CN104466133A - Nitrogen-doped graphene carbon composite material and preparation method thereof - Google Patents
Nitrogen-doped graphene carbon composite material and preparation method thereof Download PDFInfo
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- CN104466133A CN104466133A CN201410719551.3A CN201410719551A CN104466133A CN 104466133 A CN104466133 A CN 104466133A CN 201410719551 A CN201410719551 A CN 201410719551A CN 104466133 A CN104466133 A CN 104466133A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a nitrogen-doped graphene carbon composite material and a preparation method thereof. The composite material comprises nitrogen-doped graphene and a nitrogen-doped carbon material covering the periphery of the nitrogen-doped graphene. The preparation method comprises the following steps: dissolving carbohydrate into graphene oxide dispersion liquid to ensure that carbohydrate uniformly covers the graphene oxide to form a graphene oxide/carbohydrate complex; coating the surface of the graphene oxide/carbohydrate complex by a polymer to form a graphene oxide/carbohydrate/polymer complex; nitriding the graphene oxide/carbohydrate/polymer complex in a high-temperature environment at the temperature of more than 700 DEG C to form the nitrogen-doped graphene carbon composite material. The composite material is high in specific surface area, less in aggregates, high in dispersibility and high in conductivity; the preparation is simple and feasible in process, low in energy consumption, high in yield and suitable for scale industrial production; moreover, freeze drying operation is eliminated.
Description
Technical field
The present invention relates to a kind of conductive carbon material, particularly a kind of graphene carbon composite material of N doping, belongs to material science.
Background technology
The two-dimentional monolayer structure of Graphene due to its uniqueness and the physical property (high theoretical specific surface area, high conductivity, high-mechanical property etc.) of excellence, be with a wide range of applications in lithium ion battery and electrode material for super capacitor.For obtaining the graphene-based material with better electric property, industry have studied kinds of schemes, such as, a kind of mode wherein utilizes the method for physical mixed to prepare graphene composite material to improve its electric property, and the more feasible mode of another kind is chemical modification method, such as in grapheme material, introduce other element by doping etc., particularly N element and improve its electric property, because atom N has the atomic radius approximate with C atom, and can as electron donor, the nitrogen-doped graphene generated after adulterating with Graphene shows higher electric conductivity.
The method of at present carrying out N doping for Graphene mainly contains chemical vapour deposition (CVD) (CVD) method, plasma processing, arc discharge method, high energy electrothermal way, template etc.But because all easily reuniting between the sheet of Graphene class material, particularly nitrogen-doped graphene and sheet, cause its electric property to reduce, the nitrogen-doped graphene adopting cryodesiccated method to prepare bigger serface so general, but Freeze Drying Technique yields poorly, energy consumption is high, is not suitable for suitability for industrialized production.
Summary of the invention
In view of the deficiencies in the prior art, main purpose of the present invention is the graphene carbon composite material providing a kind of N doping, and it is large that it has specific area, the advantages such as decentralization is high, electric property is excellent.
Another object of the present invention is to provide a kind of method preparing the graphene carbon composite material of described N doping, the method is simple to operation, and energy consumption is low, and output is high, is suitable for large-scale industrial and produces.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
A kind of graphene carbon composite material of N doping, comprise nitrogen-doped graphene and be coated on the nitrogen-doped carbon material around nitrogen-doped graphene, and the thickness of described nitrogen-doped carbon material is 2-10 nm, the diameter of described composite material is 2-20 μm, thickness is 5-20 nm, and conductivity is 100-200 S/cm
2, specific area is 200-300 m
2/ g.
Wherein, material with carbon element is unformed form.
Further, the nitrogen content in the graphene carbon composite material of described N doping is 2-15mol%.
