CN106986332B - A kind of preparation method of the highly conductive graphene film of flexibility - Google Patents
A kind of preparation method of the highly conductive graphene film of flexibility Download PDFInfo
- Publication number
- CN106986332B CN106986332B CN201710310070.0A CN201710310070A CN106986332B CN 106986332 B CN106986332 B CN 106986332B CN 201710310070 A CN201710310070 A CN 201710310070A CN 106986332 B CN106986332 B CN 106986332B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- sponge
- graphene film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of preparation method of the highly conductive graphene film of flexibility, belongs to graphene film field.The invention solves existing graphene sponge, there are sizes by equipment limit, the technical problem of flexible difference in practical application.Graphene oxide dispersion: one, being freezed 10h~for 24 hours by the method for the present invention under the conditions of -50 DEG C~-20 DEG C, is then freeze-dried 72h~100h, is obtained graphene oxide sponge；Two, graphene oxide sponge is restored with hydrazine hydrate steam；Three, it then with inert gas to protect gas, is heat-treated；Four, pressurized treatments obtain graphene film.The method of the present invention simple process is low in cost, and high production efficiency, controllability are good, can prepare large scale sample, can satisfy the needs of different engineerings, solves the status that previous big size graphene sponge is restricted by experimental facilities；And the present invention has prepared while having had graphene film flexible, that electric conductivity is high, compactness is high.
Description
Technical field
The invention belongs to graphene film fields；More particularly to a kind of preparation method of highly conductive graphene film of flexibility.
Background technique
Graphene only has one layer of carbon atom, and tightly packed at bi-dimensional cellular shape lattice structure, each carbon atom and phase
Three adjacent carbon atoms form covalent bond.Each carbon atom has a s track and three p tracks in graphene, wherein s track
Three carbon atoms adjacent with surrounding with two p tracks form chemical bond, do not contribute the conductivity of graphene, and remaining
The one mutual hydridization of p track forms valence band and conduction band, affects the electric property of graphene.This unique two-dimensional structure makes
Graphene has excellent mechanics, electricity and heat performance.Transmission of the free electron on graphene is not susceptible to scatter, electronics
Mobility can achieve 2 × 105Cm/Vs is more than 100 times of electron mobility in silicon；Its conductivity is up to 106S/m, is
Excellent conductive material at room temperature.Graphene elasticity modulus is up to 1TPa, breaking strength 125GPa, and room temperature thermal conductivity is 5.3
× 103W/mK, specific surface area 2630m2/g.Graphene also has excellent optical property, the visible light of single-layer graphene
Absorptivity is only 2.3%.This two-dimensional graphene film is also shown excellent other than with high conductivity and transmitance
Chemical stability and thermal stability, can be used as the substitute of solar energy transparent electrode.Graphene is in composite material, catalysis material
The fields such as material, energy storage material, Gao Gongneng nanometer electronic device, gas sensor have sizable application value, also attract numerous
Graphene is deeply systematically studied in scholar's expansion.
In order to apply these excellent properties, extensive synthesizing graphite alkene is needed, and single-layer graphene is assembled into macro
See structure.The method for preparing graphene at present includes simple mechanical stripping graphite crystal, metal surface epitaxial growth, chemistry stripping
Powdered graphite is removed from graphene oxide or liquid phase ultrasound.Wherein, the method for chemical stripping graphene oxide is because of process letter
It is single, it is easy large-scale production, is widely used in assembling graphene macrostructure.Graphene uniform is dispersed in matrix material
Material is a kind of important research direction for playing graphene excellent properties in metal, macromolecule, inorganic material.However, because
Graphene big L/D ratio, the presence of strong π-π, graphene are difficult to be uniformly dispersed in polymeric matrix material between each other.
Tsinghua University Miao Zhang etc. utilizes improved Hummers legal system under the conditions of relatively low oxidizing temperature
Standby graphene oxide sheet, later in aqueous solution by its stable dispersion, it is closed later in a reservoir, 70 DEG C of thermal reduction 36h
Uniform graphene oxide hydrogel is formed, prepares graphene oxide film using the dry method of casting, conductivity can reach
To 802 ± 29S/cm.Its material shows good flexibility Fig. 1 and shows that it prepares the flexibility of material.
