CN105752962A - Three-dimensional graphene macroscopic material and preparation method thereof - Google Patents
Three-dimensional graphene macroscopic material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a three-dimensional graphene macroscopic material and a preparation method thereof, the three-dimensional macroscopic graphene macroscopic material comprises graphene tubes with the thickness of 0.3-200nm, the diameter of 0.02-50mum and the length of 0.2-100mum; the graphene tubes in the three-dimensional macroscopic graphene macroscopic material are connected by covalent bonds, an aperture of a surrounded network structure is 0.5-100 mum; the three-dimensional macroscopic graphene macroscopic material has a density of 0.1-1000mg / cm<3>, a conductivity of 0.01-500S / cm, a compression strength of 0.0001-200MPa, compression modulus of 0.001-2000MPa and recoverable elastic deformation of 0.5-0.95.
Description
Technical field
The present invention relates to a kind of field of nanometer material technology, more particularly to a kind of low-density, high connductivity, high intensity, elastomeric three-dimensional grapheme macroscopic body material and preparation method, be mainly used in photovoltaic, semiconductor electronic, energy storage device or field of compound material.
Background technology
Macroscopic three dimensional porous carbon sill has the features such as low-density, porous, high-specific surface area, can as excellent electrode and heat sink material.At present, most of three-dimensional porous material with carbon elements, due to high porosity, are a kind of friable structures, and poor mechanical property is easily caved in compression process, be significantly limit its practical application.Therefore, developing the three-dimensional porous carbon-based material with high mechanical properties, excellent resilience and high conductivity is important research direction prepared by three-dimensional porous macroscopic body material.One-dimensional CNT and two-dimensional graphene by carbon atom tightly packed become cellular lattice structure, there is mechanics and the electric property of excellence.Therefore, CNT and Graphene are considered as construct the most promising material of three dimensional structure.
The three-dimensional microstructures of CNT or Graphene and packaging technology directly affect the electricity of three-dimensional material, mechanical property.At present, the CNT of three dimensional structure and the more employing sol-gal process of Graphene assemble, obtain three-dimensional aeroge by lyophilization and supercritical drying, owing to adopting between more weak π-π between CNT or Graphene or intermolecular force bonding, cause that mechanics and electric property are poor.As: first CNT is carried out functionalization by Xu etc., evenly spread in solution, it is assembled into ultralight carbon nanotube aerogel by sol-gel process, the CNT aeroge obtained has excellent compression restorability, but electrical conductivity (0.67S/cm) and yield strength (0.25kPa) all non-normally low (ACSNano4,7293 (2010)).Hu etc. propose self assembly and cryodesiccated two step process, obtain graphene aerogel ultralight, highly compressible, recoverable compressive deformation reaches～90%, but yield strength is only 1.5kPa (Adv.Mater.25,2219 (2013)).Zhang etc. increase Graphene bulk density (～96.1mg/cm further3), yield strength and Young's modulus are respectively up to 0.66MPa and 2.2MPa.But the flexibility decrease recovered of the graphene aerogel assembled is to 40% (J.Mater.Chem.21,6494 (2011)).Graphene/carbon nano-tube composite aerogel is developed, and has super-elasticity and the fatigue resistance of excellence.But, Graphene used adopts chemical preparation, and Graphene is of poor quality, defect is more, and compared with pure nano-carbon tube aeroge, composite aerogel electrical conductivity reduces by 70% (NatureNanotech.7,562 (2012)).Recently, adopt porous metals, utilize chemical vapour deposition technique to prepare the high-quality Graphene network structure (NatureMater.10,424 (2011)) of three-dimensional UNICOM.But, this three-dimensional grapheme network has large aperture structure (～hundreds of micron), result in poor mechanical strength and low surface area, seriously hinder the application in photovoltaic, semiconductor electronic, energy storage device or field of compound material as electrode and heat sink material.In sum, this area lacks a kind of low cost, mechanics, electricity, thermal property is excellent, the low-density three-dimensional grapheme macroscopic body material that can be mass-produced.
Summary of the invention
It is contemplated that fill up the existing technological gap that cannot realize large-scale production low-density three-dimensional grapheme macroscopic body material, the invention provides three-dimensional grapheme macroscopic body material and preparation method.