A kind of preparation method of graphene carbon composite material of N doping comprises:
Can more than 700 DEG C, preferably at the temperature of 700-900 DEG C, the carbohydrate of carbonization is dissolved in graphene oxide dispersion, and makes the even coated graphene oxide of described carbohydrate, forms graphene oxide/carbohydrate compound;
Can the polymer of carbonization at the temperature of 700-900 DEG C at described graphene oxide/carbohydrate compound surface parcel, form graphene oxide/carbohydrate/polymer complex,
And, by the nitrogenize in the hot environment of 700-900 DEG C of described graphene oxide/carbohydrate/polymer complex, form the graphene carbon composite material of described N doping.
As one of comparatively preferred embodiment, the preparation method of the graphene carbon composite material of described N doping comprises the steps:
(1) fully mix in the aqueous solution described carbohydrate being dissolved in graphene oxide, make the even coated graphene oxide of described carbohydrate and form graphene oxide/carbohydrate compound, more described graphene oxide/carbohydrate compound is isolated from the aqueous solution;
(2) described graphene oxide/carbohydrate compound is scattered in water, and add the monomer of described polymer, after abundant mixing, add acidic materials and catalyst, the monomer polymerization of described polymer is made to form polymer, and make described polymer uniform wrap up described graphene oxide/carbohydrate compound, form graphene oxide/carbohydrate/polymer complex, again described graphene oxide/carbohydrate/polymer complex is isolated from reactant mixture, and wash, dry;
(3) described graphene oxide/carbohydrate/polymer complex is placed in nitrogen containing atmosphere, nitrogenize under the temperature conditions more than 700 DEG C, forms the graphene carbon composite material of described N doping.
Further, abovementioned steps (1) comprising: be fully uniformly mixed in the aqueous solution described carbohydrate being dissolved in graphene oxide, add ammoniacal liquor again, continue to stir more than 2h at 80-95 DEG C, then add CTAB to continue to stir, then leach precipitum, washing, vacuumize, obtain described graphene oxide/carbohydrate compound.
Further, abovementioned steps (3) comprising: described graphene oxide/carbohydrate/polymer complex is placed in inert atmosphere, and pass into ammonia, 700-900 DEG C is warming up to the heating rate of 10-30 DEG C/min, and nitrogenize under this temperature conditions, form the graphene carbon composite material of described N doping.
Further, described carbohydrate can be selected from but be not limited to glucose, fructose or sucrose.
Further, described polymer is preferably from polypyrrole.
Further, abovementioned steps (2) comprising: be scattered in water by described graphene oxide/carbohydrate compound, and add the monomer of described polymer, after abundant mixing, add acidic materials (such as hydrochloric acid, but be not limited thereto), regulate the pH value of mixture system to 1-2, be beneficial to subsequent polymerisation reaction.
Further, described catalyst comprises persulfate, such as ammonium persulfate.
Such as, in a comparatively typical case study on implementation, a kind of preparation method of graphene carbon composite material of N doping comprises: the glucose of 1-25g is joined in the graphene oxide water solution of 1000ml that (concentration is 0.2-5 mg mL
-1), stir 30 minutes, rotating speed 100-300 rev/min.Then add the ammonia spirit (25-28%) of 1-25ml, at 95 DEG C, continue stirring 2 hours.Then the CTAB(hexadecyltrimethylammonium bromide of 20-500mg is added, softex kw), stir after ten minutes and filter, washing.60 DEG C of dryings 12 hours, obtain graphene oxide/glucose mixture under vacuo.Get ultrasonic 30 minutes of the graphene oxide/glucose mixture of 100mg, power 100W, be dispersed in 100 ml water, add the pyrroles of 0.1 ml, stir 30 minutes, add the concentrated hydrochloric acid solution of 0.1 ml, more ultrasonic 5 minutes, then the aqueous solution of the ammonium persulfate (1 mmol) of 5ml is added, 0 DEG C of reaction 2 hours.Then product is filtered, washing, vacuumize.Product, under the atmosphere of argon gas, passes into ammonia, and 700 DEG C of ammonifications 30 minutes, heating rate is 30 DEG C/min.