The flexible highly conductive graphene film of preparation at present is a difficult point, and it is thin to prepare graphene using the dry method of casting
Film, although flexible, compactness is poor, influences electric conductivity.This patent proposes to cause using graphene sponge preparation for the first time
Close highly conductive fexible film.
Summary of the invention
The invention solves existing graphene fexible film preparation methods, and there are preparation process complexity, and uniformity is poor, material
Expect that conductivity is low, compactness is low, flexible poor problem；Provide a kind of highly conductive fine and close stone of the new flexibility based on graphene sponge
The preparation method of black alkene film.Graphene oxide is assembled into three-dimensional porous structure by the present invention --- and graphene oxide sponge is led to
It crosses electronation to be heat-treated later, the graphene film of flexible highly conductive densification is prepared in finally pressurization；To solve
Graphene film has the problem of flexibility, compactness, high conductivity simultaneously.A kind of highly conductive graphene film of flexibility in the present invention
Preparation method carry out in the steps below:
Step 1: graphene oxide dispersion to be freezed to 10h~for 24 hours under the conditions of -50 DEG C~-20 DEG C, then freezing is dry
Dry 72h~100h obtains graphene oxide sponge (brown color)；
Step 2: to the reduction of graphene oxide sponge, (Dark grey, density are 6~22mg/cm with hydrazine hydrate steam3)；
Step 3: then with inert gas be protection gas, carried out under the conditions of 1000 DEG C~5000 DEG C heat treatment 0.5h~
2h (thickness 1mm~10mm, 0.01~0.08g/cm of density-3)；
Step 4: being then 10~400Pa in vacuum degree, pressure carries out pressurized treatments under the conditions of being 30Mpa~500Mpa,
It keeps pressure 1min, obtains graphene film (with a thickness of 20~50 microns).
Graphene oxide described in step 1 is prepared as follows: natural flake graphite is added in nitration mixture,
20min~60min is stirred with 200r/min~700r/min revolving speed, divides 5~8 minor tick 20~30min equivalent to be added later high
Potassium manganate strong oxidizer, then adjusting whipping temp and rate is 35 DEG C~80 DEG C, 200r/min~800r/min, and is placed in water
Constant temperature stirs 5h~18h in bath, is then added in ice water, and the hydrogen peroxide that mass fraction is 30% is added into ice water,
Reaction system color becomes glassy yellow from brownish red, obtains suspension, filters, and centrifuge washing obtains graphene oxide；
Wherein, the mass ratio of the volume of the nitration mixture and natural flake graphite is (10mL~300mL): 1g；Described
The quality of potassium permanganate and the volume ratio of nitration mixture are (8g~100g): 1L；The quality and hydrogen peroxide of the natural flake graphite
Volume ratio be 1g:(2mL~8mL)；
The phosphoric acid that nitration mixture is the sulfuric acid that mass fraction is 15%~98% and mass fraction is 15%~80% according to (3~
7): 1 volume ratio mixes.
The described centrifuge washing processing carries out according to the following steps: using centrifugal separator, and be added deionized water from
The heart rinses 3~7 times, then adds hydrochloric acid solution centrifugal rinsing 3~7 times of 0.1mol/L~1mol/L, is eventually adding ethyl alcohol
Centrifugal rinsing 3~7 times；
Graphene oxide dispersion is by graphene oxide deionized water by (0.3mg~24mg): 1mL in step 1
Made of proportion mixes.
It is freeze-dried under the conditions of -50 DEG C~-10 DEG C in step 1.
It is specifically that 80wt% hydrazine hydrate aqueous solution and graphene oxide sponge are placed in closed drier in step 2,
Drier places hydrazine hydrate solution below, and graphene oxide sponge is placed in top, is heated to 50 DEG C~100 DEG C and is steamed using hydrazine hydrate
Vapour obtains the graphene sponge of Dark grey to graphene oxide sponge reductase 12 h~5h.