The invention provides a kind of three-dimensional grapheme macroscopic body material, described three-dimensional grapheme macroscopic body material is made up of grapheme tube, and the thickness of grapheme tube is 0.3～200nm, diameter is 0.02～50 μm, length 0.2～100 μm；In described three-dimensional grapheme macroscopic body material, grapheme tube is connected by covalent bond, and the cancellated aperture surrounded is 0.5～100 μm；The density of described three-dimensional grapheme macroscopic body material is 0.1～1000mg/cm3, electrical conductivity is 0.01～500S/cm, and compressive strength is 0.0001～200MPa, and modulus of compressibility is 0.001～2000MPa, and can recover elastic deformation is 0.5～0.95.
Described grapheme tube is doped with at least one in N, P, S, B and/or oxygen element, and wherein, in grapheme tube, the content of C calculates for 90%～100%, doping sum≤10% of N, P, S, B, content≤1% of oxygen element.
The specific surface area of described three-dimensional grapheme macroscopic body material can be 10～2500m2/g。
Again, the preparation method that present invention also offers a kind of above-mentioned three-dimensional grapheme macroscopic body material, described preparation method includes:
1) adopt the three-dimensional porous substrate constituted using oxide as template, grow grapheme tube by chemical vapour deposition technique；
2) by step 1) prepare grapheme tube successively through removing template, dry, 1600-2500 DEG C of high-temperature process, obtain described three-dimensional grapheme macroscopic body material.
Preferably, step 1) in, porous oxide includes at least one in copper oxide, ferrum oxide, nickel oxide, cobalt oxide, stannum oxide, manganese oxide, magnesium oxide, aluminium oxide, silicon oxide, zirconium oxide, titanium oxide, and three-dimensional porous substrate comprises macropore that aperture is 0.5～100 μm, aperture is the mesoporous of 2.0～50nm and/or aperture is the micropore of 0.01～2nm；The fibre diameter 0.05～50 μm that mesoporous and micropore is constituted；Three-dimensional porous substrate is prepared by hydro-thermal, sol-gal process.
Step 1) in, the technological parameter of described chemical vapour deposition technique includes:
After described three-dimensional porous silicon to reaction temperature 300-1400 DEG C and constant temperature 0-60 minute, importing carbon source, doped source, hydrogen and/or protection gas, gas flow is 1-1000sccm, carries out chemical vapour deposition reaction, 1-600 minute response time；Control rate of temperature fall after completion of the reaction and be 10-100 DEG C/min, be cooled to room temperature.
Carbon source used includes at least one in methane, ethylene, acetylene, propane, ethanol, acetone, benzene, toluene；Described doped source includes in ammonia, tripolycyanamide, thiophene, pyrroles, borine, boron oxide, five phosphorous oxide, phosphorus chloride, boric acid at least one.
Step 2) in, adopt the aqueous solution of iron chloride, ferric nitrate, hydrochloric acid, sulphuric acid, perchloric acid, nitric acid, Fluohydric acid., hydrogen peroxide, sodium hydroxide, potassium hydroxide and their mixture, remove template.
Step 2) in, drying means includes at least one of direct vacuum drying, lyophilization and supercritical drying.
Step 2) in, the time of high-temperature process is 0.1～12 hour, and protective atmosphere is argon and/or nitrogen.
Beneficial effects of the present invention:
The invention discloses the low-density of a kind of new structure, high connductivity, high intensity, elastomeric three-dimensional grapheme macroscopic body material and preparation method, three-dimensional grapheme is made up of grapheme tube, is formed by connecting by covalent bond between grapheme tube.Three-dimensional grapheme macroscopic body material has the conduction of excellence, mechanics, thermal property, and wherein, electrical conductivity, mechanical strength are higher than 1～5 order of magnitude reporting known porous material performance at present；Additionally, this preparation method technique is simple, process is easy to control, it is not necessary under vacuum, and equipment investment is few, it is possible to large-scale production.Can be applicable to photovoltaic, semiconductor electronic, energy storage device or field of compound material.