The present invention does not need to use freeze drying just can prepare and reunites less, the graphene/carbon material of the N doping that surface area is large, its principle is: graphene oxide is good dispersion in aqueous, use carbohydrate in aqueous, such as glucose is coated by surface of graphene oxide uniformly, settled down preferably by CTAB etc. again, convenient filtration or centrifugation, subsequently again at graphene oxide/carbohydrate Surface coating one layer of polymeric, such as polypyrrole, during high-temperature ammonolysis graphene oxide/glucose/polypyrrole compound, glucose and polypyrrole etc. can produce gas, oxygen Graphene is stoped to be reunited, and under nitrogen effect, form the graphene/carbon composite material of N doping.
Compared with prior art, advantage of the present invention comprises: the graphene carbon composite material specific area of this N doping is large, reunites few, favorable dispersibility; conductivity is high, and its preparation is simple, operate without the need to freeze drying; energy consumption is low, and output is high, is suitable for large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 be embodiment 1 obtain the carbon pipe/carbon fiber complex carbon material of hierarchy SEM figure;
Fig. 2 be embodiment 2 obtain the carbon pipe/carbon fiber complex carbon material of hierarchy SEM figure;
Fig. 3 be embodiment 3 obtain the carbon pipe/carbon fiber complex carbon material of hierarchy SEM figure;
Fig. 4 be embodiment 1 obtain the carbon pipe/carbon fiber complex carbon material of hierarchy XPS test collection of illustrative plates.
Embodiment
Below in conjunction with some embodiments and accompanying drawing, technical scheme of the present invention is further described.
embodiment 1the glucose of 1g joins in the graphene oxide water solution of 1000ml that (concentration is 0.2 mg mL
-1), stir 30 minutes, rotating speed 100-300 rev/min.Then add the ammonia spirit (25-28%) of 1ml, at 95 DEG C, continue stirring 2 hours.Then add the CTAB of 20mg, stir after ten minutes and filter, washing.60 DEG C of dryings 12 hours, obtain graphene oxide/glucose mixture under vacuo.Get ultrasonic 30 minutes of the graphene oxide/glucose mixture of 100mg, power 100W, be dispersed in 100 ml water, add the pyrroles of 0.1 ml, stir 30 minutes, add the concentrated hydrochloric acid solution of 0.1 ml, more ultrasonic 5 minutes, then the aqueous solution of the ammonium persulfate (1 mmol) of 5ml is added, 0 DEG C of reaction 2 hours.Then product is filtered, washing, freeze drying.Product, under the atmosphere of argon gas, passes into ammonia, and 700 DEG C of ammonifications 30 minutes, heating rate is 30 DEG C/min.As shown in Figure 1, to pattern material with carbon element be coated on around nitrogen-doped graphene, thickness about 5 nm, conductivity 200 S/cm
2, surface area is 300 m
2/ g.Fig. 4 is the XPS test of composite material, can find out that nitrogen mixes in compound.
embodiment 2the glucose of 25g joins in the graphene oxide water solution of 1000ml that (concentration is 5 mg mL
-1), stir 30 minutes, rotating speed 100-300 rev/min.Then add the ammonia spirit (25-28%) of 25ml, at 95 DEG C, continue stirring 2 hours.Then add the CTAB of 500mg, stir after ten minutes and filter, washing.60 DEG C of dryings 12 hours, obtain graphene oxide/glucose mixture under vacuo.Get ultrasonic 30 minutes of the graphene oxide/glucose mixture of 100mg, power 100W, be dispersed in 100 ml water, add the pyrroles of 0.1 ml, stir 30 minutes, add the concentrated hydrochloric acid solution of 0.1 ml, more ultrasonic 5 minutes, then the aqueous solution of the ammonium persulfate (1 mmol) of 5ml is added, 0 DEG C of reaction 2 hours.Then product is filtered, washing, freeze drying.Product, under the atmosphere of argon gas, passes into ammonia, and 750 DEG C of ammonifications 30 minutes, heating rate is 30 DEG C/min.As shown in Figure 2, to pattern material with carbon element be coated on around nitrogen-doped graphene, and thickness is 10 nm, conductivity 160 S/cm
2, surface area is 250 m
2/ g.