Hydrazine reducing agent described in step 2 is hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.
Inert gas described in step 3 is argon gas or nitrogen.
Flexible graphene film metal gloss prepared by the present invention.
The method of the present invention simple process is low in cost, and high production efficiency, controllability are good, can prepare large scale sample, energy
Enough meet the needs of different engineerings, solve the status that previous big size graphene sponge is restricted by experimental facilities；System of the present invention
Standby graphene film is flexible, can arbitrarily bend, and it is flexible poor in graphene sponge practical application to solve the problems, such as.
The stability of the preparation process of the method for the present invention, strong operability can large-scale industrial production.
Graphene oxide is assembled into three-dimensional porous structure by the present invention --- graphene oxide sponge, by electronation it
After be heat-treated, the graphene film of flexible highly conductive densification is prepared in finally pressurization；It is same to solve graphene film
When there is the problem of flexibility, compactness, high conductivity, conductivity can achieve 105S/m。
Detailed description of the invention
Fig. 1 is the Flexible graphene film photo of the preparations such as Tsinghua University Miao Zhang；
Fig. 2 is the graphene sponge prepared；
Fig. 3 is the photo for the Flexible graphene film prepared；
Fig. 4 is the section SEM picture of graphene fexible film.
Specific embodiment
Specific embodiment 1: present embodiment is provided and a kind of is answered using graphene sponge and dimethyl silicone polymer
The method and step that conjunction prepares highly conductive flexible composite is as follows:
One, it prepares graphene oxide: 40g natural flake graphite is added in nitration mixture, stir, condition 500r/min,
40min.Divide 7 every minor tick 20min equivalent that potassium permanganate (time interval 20min) is added later, adjustment whipping temp and
Rate is 35 DEG C, 500r/min, and is placed in constant temperature in water-bath and stirs 5h, and stirring mixture is added in ice water later, and
And the hydrogen peroxide that mass fraction is 30% is added into ice water, suspension is obtained, is finally filtered, centrifuge washing obtains oxygen
Graphite alkene, every milliliter of addition 24mg graphene oxide proportion plus deionized water obtain dispersion liquid.
The quality of the potassium permanganate and the volume ratio of nitration mixture are 6g:1L；The quality of the natural flake graphite with
The volume ratio of hydrogen peroxide is 1g:2mL；
Nitration mixture be 50% by mass fraction sulfuric acid and mass fraction be 50% phosphoric acid by 3:1 volume ratio mixing and
At；
Centrifuge washing processing carries out according to the following steps: using centrifugal separator, and deionized water centrifugal rinsing 5 is added
It is secondary, hydrochloric acid solution centrifugal rinsing 5 times of 0.2mol/L are then added, are eventually adding ethyl alcohol centrifugal rinsing 5 times；
Two, prepare graphene oxide sponge: the graphene oxide dispersion that step 1 is obtained is poured into mold ,-
It is freezed for 24 hours under the conditions of 20 DEG C, then is freeze-dried 72h under the conditions of 30 DEG C and obtains brown color graphene oxide sponge (see Fig. 2), it is thick
Degree is 4mm.
Three, redox graphene sponge: 80wt% hydrazine hydrate aqueous solution redox graphene sponge is utilized, by two kinds
Reactant is placed in drier, and drier places hydrazine hydrate solution below, and top places graphene oxide sponge, is placed in baking oven
In, 90 DEG C are heated to using hydrazine hydrate steam, and reduction 3h is carried out to graphene oxide sponge, the graphene oxide sponge after reduction
Fig. 2 is seen for Dark grey, and obtaining density is 22mg/cm3Graphene sponge.
Four, heat-treated graphite alkene sponge: by the graphene sponge of preparation, protection gas is done in Ar, is carried out under the conditions of 1900 DEG C
It is heat-treated 1h.