Accompanying drawing explanation
Fig. 1 illustrates the digital photograph of the three-dimensional grapheme macroscopic body material of preparation in an embodiment of the invention；
Fig. 2 illustrates the stereoscan photograph of the three-dimensional grapheme macroscopic body material of preparation in an embodiment of the invention；
Fig. 3 illustrates the Raman spectrum of the three-dimensional grapheme macroscopic body material of preparation in an embodiment of the invention, wherein vertical coordinate is the intensity (intensity) gathering signal, unit is dimensionless, and abscissa is Raman displacement (Ramenshift), and unit is cm-1；
Fig. 4 illustrates the EELS spectrum of the three-dimensional grapheme macroscopic body material of preparation in an embodiment of the invention, vertical coordinate is the intensity (intensity) gathering signal, unit is dimensionless, and abscissa is off-energy (Energyloss), and unit is eV；
Fig. 5 illustrates the digital photograph of the three-dimensional grapheme macroscopic body materials for support 200g counterweight of preparation in an embodiment of the invention；
Fig. 6 illustrates the three-dimensional grapheme macroscopic body material stress-strain curve of preparation in an embodiment of the invention, vertical coordinate is intensity (stress), unit is MPa, abscissa is strain (Strain), unit is (%) (in Fig. 6, big figure is load-deformation curve, and little figure is big figure amplifier section).
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are merely to illustrate the present invention below in conjunction with accompanying drawing and following embodiment, and the unrestricted present invention.
Solve the technical problem that
In order to construct new structure three-dimensional grapheme material and improve the conductive and mechanical properties of three-dimensional grapheme, the present invention proposes a kind of low-density, high connductivity, high intensity, elastomeric three-dimensional grapheme macroscopic body material and preparation method, using three-dimensional porous substrate as template, utilize chemical vapour deposition technique growth Graphene；Growth templates is removed, drying, it is thus achieved that three-dimensional grapheme macroscopic body material.The preparation method technique of this three-dimensional grapheme macroscopic body material is simple, and process is easy to control, and conduction, excellent in mechanical performance, preparation cost is low, is suitable for photovoltaic, semiconductor electronic, energy storage device or field of compound material.
Technical scheme
The present invention provides a kind of low-density, high connductivity, high intensity, elastomeric three-dimensional grapheme macroscopic body material and preparation method thereof, and described three-dimensional grapheme is made up of grapheme tube, is formed by connecting by covalent bond between grapheme tube.Described Graphene thickness is 0.3～200nm, and grapheme tube diameter is 0.02～50 μm, grapheme tube length 0.2～100 μm, 0.5～100 μm of the aperture surrounded between grapheme tube, and three-dimensional grapheme macroscopic body density of material is 0.1～1000mg/cm3, it is preferable that three-dimensional grapheme macroscopic body density of material is 0.5～200mg/cm3；Wherein, the content 90%～100% of C, N, P, S, B single-element content or their total contents 0～10%, oxygen element content 0～1%.
The electrical conductivity of three-dimensional grapheme macroscopic body material is 0.01～500S/cm.
The compressive strength of three-dimensional grapheme macroscopic body material is 0.0001～200MPa；Modulus of compressibility is 0.001～2000MPa；Can recover elastic deformation is 0.5～0.95.
The preparation method that the present invention also provides for described three-dimensional grapheme material, the method adopts the pottery with three dimensional structure as template, utilize chemical vapour deposition technique growth Graphene, adopt etching liquid to remove ceramic die panel material, it is thus achieved that three-dimensional continuous graphite alkene skeleton composite construction.
Said method comprising the steps of:
A () prepares three-dimensional porous substrate as template, grow Graphene by chemical vapour deposition technique；
B growth is had the three-dimensional porous substrate of Graphene to put in etching liquid by (), remove template；
C (), by dry, obtains described three-dimensional grapheme material；
D three-dimensional grapheme material is carried out high-temperature process by (), it is thus achieved that high-quality three-dimensional grapheme macroscopic body material.
In described step (a) constitute porous three-dimensional substrate material consist of copper oxide, ferrum oxide, nickel oxide, cobalt oxide, stannum oxide, manganese oxide, magnesium oxide, aluminium oxide, silicon oxide, zirconium oxide, titanium oxide and their mixture thereof, preferentially go through hydro-thermal, sol-gal process prepares big sky, mesoporous and micropore or their combination three-dimensional porous substrate.Big emptying aperture footpath is 0.5～100 μm, and mesoporous pore size is 2.0～50nm, and micropore size is 0.01～2nm；The fibre diameter 0.05～50 μm that mesoporous and micropore is constituted.
Graphene in described step (a) is obtained by chemical vapour deposition technique.
