liquid again, product after vacuumize is placed in tube furnace, the first hydrogen 3 hours of logical 600 ml/min, then in the liquefied petroleum entraining air stream of 600 ml/min, at 750 ℃, be deposited as 3 hours, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, it is in 8% phenolic resins organic solution that the graphite of vapour deposition nano-sized carbon is immersed in to mass percent, stir after 3 hours, at 70 ℃, stir evaporate to dryness, at 800 ℃ of high temperature pyrolysis, after 5 hours, obtain core/shell structure carbon anode material.
With the test of identical electrochemical method, obtain, under 0.2C multiplying power, discharge and recharge, reversible capacity is 354mAh/g, and coulombic efficiency is 91% first, and capability retention 93% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 340 and 323 mAh/g, and coulombic efficiency is higher than 85% first, and the capability retention that circulates after 100 times is higher than 84%.
Embodiment 3:
It is in the ammonium persulfate solution of 0.5M that MCMB is slowly added to 200ml concentration, the weight ratio of graphite and liquid solution is 3, at 40 ℃, stir 5 hours, through Separation of Solid and Liquid, after cyclic washing, in concentration, be in 0.4M nickel nitrate solution, 40 ℃ flood 5 hours, to carry out Separation of Solid and Liquid again, product after vacuumize is placed in tube furnace, the first hydrogen 3 hours of logical 600 ml/min, then in the methane gas stream of 600 ml/min, at 750 ℃, be deposited as 3 hours, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, it is in 10% D/W that the graphite of vapour deposition nano-sized carbon is immersed in to mass percent, stir after 3 hours, at 70 ℃, stir evaporate to dryness, at 800 ℃ of high temperature pyrolysis, after 5 hours, obtain core/shell structure carbon anode material.
With the test of identical electrochemical method, obtain, under 0.2C multiplying power, discharge and recharge, reversible capacity is 328mAh/g, and coulombic efficiency is 95% first, and capability retention 96% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 322 and 313 mAh/g, and coulombic efficiency is higher than 92% first, and the capability retention that circulates after 100 times is higher than 93%.
Embodiment 4:
It is in the potassium peroxydisulfate and hydrogen peroxide solution of 0.5M that natural flake graphite is slowly added to 200ml concentration, the weight ratio of graphite and liquid solution is 2, at 50 ℃, stir 5 hours, through Separation of Solid and Liquid, after cyclic washing, in concentration, be in 0.8M nickel nitrate solution, 50 ℃ flood 5 hours, to carry out Separation of Solid and Liquid again, product after vacuumize is placed in tube furnace, the first hydrogen 2 hours of logical 900 ml/min, then in the acetylene air-flow of 900 ml/min, at 750 ℃, be deposited as 3 hours, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, the graphite of vapour deposition nano-sized carbon is immersed in the ethanol and water mixed solution that mass percent is 12% glucose, stir after 3 hours, at 60 ℃ of vacuum stirring evaporates to dryness, at 750 ℃ of high temperature pyrolysis, after 10 hours, obtain core/shell structure carbon anode material.
With the test of identical electrochemical method, obtain, under 0.2C multiplying power, discharge and recharge, reversible capacity is 366mAh/g, and coulombic efficiency is 95% first, and capability retention 95% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 358 and 349 mAh/g, and coulombic efficiency is higher than 90% first, and the capability retention that circulates after 100 times is higher than 95%.
Embodiment 5:
It is in the cerous sulfate solution of 1M that natural flake graphite is slowly added to 200ml concentration, the weight ratio of graphite and liquid solution is 2, at 50 ℃, stir 3 hours, through Separation of Solid and Liquid, after cyclic washing, in concentration, be in 0.5M nickel nitrate solution, 50 ℃ flood 5 hours, to carry out Separation of Solid and Liquid again, product after vacuumize is placed in tube furnace, the first hydrogen 3 hours of logical 800 ml/min, then in the acetylene air-flow of 800 ml/min, at 760 ℃, be deposited as 5 hours, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, it is in 10% polyvinyl chloride organic solution that the graphite of vapour deposition nano-sized carbon is immersed in to mass percent, stir after 5 hours, at 70 ℃, stir evaporate to dryness, at 760 ℃ of high temperature pyrolysis, after 6 hours, obtain core/shell structure carbon anode material.
With the test of identical electrochemical method, obtain, under 0.2C multiplying power, discharge and recharge, reversible capacity is 356mAh/g, and coulombic efficiency is 95% first, and capability retention 96% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is respectively higher than 348 and 332 mAh/g, and coulombic efficiency is higher than 86% first, and the capability retention that circulates after 100 times is higher than 92%.