Five, pressurization graphite alkene sponge: the graphene sponge that heat treatment terminates is put into mold, later in 300Mpa,
Pressurized treatments are carried out under the conditions of 11Pa, obtain seeing Fig. 3 with a thickness of 50 micron graphite alkene films.
The present embodiment by the thickness of test sample it is observed that the graphene film prepared it is micro- with a thickness of 30
Rice is observed that significant change will not occur for graphene film by the repetitive process that bending is opened, specific as shown in Figure 3.
The Flexible graphene film conductivity of present embodiment preparation is 1.3 × 105S/m。
As shown in Figure 4, under the conditions of 10 microns of scale, gap existing for graphene fexible film section is seldom, performance
Very high compactness extent out.
Specific embodiment 2: a kind of preparation method of the highly conductive graphene film of flexibility is by following in present embodiment
What step carried out:
One, it prepares graphene oxide: 20g natural flake graphite being added in sulfuric acid and phosphoric acid, mixture is made, stirring,
Condition is 500r/min, 40min.Divide 7 every minor tick 20min equivalent that potassium permanganate is added later, adjusts whipping temp and speed
Rate is 35 DEG C, 500r/min, and is placed in constant temperature in water-bath and stirs 5h, and stirring mixture is added in ice water later, and
Into ice water be added mass fraction be 30% hydrogen peroxide, obtain graphene suspension, finally by graphene oxide suspension into
Row filters, and centrifuge washing obtains graphene oxide, is diluted 12mg/ml using deionized water.
The quality of the potassium permanganate and the volume ratio of nitration mixture are 6g:1L；The quality of the natural flake graphite with
The volume ratio of hydrogen peroxide is 1g:2mL；
Nitration mixture be 50% by mass fraction sulfuric acid and mass fraction be 50% phosphoric acid by 3:1 volume ratio mixing and
At；
Centrifuge washing processing carries out according to the following steps: using centrifugal separator, and deionized water centrifugal rinsing 5 is added
It is secondary, hydrochloric acid solution centrifugal rinsing 5 times of 0.2mol/L are then added, are eventually adding ethyl alcohol centrifugal rinsing 5 times；
Two, it prepares graphene oxide sponge: obtained graphene oxide dispersion is poured into mold, in -20 DEG C of items
It is freezed for 24 hours under part, then is freeze-dried 72h under the conditions of -30 DEG C and obtains brown color with a thickness of the graphene oxide sponge of 4mm.
Three, redox graphene sponge: 80wt% hydrazine hydrate aqueous solution redox graphene sponge is utilized, by two kinds
Reactant is placed in closed reaction vessel, and interlayer is placed, and places hydrazine hydrate solution below, and graphene oxide sea is placed in top
Silk floss is placed in baking oven, is heated to 90 DEG C and is carried out reduction 3h to graphene oxide sponge using hydrazine hydrate steam, the oxidation after reduction
Graphene sponge is Dark grey 3, and obtaining density is 12mg/cm3Graphene sponge.
Four, heat-treated graphite alkene sponge: by the graphene sponge of preparation, protection gas is done in Ar, is carried out under the conditions of 2000 DEG C
It is heat-treated 1h.
Five, pressurization graphite alkene sponge: the graphene sponge that heat treatment terminates is put into mold, later in 500Mpa,
Pressurized treatments are carried out under the conditions of 11Pa, obtain graphene film, see Fig. 3.
The present embodiment by the thickness of test sample it is observed that the graphene film prepared it is micro- with a thickness of 30
Rice is observed that significant change will not occur for graphene film by the repetitive process that bending is opened.