Described chemical vapour deposition technique comprises the steps:
After described three-dimensional porous silicon to reaction temperature 300-1400 DEG C and constant temperature 0-60min; import carbon source, doped source, hydrogen and protection gas; gas flow is 1-1000sccm (ml/min), carries out chemical vapour deposition reaction, response time 1-600min；
Controlling rate of temperature fall after completion of the reaction is 10-100 DEG C/min, is cooled to room temperature；
The product obtained is removed template, obtains described three-dimensional grapheme macroscopic body material；
Carbon source used is: methane, ethylene, acetylene, propane, ethanol, acetone, benzene, toluene and their mixing；
Doped source used is: ammonia, tripolycyanamide, thiophene, pyrroles, borine, boron oxide, five phosphorous oxide, phosphorus chloride, boric acid and their mixing.
Etching liquid in described step (b) adopts the aqueous solution of iron chloride, ferric nitrate, hydrochloric acid, sulphuric acid, perchloric acid, nitric acid, Fluohydric acid., hydrogen peroxide, sodium hydroxide, potassium hydroxide and their mixture.
Drying means in described step (c): the directly one in vacuum drying, lyophilization or supercritical drying, it is thus achieved that three-dimensional grapheme macroscopic body material.
High-temperature processing method in described step (d): treatment temperature is 1600 DEG C～2500 DEG C, processes 0.1～12 hour time, and protective atmosphere is one or both in argon, nitrogen.
The invention provides a kind of low cost, electricity, excellent in mechanical performance, the three-dimensional grapheme material that can be mass-produced.The application in photovoltaic, semiconductor electronic, energy storage device or field of compound material as electrode and heat sink material of described three-dimensional grapheme macroscopic body material.
Beneficial effect
The invention discloses the low-density of a kind of new structure, high connductivity, high intensity, elastomeric three-dimensional grapheme macroscopic body material and preparation method, three-dimensional grapheme is made up of grapheme tube, is formed by connecting by covalent bond between grapheme tube.Three-dimensional grapheme macroscopic body material has the conduction of excellence, mechanics, thermal property, and wherein, electrical conductivity, mechanical strength are higher than 1～5 order of magnitude reporting known porous material performance at present；Additionally, this preparation method technique is simple, process is easy to control, it is not necessary under vacuum, and equipment investment is few, it is possible to large-scale production.Can be applicable to photovoltaic, semiconductor electronic, energy storage device or field of compound material.
Enumerate embodiment further below to describe the present invention in detail.It is also understood that; following example are served only for the present invention is further described; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in hereafter example.
Comparative example 1
Adopt Hummer method to prepare graphene oxide, adopt the graphene oxide water solution of 6mg/ml through hydro-thermal, at 180 DEG C, be incubated 24 hours.Obtaining three-dimensional grapheme macroscopic body material, density is 25.8mg/cm3, electrical conductivity is 0.01S/cm, and compressive strength is 5kPa, and modulus of compressibility is 30kPa, and the compressive deformation of restorability is less than 0.5.
Comparative example 2
Adopt CVD, utilize nickel foam as template, under 1000 DEG C of conditions, introduce CH4:H2: Ar=10:50:300,15 minutes response time, in the HCl solution of dilution, remove metal form, it is thus achieved that three-dimensional grapheme macroscopic body material, density is 5.8mg/cm3, electrical conductivity is 0.5S/cm, and compressive strength is 0.1kPa, and modulus of compressibility is 1kPa, and the compressive deformation of restorability is less than 0.2.
Embodiment 1
Sol-gel process is utilized to prepare alchlor porous-substrates, put in chemical vapour deposition reactor furnace, heat to reaction temperature 1200 DEG C constant temperature 30min, import methane, hydrogen and argon, they gas flows respectively 6,60 and 700sccm (ml/min), carry out chemical vapour deposition reaction, response time 90min；There is the compound substrate of Graphene to put in 10% Fluohydric acid. and 15% hydrochloric acid etching liquid growth, enter back in 10M sodium hydroxide solution, remove template；In ethanol through vacuum drying, high-temperature process temperature 2500 DEG C, the process time is 1 hour, it is thus achieved that three-dimensional grapheme macroscopic body material, as shown in Figure 1.Grapheme tube diameter 50-200nm (Fig. 2), Graphene thickness is 1.～1.2nm, and very well (Fig. 3 and Fig. 4), three-dimensional grapheme macroscopic body density of material is 3.3mg/cm to Graphene quality3, specific surface area is 1800m2/ g, electrical conductivity is 1.1S/cm；Compressive strength is 0.025MPa, and modulus of compressibility is 0.35MPa, and compressive deformation is more than 0.8.