Claims (6)
1. the preparation method of the graphite-based carbon anode material of a special shell structurre, it is characterized in that: by growth in situ CNT (carbon nano-tube) or carbon fiber, be pinned between graphite and amorphous carbon, form high conductivity and high structural stability, there is the carbon anode material of the core // shell structure of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON.This preparation method's concrete steps are:
(1) microporous: it is in the liquid solution of 0.05-3M that graphite is slowly added to concentration, and the weight ratio of graphite and liquid solution is 0.2-8, stirs after 0.5-10 hour Separation of Solid and Liquid, cyclic washing at 0-80 ℃.
(2) dipping: it is in 0.05-1M salting liquid that surface micropore fossil China ink is immersed in to concentration, and dipping temperature is 0-80 ℃, and the time is 0.5-10 hour, through Separation of Solid and Liquid, vacuumize.
(3) vapour deposition: the hydrogen 0.5-5 hour that first leads to 1-1000 ml/min, carry out reduction reaction, then at flow velocity, be in the carbon-source gas of 1-1000 ml/min, at 500-1200 ℃, be deposited as 0.1-5 hour, constant temperature growth in situ CNT (carbon nano-tube) or carbon fiber, diluent gas is all high pure nitrogen.
(4) surface is coated: the graphite of vapour deposition nano-sized carbon is immersed in the organic carbon source solution that mass percent is 3-15%, stir 0.5-6 hour, at 50-120 ℃, continue to stir after evaporating solvent again, at 700-1200 ℃ of high temperature pyrolysis 2-10 hour, must there is the carbon anode material of the core // shell structure of graphite // CNT (carbon nano-tube) or carbon fiber/metal/RESEARCH OF PYROCARBON.
2. according to preparation method claimed in claim 1, the described graphite of step (1) comprises one or more in natural flake graphite, micro crystal graphite, Delanium and high temperature graphitization material with carbon element (MCMB and CMS).
3. according to preparation method claimed in claim 1, the described liquid solution of step (1) is oxidizing solution, comprises one or more in sulfuric acid and sulfate, persulfate, hydrogen peroxide, nitric acid and nitrate.
4. according to preparation method claimed in claim 1, the described salting liquid of step (2) is metallic catalyst salting liquid, comprises one or more in the soluble-salt of Fe, Co, Ni.
5. according to preparation method claimed in claim 1, the described carbon-source gas of step (3) is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas.
6. according to preparation method claimed in claim 1, the described organic carbon source of step (4) is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile; Selecting solvent is one or more in water, ethanol, acetone, carbon disulfide, oxolane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105070916A (en) * | 2015-09-08 | 2015-11-18 | 湖南星城石墨科技股份有限公司 | Preparation method of highly compacted carbon-coated natural graphite material |
| CN105642917A (en) * | 2016-03-15 | 2016-06-08 | 苏州赛福德备贸易有限公司 | Preparation method for metal-clad carbon nano tube |
| WO2017206299A1 (en) * | 2016-06-03 | 2017-12-07 | 田东 | Method for preparing modified graphite cathode material for lithium-ion batteries |
| WO2020199354A1 (en) * | 2019-04-04 | 2020-10-08 | 碳翁(北京)科技有限公司 | High-temperature-resistant electrothermal fiber and application thereof |
| CN112234197A (en) * | 2020-09-08 | 2021-01-15 | 中南大学 | Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof |
| CN114094097A (en) * | 2020-08-24 | 2022-02-25 | 洛阳月星新能源科技有限公司 | Preparation method of long-life high-power graphite composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105070916A (en) * | 2015-09-08 | 2015-11-18 | 湖南星城石墨科技股份有限公司 | Preparation method of highly compacted carbon-coated natural graphite material |
| CN105070916B (en) * | 2015-09-08 | 2017-11-21 | 湖南中科星城石墨有限公司 | A kind of preparation method of high-pressure solid carbon coating natural graphite material |
| CN105642917A (en) * | 2016-03-15 | 2016-06-08 | 苏州赛福德备贸易有限公司 | Preparation method for metal-clad carbon nano tube |
| WO2017206299A1 (en) * | 2016-06-03 | 2017-12-07 | 田东 | Method for preparing modified graphite cathode material for lithium-ion batteries |
| WO2020199354A1 (en) * | 2019-04-04 | 2020-10-08 | 碳翁(北京)科技有限公司 | High-temperature-resistant electrothermal fiber and application thereof |
| CN114094097A (en) * | 2020-08-24 | 2022-02-25 | 洛阳月星新能源科技有限公司 | Preparation method of long-life high-power graphite composite material |
| CN112234197A (en) * | 2020-09-08 | 2021-01-15 | 中南大学 | Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof |
| CN114481370A (en) * | 2022-02-25 | 2022-05-13 | 山东大学 | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140129 |