embodiment 3the glucose of 10g joins in the graphene oxide water solution of 1000ml that (concentration is 2 mg mL
-1), stir 30 minutes, rotating speed 100-300 rev/min.Then add the ammonia spirit (25-28%) of 10 ml, at 95 DEG C, continue stirring 2 hours.Then add the CTAB of 200mg, stir after ten minutes and filter, washing.60 DEG C of dryings 12 hours, obtain graphene oxide/glucose mixture under vacuo.Get ultrasonic 30 minutes of the graphene oxide/glucose mixture of 100mg, power 100W, be dispersed in 100 ml water, add the pyrroles of 0.1 ml, stir 30 minutes, add the concentrated hydrochloric acid solution of 0.1 ml, more ultrasonic 5 minutes, then the aqueous solution of the ammonium persulfate (1 mmol) of 5ml is added, 0 DEG C of reaction 2 hours.Then product is filtered, washing, freeze drying.Product, under the atmosphere of argon gas, passes into ammonia, and 750 DEG C of ammonifications 30 minutes, heating rate is 30 DEG C/min.As shown in Figure 3, to pattern material with carbon element be coated on around nitrogen-doped graphene, and thickness is 20 nm, conductivity 120 S/cm
2, surface area is 200 m
2/ g.
It should be pointed out that the above the specific embodiment of the present invention, do not form limiting the scope of the present invention.Any various other done by technical conceive of the present invention change and distortion accordingly, all should be included in the protection range of the claims in the present invention.
Claims (10)
1. the graphene carbon composite material of a N doping, it is characterized in that described composite material comprises nitrogen-doped graphene and is coated on the nitrogen-doped carbon material around nitrogen-doped graphene, and the thickness of described nitrogen-doped carbon material is 2-10 nm, the diameter of described composite material is 2-20 μm, thickness is 5-20 nm, and conductivity is 100-200 S/cm
2, specific area is 200-300 m
2/ g.
2. the preparation method of the graphene carbon composite material of N doping described in claim 1, is characterized in that comprising:
Can more than 700 DEG C at temperature the carbohydrate of carbonization be dissolved in graphene oxide dispersion, and make the even coated graphene oxide of described carbohydrate, form graphene oxide/carbohydrate compound;
Can the polymer of carbonization at the temperature of 700-900 DEG C at described graphene oxide/carbohydrate compound surface parcel, form graphene oxide/carbohydrate/polymer complex,
And, by the nitrogenize in the hot environment of 700-900 DEG C of described graphene oxide/carbohydrate/polymer complex, form the graphene carbon composite material of described N doping.
3. the preparation method of the graphene carbon composite material of N doping according to claim 2, is characterized in that comprising the steps:
(1) fully mix in the aqueous solution described carbohydrate being dissolved in graphene oxide, make the even coated graphene oxide of described carbohydrate and form graphene oxide/carbohydrate compound, more described graphene oxide/carbohydrate compound is isolated from the aqueous solution;
(2) described graphene oxide/carbohydrate compound is scattered in water, and add the monomer of described polymer, after abundant mixing, add acidic materials and catalyst, the monomer polymerization of described polymer is made to form polymer, and make described polymer uniform wrap up described graphene oxide/carbohydrate compound, form graphene oxide/carbohydrate/polymer complex, again described graphene oxide/carbohydrate/polymer complex is isolated from reactant mixture, and wash, dry;
(3) described graphene oxide/carbohydrate/polymer complex is placed in nitrogen containing atmosphere, nitrogenize under the temperature conditions more than 700 DEG C, forms the graphene carbon composite material of described N doping.
4. the preparation method of the graphene carbon composite material of N doping according to claim 3, it is characterized in that step (1) comprising: be fully uniformly mixed in the aqueous solution described carbohydrate being dissolved in graphene oxide, add ammoniacal liquor again, continue to stir more than 2h at 80-95 DEG C, then add CTAB to continue to stir, then leach precipitum, washing, vacuumize, obtain described graphene oxide/carbohydrate compound.