Find by contrasting, the three-dimensional graphene macroform material assembled has continuous print macrostructure, between Graphene, covalent bond connects, and compared with conventional three-dimensional graphene macroform material (comparative example 1 and comparative example 2), has the elasticity of more excellent conduction, mechanical strength and excellence.
Embodiment 2
Adopting methane flow as different from Example 1 is 20sccm, and the response time is 60 minutes, high-temperature process temperature 2200 DEG C, and the process time is 3 hours, Graphene thickness 3nm.Three-dimensional grapheme macroscopic body density of material is 15.6mg/cm3, specific surface area is 460m2/ g, electrical conductivity is 12.3S/cm；This Graphene three-dimensional macro body material can support the counterweight of own wt more than 30,000 times, without obvious deformation (Fig. 5) occurs, compressive strength is 0.3MPa, modulus of compressibility is 3.5MPa, restorability compressive deformation is more than 0.95, has the cyclical stability (Fig. 6) of excellence.
Embodiment 3
Adopting aluminium oxide and the compound porous template of nickel oxide as different from Example 1, nickel oxide accounts for the 20% of gross mass, and acetylene flow is 15sccm, and ammonia flow is 10sccm, reaction temperature 800 DEG C, and the response time is 90 minutes, 1800 DEG C of high-temperature process 5 hours.Graphene thickness 10～12nm.Graphene macroform density is 35.6mg/cm3, specific surface area is 280m2/ g, electrical conductivity is 18.1S/cm, and compressive strength is 0.4MPa, and modulus of compressibility is 3.8MPa, and compressive deformation is more than 0.9.
Embodiment 4
Hydro-thermal method is adopted to obtain magnesium oxide porous-substrates as different from Example 1, carbon source adopts ethanol (bubbling argon), argon flow amount is 300sccm, borine flow 5sccm, response time is 75 minutes, does not carry out high-temperature process, Graphene thickness 30nm, boron content is 1.5%, and graphene macroform density is 75mg/cm3, specific surface area is 85m2/ g, electrical conductivity is 35S/cm, and compressive strength is 0.9MPa, and modulus of compressibility is 8.7MPa, and compressive deformation is more than 0.8.
Embodiment 5
Hydro-thermal method is adopted to obtain silicon oxide porous-substrates as different from Example 4, carbon source adopts propane, flow is 50, and reaction temperature is 1000 DEG C, and argon flow amount is 100, thiophene is sulfur source (bubbling argon), response time is 90 minutes, does not carry out high-temperature process, Graphene thickness 30nm, sulfur content is 2.3%, and graphene macroform density is 105mg/cm3, specific surface area is 21m2/ g, electrical conductivity is 53S/cm, and compressive strength is 1.5MPa, and modulus of compressibility is 35MPa, and compressive deformation is more than 0.6.
Embodiment 6
Reaction temperature is 1100 DEG C as different from Example 5, Graphene thickness 65nm, and sulfur content is 3.3%, does not carry out high-temperature process, and graphene macroform density is 189mg/cm3, specific surface area is 15.6m2/ g, electrical conductivity is 78S/cm, and compressive strength is 2.3MPa, and modulus of compressibility is 58MPa, and compressive deformation is more than 0.5.
Embodiment 7
Reaction temperature is 900 DEG C as different from Example 5, Graphene thickness 15nm, and nitrogenous source adopts ammonia, and 10sccm, the response time is 60 minutes, does not carry out high-temperature process.Nitrogen element content is 1.5%, and graphene macroform density is 48.2mg/cm3, specific surface area is 150m2/ g, electrical conductivity is 25.3S/cm, and compressive strength is 0.4MPa, and modulus of compressibility is 4.9MPa, and compressive deformation is more than 0.5.
Embodiment 8
Reaction temperature is 600 DEG C as different from Example 5, Graphene thickness 0.4-0.6nm, it is not necessary to thiophene, and the response time is 20 minutes, and 2500 DEG C carry out high-temperature process 5 hours.Graphene macroform density is 0.7mg/cm3, specific surface area is 2200m2/ g, electrical conductivity is 0.5S/cm, and compressive strength is 0.01MPa, and modulus of compressibility is 0.15MPa, and compressive deformation is more than 0.8.
Claims (10)
1. a three-dimensional grapheme macroscopic body material, it is characterised in that described three-dimensional grapheme macroscopic body material is made up of grapheme tube, the thickness of grapheme tube is 0.3～200nm, diameter is 0.02～50 μm, length 0.2～100 μm；In described three-dimensional grapheme macroscopic body material, grapheme tube is connected by covalent bond, and the cancellated aperture surrounded is 0.5-100 μm；The density of described three-dimensional grapheme macroscopic body material is 0.1-1000mg/cm3, electrical conductivity is 0.01-500S/cm, and compressive strength is 0.0001-200MPa, and modulus of compressibility is 0.001-2000MPa, and can recover elastic deformation is 0.5-0.95.
2. three-dimensional grapheme macroscopic body material according to claim 1, it is characterized in that, described grapheme tube is doped with at least one in N, P, S, B and/or oxygen element, wherein, in grapheme tube, the content of C calculates for 90%-100%, the doping sum of N, P, S, B is≤10%, content≤1% of oxygen element.
3. three-dimensional grapheme macroscopic body material according to claim 1 and 2, it is characterised in that the specific surface area of described three-dimensional grapheme macroscopic body material is 10-2500m2/g。
4. the preparation method of arbitrary described three-dimensional grapheme macroscopic body material in a claim 1-3, it is characterised in that described preparation method includes:
1) adopt the three-dimensional porous substrate constituted using oxide as template, grow grapheme tube by chemical vapour deposition technique；
2) prepared by step 1) grapheme tube successively through removing template, dry, 1600-2500 DEG C of high-temperature process, obtain described three-dimensional grapheme macroscopic body material.
5. preparation method according to claim 1, it is characterized in that, in step 1), porous oxide includes at least one in copper oxide, ferrum oxide, nickel oxide, cobalt oxide, stannum oxide, manganese oxide, magnesium oxide, aluminium oxide, silicon oxide, zirconium oxide, titanium oxide, and three-dimensional porous substrate comprises macropore that aperture is 0.5-100 μm, aperture is the mesoporous of 2.0-50nm and/or aperture is the micropore of 0.01-2nm；The fibre diameter 0.05～50 μm that mesoporous and micropore is constituted；Three-dimensional porous substrate is prepared by hydro-thermal, sol-gal process.
6. the preparation method according to claim 4 or 5, it is characterised in that in step 1), the technological parameter of described chemical vapour deposition technique includes:
After described three-dimensional porous silicon to reaction temperature 300-1400 DEG C and constant temperature 0-60 minute, importing carbon source, doped source, hydrogen and/or protection gas, gas flow is 1-1000sccm, carries out chemical vapour deposition reaction, 1-600 minute response time；Control rate of temperature fall after completion of the reaction and be 10-100 DEG C/min, be cooled to room temperature.
7. preparation method according to claim 6, it is characterised in that carbon source used includes at least one in methane, ethylene, acetylene, propane, ethanol, acetone, benzene, toluene；
Described doped source includes in ammonia, tripolycyanamide, thiophene, pyrroles, borine, boron oxide, five phosphorous oxide, phosphorus chloride, boric acid at least one.
8. according to described preparation method arbitrary in claim 4-7, it is characterized in that, step 2) in, adopt the aqueous solution of iron chloride, ferric nitrate, hydrochloric acid, sulphuric acid, perchloric acid, nitric acid, Fluohydric acid., hydrogen peroxide, sodium hydroxide, potassium hydroxide and their mixture, remove template.
9. according to described preparation method arbitrary in claim 4-8, it is characterised in that step 2) in, drying means includes direct vacuum drying, lyophilization and supercritical drying.
10. according to described preparation method arbitrary in claim 4-9, it is characterised in that step 2) in, the time of high-temperature process is 0.1-12 hour, and protective atmosphere is argon and/or nitrogen.
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| CN112010288A (en) * | 2019-05-29 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Tubular graphene aerogel and preparation method and application thereof |
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| CN111977644A (en) * | 2020-08-27 | 2020-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene composite aerogel film with rivet structure, and preparation method and application thereof |
| CN111977644B (en) * | 2020-08-27 | 2022-12-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene composite aerogel film with rivet structure, and preparation method and application thereof |
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