The Flexible graphene film conductivity of present embodiment preparation is 1.2 × 105S/m。
Claims (9)
1. a kind of preparation method of the highly conductive graphene film of flexibility, it is characterised in that this method carries out in the steps below:
Step 1: graphene oxide dispersion to be freezed to 10h~for 24 hours under the conditions of -50 DEG C~-20 DEG C, it is then freeze-dried 72h
~100h obtains graphene oxide sponge；
Step 2: being restored with hydrazine reducing agent steam to graphene oxide sponge；
Step 3: being then protection gas with inert gas, heat treatment 0.5h~2h is carried out under the conditions of 1000 DEG C~5000 DEG C；
Step 4: being then 10~400Pa in vacuum degree, pressure carries out pressurized treatments under the conditions of being 30MP a~500MP a, protects
Pressure 1min is held, graphene film is obtained；
Wherein, graphene oxide dispersion is by graphene oxide deionized water by (0.3~24) mg:1mL in step 1
Made of proportion mixes.
2. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that step 1 institute
The graphene oxide stated is prepared as follows: natural flake graphite being added in nitration mixture, with 200r/min~700r/
Min revolving speed stirs 20min~60min, then divides 5~8 times and potassium permanganate is added every 20min equivalent, then adjust whipping temp
Be 35 DEG C~80 DEG C, 200r/min~800r/min with rate, and be placed in water-bath constant temperature and stir 5h~18h, then plus
Into ice water, and the hydrogen peroxide that mass fraction is 30% is added into ice water, obtains suspension, filter, centrifuge washing obtains
Graphene oxide；
Wherein, the mass ratio of the volume of the nitration mixture and natural flake graphite is (10mL~300mL): 1g；The Gao Meng
The quality of sour potassium and the volume ratio of nitration mixture are (8g~100g): 1L；The quality of the natural flake graphite and the body of hydrogen peroxide
Product is than being 1g:(2mL~8mL)；
The phosphoric acid that nitration mixture is the sulfuric acid that mass fraction is 15%~98% and mass fraction is 15%~80% is according to (3~7): 1
Volume ratio mix.
3. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 1
Graphene oxide dispersion is made of mixing graphene oxide deionized water by the proportion of 0.8mg:1mL.
4. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 1
Graphene oxide dispersion is freezed for 24 hours under the conditions of -20 DEG C.
5. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 1
It is freeze-dried under the conditions of -50 DEG C~-20 DEG C.
6. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 2
Specifically 80wt% hydrazine reducing agent aqueous solution and graphene oxide sponge are placed in closed drier, place hydrazine below
Graphene oxide sponge is placed in reducing agent aqueous solution, top, is heated to 50 DEG C~100 DEG C using hydrazine reducing agent water vapour to oxygen
Graphite alkene sponge reductase 12 h~5h, obtains the graphene sponge of Dark grey.
7. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 2
The hydrazine reducing agent is hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.
8. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that in step 3
The inert gas is argon gas or nitrogen.
9. a kind of preparation method of the highly conductive graphene film of flexibility according to claim 1, it is characterised in that step 5 exists
Vacuum degree is 11Pa, and pressure carries out vacuum pressed processing under the conditions of being 300MP a, keeps pressure 1min, obtain graphene film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710310070.0A CN106986332B (en) | 2017-05-04 | 2017-05-04 | A kind of preparation method of the highly conductive graphene film of flexibility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710310070.0A CN106986332B (en) | 2017-05-04 | 2017-05-04 | A kind of preparation method of the highly conductive graphene film of flexibility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106986332A CN106986332A (en) | 2017-07-28 |
| CN106986332B true CN106986332B (en) | 2019-04-09 |
Family
ID=59418468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710310070.0A Active CN106986332B (en) | 2017-05-04 | 2017-05-04 | A kind of preparation method of the highly conductive graphene film of flexibility |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106986332B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107758644B (en) * | 2017-10-13 | 2019-08-20 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
| CN108910865A (en) * | 2018-07-21 | 2018-11-30 | 哈尔滨工业大学 | A method of preparing graphene/graphene nanobelt mixed film |