5. the preparation method of the graphene carbon composite material of N doping according to claim 3, it is characterized in that step (3) comprising: described graphene oxide/carbohydrate/polymer complex is placed in inert atmosphere, and pass into ammonia, 700-900 DEG C is warming up to the heating rate of 10-30 DEG C/min, and nitrogenize under this temperature conditions, form the graphene carbon composite material of described N doping.
6. the preparation method of the graphene carbon composite material of N doping according to any one of claim 2-4, is characterized in that described carbohydrate comprises glucose, fructose or sucrose.
7. the preparation method of the graphene carbon composite material of N doping according to any one of claim 2-4, is characterized in that described polymer comprises polypyrrole.
8. the preparation method of the graphene carbon composite material of N doping according to claim 3, it is characterized in that step (2) comprising: be scattered in water by described graphene oxide/carbohydrate compound, and add the monomer of described polymer, after abundant mixing, add acidic materials, regulate the pH value of mixture system to 1-2.
9. the preparation method of the graphene carbon composite material of N doping according to any one of claim 3-4,8, is characterized in that described acidic materials comprise hydrochloric acid.
10. the preparation method of the graphene carbon composite material of N doping according to any one of claim 3-4, it is characterized in that described catalyst comprises persulfate, described persulfate comprises ammonium persulfate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328904A (en) * | 2016-10-26 | 2017-01-11 | 北京光科博冶科技有限责任公司 | High-specific-capacity nitrogen doped graphene nickel-cobalt lithium manganate composite material and preparation method thereof |
| CN106711457A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nitrogen-enriched carbon shell cladded nano core-shell-structure carbonaceous carrier as well as preparation method and application thereof |
| CN108735999A (en) * | 2018-05-29 | 2018-11-02 | 上海应用技术大学 | A kind of preparation method and applications of the graphene-based N doping carbon-coating composite material of three-dimensional structure |
| CN110526231A (en) * | 2019-09-05 | 2019-12-03 | 黑龙江省科学院高技术研究院 | A kind of preparation method of nitrogen-doped carbon fiber cladding class graphene interlayer composite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN103626151A (en) * | 2013-11-28 | 2014-03-12 | 复旦大学 | Preparation method of graphene/carbon composite material |
| CN103723716A (en) * | 2013-12-23 | 2014-04-16 | 北京化工大学 | Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof |
| CN103896254A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN103979532A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Nitrogen-doped graphene sheet and preparation method and application thereof |
-
2014
- 2014-12-02 CN CN201410719551.3A patent/CN104466133B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN103896254A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN103626151A (en) * | 2013-11-28 | 2014-03-12 | 复旦大学 | Preparation method of graphene/carbon composite material |
| CN103723716A (en) * | 2013-12-23 | 2014-04-16 | 北京化工大学 | Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof |
| CN103979532A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Nitrogen-doped graphene sheet and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711457A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nitrogen-enriched carbon shell cladded nano core-shell-structure carbonaceous carrier as well as preparation method and application thereof |
| CN106711457B (en) * | 2015-11-13 | 2019-08-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano-core-shell structure carbonaceous carrier, its preparation method and the application of rich nitrogen carbon shell cladding |
| CN106328904A (en) * | 2016-10-26 | 2017-01-11 | 北京光科博冶科技有限责任公司 | High-specific-capacity nitrogen doped graphene nickel-cobalt lithium manganate composite material and preparation method thereof |
| CN108735999A (en) * | 2018-05-29 | 2018-11-02 | 上海应用技术大学 | A kind of preparation method and applications of the graphene-based N doping carbon-coating composite material of three-dimensional structure |
| CN110526231A (en) * | 2019-09-05 | 2019-12-03 | 黑龙江省科学院高技术研究院 | A kind of preparation method of nitrogen-doped carbon fiber cladding class graphene interlayer composite |
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