| CN110255535A (en) * | 2019-06-14 | 2019-09-20 | 中国航发北京航空材料研究院 | A kind of preparation method of conductive graphene film |
| CN110342498B (en) * | 2019-07-08 | 2021-05-07 | 浙江大学 | Graphene-based elastic structure and preparation method thereof |
| CN110775966B (en) * | 2019-11-21 | 2021-07-27 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
| CN114190947A (en) * | 2021-12-09 | 2022-03-18 | 上海交通大学 | Non-invasive electroencephalogram sensor based on flexible substrate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140019642A (en) * | 2012-08-07 | 2014-02-17 | 정은아 | Manufacturing method of graphene oxide sponge using freezing drying method |
| CN104291329A (en) * | 2014-09-28 | 2015-01-21 | 北京理工大学 | Graphene sponge and preparation method thereof |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
| CN105860939A (en) * | 2016-03-30 | 2016-08-17 | 上海上大瑞沪微系统集成技术有限公司 | Preparation method for graphene film with high thermal conductivity and heat dissipation method based on graphene film |
-
2017
- 2017-05-04 CN CN201710310070.0A patent/CN106986332B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140019642A (en) * | 2012-08-07 | 2014-02-17 | 정은아 | Manufacturing method of graphene oxide sponge using freezing drying method |
| CN104291329A (en) * | 2014-09-28 | 2015-01-21 | 北京理工大学 | Graphene sponge and preparation method thereof |
| CN105523547A (en) * | 2016-01-25 | 2016-04-27 | 浙江大学 | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film |
| CN105860939A (en) * | 2016-03-30 | 2016-08-17 | 上海上大瑞沪微系统集成技术有限公司 | Preparation method for graphene film with high thermal conductivity and heat dissipation method based on graphene film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106986332A (en) | 2017-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106986332B (en) | A kind of preparation method of the highly conductive graphene film of flexibility | |
| CN107041113B (en) | A method of it carries out compound preparing highly conductive high electromagnetic shielding flexible composite using graphene sponge and dimethyl silicone polymer | |
| CN104743551B (en) | A kind of preparation method of redox graphene heat conduction thin film | |
| CN105523546B (en) | A kind of preparation method of three-dimensional grapheme | |
| CN105254302B (en) | Preparing method for graphene heat conduction sheet | |
| Yu et al. | Fe nanoparticles and CNTs co-decorated porous carbon/graphene foam composite for excellent electromagnetic interference shielding performance | |
| Jiao et al. | Photothermal healable, stretchable, and conductive MXene composite films for efficient electromagnetic interference shielding | |
| CN101786620B (en) | Method for chemical synthesis of graphene | |
| CN102730667B (en) | Method for preparing monolayer graphite | |
| WO2012167700A1 (en) | Method for preparing graphene by using solid carbon source | |
| CN103011135A (en) | Graphene preparation method | |
| CN108929542A (en) | A kind of dimethyl silicone polymer with negative permittivity/graphene flexible composite film and preparation method thereof | |
| CN108772079A (en) | A kind of preparation method of nanometer of black phosphorus/graphene composite material | |
| CN107151002A (en) | A kind of method that individual layer or few layer boron nitride nanosheet are prepared by intercalator of the concentrated sulfuric acid | |
| CN110835099A (en) | Preparation method of thin-layer boron nitride nanosheet | |
| CN110745827A (en) | Preparation method of two-dimensional flaky SiC material | |
| CN113185834A (en) | Preparation method of polymer-based carbon nano composite microporous electromagnetic shielding material | |
| CN106431407B (en) | A method of two selenizing platinum of sheet is prepared using superhigh-pressure high-temp | |
| CN105565300A (en) | Method for preparing graphene films with high heat conductivity | |
| CN114751387A (en) | Method for efficiently preparing boron nitride nanosheet | |
| CN107010619B (en) | A kind of preparation method for taking into account sound insulation and the difunctional graphene paper of electromagnetic shielding | |
| CN111017916A (en) | Preparation method of graphene with controllable layer number | |
| CN112661992B (en) | Preparation method of high-thermal-conductivity polymer composite film with forest tree distributed structure | |
| CN107128907A (en) | A kind of size classification method of improved graphene oxide and graphene | |
| CN110407196A (en) | A kind of preparation method of the low defect graphene film based on grapheme foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |