CN115893388A - High-modulus and high-elasticity graphene foam material and preparation method and application thereof - Google Patents
High-modulus and high-elasticity graphene foam material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 238000007906 compression Methods 0.000 claims abstract description 51
- 239000006260 foam Substances 0.000 claims abstract description 32
- 238000002485 combustion reaction Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 230000002441 reversible effect Effects 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 239000003063 flame retardant Substances 0.000 claims description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkyl glycoside Chemical class 0.000 claims description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229930182470 glycoside Natural products 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
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- 230000001105 regulatory effect Effects 0.000 abstract description 6
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910021392 nanocarbon Inorganic materials 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a high-modulus and high-elasticity graphene foam material and a preparation method and application thereof, relating to the field of graphene and comprising the following steps: fixing the compressed graphene oxide foam material by using a clamp, and then carrying out flame complete combustion; taking down the clamp, and carrying out heat treatment on the product after combustion for more than 0.1h in an inert atmosphere or a vacuum environment to prepare a high-modulus and high-elasticity graphene foam material; the compressed graphene oxide foam material is a compressed product of the graphene oxide foam material with the compression ratio controlled to be 50% -95%. According to the invention, the three-dimensional structure and density of the graphene oxide foam are regulated and controlled by adjusting the compression degree, then flame combustion in a limited space is carried out with a clamp, the densely-stacked continuous graphene oxide walls are heated to rapidly expand and further foam in the limited cell space, so that a dense small-size (10 nm-50 μm) cell structure is formed, and high elastic modulus and high elasticity can be endowed to the graphene oxide foam.
Description
Technical Field
The invention relates to the field of graphene, in particular to a high-modulus and high-elasticity graphene foam material and a preparation method and application thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Graphene is a two-dimensional nanocarbon material with a thickness of only a single layer of carbon atoms, and the thickness is about 0.334 nm. The light macroscopic body material which is formed by assembling graphene serving as an assembling unit in a certain three-dimensional structure is called graphene foam or aerogel material. The graphene foam material has the characteristics of light weight, porosity, electric conduction, large specific surface area and the like, and has a good application prospect in the fields of energy, environment, electronics and the like. Depending on whether the graphene foam material has good compression elasticity, it can be simply classified into two categories: elastic graphene foam and inelastic graphene foam. Through the three-dimensional structure design, the graphene foam material can have good mechanical elasticity, for example, the reversible compression strain of the material can reach 99%, and the material can keep excellent resilience in an extremely wide temperature range of-269-1000 ℃. However, the elastic modulus of the high-elasticity graphene foam material is generally small and not more than 1mpa at most, so that the material is difficult to use under a high stress condition, and the application range of the material is limited. For graphene foam materials with high modulus, which are generally non-elastic materials, plastic deformation or rigid fracture is shown. Therefore, the current graphene foam material has difficulty in having both high modulus and high elasticity.
The mainstream preparation method of the graphene foam material is as follows: the method comprises the steps of taking graphene oxide as a raw material, obtaining wet gel with a specific three-dimensional structure by a liquid phase assembly and template method, and removing a solvent by means of freeze drying, supercritical drying, normal pressure drying and the like to obtain the aerogel or foam material. The method for reducing the graphene oxide into the graphene comprises chemical reduction and thermal reduction, and common templates comprise an ice template, a bubble template, an emulsion template and the like. In addition, graphene foam materials can also be obtained by rapidly reducing graphene oxide films by chemical or thermal reduction methods. Summarizing the method, the porous structure of the graphene foam material can be prepared by one-step molding, and pores are formed by a physical template or a chemical foaming means.
At present, the structure of high-elasticity graphene foam materials generally presents that graphene is stacked into a continuous macroporous network through pi-pi action, the size of macropores is between dozens of micrometers and hundreds of micrometers, and the materials present lower density, generally lower than 10 mg/cubic centimeter. Therefore, the elastic modulus of the material is generally small, and the material can be deformed by slight stress. Although the inelastic graphene foam material can obtain a dense small-hole structure, graphene is difficult to assemble orderly, generally presents an unordered stacking structure, a graphene chain joint is easy to damage when stress is applied, and a three-dimensional structure cannot be recovered after the stress is removed.
It is difficult to obtain a dense cell structure of nanometer size in the prior art, resulting in a material with a small elastic modulus (< 1 MPa).
Disclosure of Invention
Object of the Invention
The invention aims to provide a high-modulus and high-elasticity graphene foam material and a preparation method and application thereof, the three-dimensional structure and the density of graphene oxide foam are regulated and controlled by adjusting the compression degree, then flame combustion in a limited space is carried out by a clamp, densely-packed continuous graphene oxide walls are heated to rapidly expand and further foam in a limited cell space to form a dense small-size (10 nm-50 mu m) cell structure, and the structure can endow the graphene foam material with high modulus and high elasticity.
Solution scheme
In order to achieve the object of the present invention, in a first aspect, the present invention provides a method for preparing a high modulus and high elasticity graphene foam material, comprising the following steps:
fixing the compressed graphene oxide foam material by using a clamp, and completely burning the flame; taking down the clamp, and carrying out heat treatment on the product after combustion for more than 0.1h in an inert atmosphere or a vacuum environment to prepare a high-modulus and high-elasticity graphene foam material;
the compressed graphene oxide foam material is a compressed product of the graphene oxide foam material with the compression ratio of 50% -95% controlled.
Optionally, the clamp is a plate clamp.
In the invention, the sample can be combusted because the graphene oxide has oxygen-containing groups, the oxygen-containing groups are rapidly removed and reduced after combustion to obtain the graphene, and then the fire is extinguished. The high modulus in the present invention means a high elastic modulus.
The compression ratio of 50% to 95% in the invention refers to 50% to 95% of the original height of the compressed graphene oxide foam material, for example, when the compression ratio is 60%, the compressed height is lower than the original height by 60%.
Further, the complete combustion of the flame means that all areas of the sample are subjected to flame combustion treatment once, so that oxygen-containing groups in the graphene oxide are rapidly removed and reduced to obtain the graphene.
Further, the heat treatment temperature is 200-3000 ℃; optionally 400 to 2000 ℃, optionally 800 to 1600 ℃, optionally 800 ℃.
Further, the heat treatment time is more than 0.5h, optionally 0.5h to 15h, optionally 0.5h to 5h, optionally 0.8h to 3h, optionally 0.5h to 2h, optionally 0.5h to 1h, optionally 1h.
Further, the compression ratio is controlled at 50% to 95%, alternatively 70% to 90%.
Further, the compression method of the graphene oxide foam material comprises the following steps: bonding and assembling a plurality of graphene oxide foam sheets in a high humidity environment, and then compressing the graphene oxide foam sheets by using a flat plate clamp; optionally, the plurality of graphene oxide foam sheets comprises at least two sheets.
Further, the preparation method of the graphene oxide foam sheet comprises the following steps: mixing the graphene oxide aqueous dispersion, a surfactant and a flame retardant under the stirring condition, foaming to 1.5-3 times, tiling, and drying to obtain a graphene oxide foam sheet; optionally, the graphene oxide foam sheet has a thickness of 2 to 8mm.
Further, the weight ratio of the graphene oxide to the surfactant to the flame retardant is (8-20): (2-16): (0.8-4), optionally (12-20): (3-8): (1.2-4), optionally (16-20): (4-8): (1.6-3), optionally 16:4:2.4.
optionally, the surfactant is a nonionic surfactant and/or an anionic surfactant; optionally the surfactant is selected from sodium dodecylbenzene sulphonate, and/or an alkyl glycoside, and/or tween 20.
Optionally, the flame retardant is selected from a phosphorus-based, nitrogen-based, and/or bromine-based flame retardant; optionally, the flame retardant is ammonium polyphosphate, and/or melamine, and/or decabromodiphenyl ether.
Further, the concentration of the graphene oxide aqueous dispersion is 8-20 mg/mL, optionally 12-20 mg/mL, optionally 16mg/mL.
Further, in the preparation of the graphene oxide foam sheet, the expansion ratio is controlled to be 1.5 to 2.0 times, optionally 2.0 to 2.5 times, optionally 2.0 times.
Further, the drying temperature is between room temperature and 100 ℃, optionally between 30 and 80 ℃, optionally between 50 and 70 ℃, optionally 60 ℃. The graphene foam material with the characteristics can be obtained after drying at normal pressure.
Further, the elastic modulus of the high-modulus and high-elasticity graphene foam material is 0.1-20 MPa, and the reversible compressive strain is 10% -90%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 10% -70%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 50% -70%; optionally the elastic modulus is 2-20 MPa, and the reversible compression strain is 10% -50%.
Furthermore, the high-modulus and high-elasticity graphene foam material is provided with elastic grids with the hole wall thickness of 10nm or below 10nm and the hole diameter size of 10 nm-50 mu m.
In a second aspect, there is provided a high modulus, high elasticity graphene foam having an elastic lattice with a cell wall thickness of 10nm or less and a pore size between 10nm and 50 μm.
Furthermore, the elastic modulus of the high-modulus and high-elasticity graphene foam material is 0.1-20 MPa, and the reversible compressive strain is 10% -90%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 10-70%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 50-70%; optionally the elastic modulus is 2-20 MPa, and the reversible compression strain is 10% -50%.
Further, the feed comprises the following raw materials in percentage by weight: the weight ratio of the graphene oxide to the surfactant to the flame retardant is (8-20): (2-16): (0.8-4), optionally (12-20): (3-8): (1.2-4), optionally (16-20): (4-8): (1.6-3), optionally 16:4:2.4.
optionally, the surfactant is a nonionic surfactant and/or an anionic surfactant; optionally the surfactant is selected from sodium dodecylbenzene sulphonate, and/or an alkyl glycoside, and/or tween 20.
Optionally, the flame retardant is selected from a phosphorus-based, nitrogen-based, and/or bromine-based flame retardant; optionally, the flame retardant is ammonium polyphosphate, and/or melamine, and/or decabromodiphenyl ether;
further, the preparation method is adopted.
In a third aspect, the high modulus, high elasticity graphene foam material prepared by the preparation method of the first aspect or the high modulus, high elasticity graphene foam material of the second aspect is applied to stretchable conductors, intelligent sensors or aerospace fields.
Advantageous effects
(1) According to the invention, the three-dimensional structure and density of the graphene oxide foam can be regulated and controlled by adjusting the compression degree, then flame combustion in a limited space is carried out by the clamp, the densely-stacked continuous graphene oxide walls are heated to rapidly expand and further foam in the limited cell space to form a dense small-size cell structure, and the structure can endow the graphene foam material with high elastic modulus (0.1-20 MPa) and high elasticity (reversible compression strain). The compression ratio of the invention is controlled below 50% of the original height of the sample, and the sample is subjected to flame combustion treatment with the clamp in a compression state, the thickness direction of the sample is not changed, the range of the sample is limited by the clamp, the space in which the graphene oxide wall can expand is limited, and the expanded graphene is fully extruded in the limited space, so that a small-size dense graphene elastic network (10 nanometers to 50 micrometers) is obtained.
(2) According to the invention, the modified graphene oxide foam material is obtained by adding the flame retardant, and is bonded and assembled in a high humidity environment, so that the graphene oxide foam material with high thickness can be obtained, the graphene oxide foam material with a hierarchical structure can be obtained by flame combustion and rapid reduction, the density of the graphene oxide can be regulated and controlled by regulating and controlling the compression ratio, and the size of the cells can be regulated and controlled, so that high elastic modulus and high elasticity (reversible compression strain) are obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations such as "comprises" or "comprising", etc., will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention. All the percentages in the formula are in weight ratio.
The graphene oxide foam materials in the following examples were prepared as follows:
1) Graphite powder is used as a raw material, the number of graphene powder meshes is 325 meshes, and graphene oxide aqueous dispersion is obtained through oxidation by an improved hummers method;
2) Dispersing 100mL of graphene oxide water, wherein the graphene oxide is 16mg/mL (the range can be 8-20 mg/mL), adding 400mg (the range can be 200-1600 mg) of surface active agent sodium dodecyl benzene sulfonate (non-ionic surface active agents such as alkyl glycoside and the like or anionic surface active agents) and 240mg (the range can be 180-480 mg) of flame retardant ammonium polyphosphate (common flame retardants such as phosphorus, nitrogen, bromine and the like), and foaming by violent stirring, wherein the foaming multiplying power is controlled to be 2.0 times (the range is 1.5-3.0);
3) And (3) spreading a layer of foaming slurry on a substrate, controlling the thickness to be 6mm (the range can be 2-8 mm), controlling the drying temperature to be 60 ℃ (room temperature-100 ℃), and obtaining the flaky graphene oxide foam material after the slurry is completely dried.
No elasticity, plastic deformation caused by compression, and modulus lower than 0.01MPa. In the following examples, the compression method is plate compression, i.e. the sample is compressed by being clamped between parallel plate clamps, and the compression ratio is = (height before compression-height after compression)/height before compression.
In the following examples, complete combustion means that all regions of a sample are subjected to flame combustion once, so that oxygen-containing groups in graphene oxide are rapidly removed and reduced to obtain graphene.
In the following examples, the elastic modulus refers to the elastic modulus of a material subjected to compression detection, specifically: stress in the unidirectional stress state is divided by strain in that direction.
In the following examples, the elastic test refers to detecting the reversible compressive strain of a material by compression, specifically, the compression ratio of the material which can be recovered to the original height of the material after compression, for example, the reversible compressive strain of 60% refers to that when the material is compressed to 60% lower than the original height (= 100% -40%, wherein, the original height of the material is 100%, and the height after compression is 40% of the original height), the material can still be recovered to the original height of the material, and the reversible compressive strain at this time is 60%.
Example 1
(1) Cutting the sheet graphene oxide foam sheet into regular shapes with the same size, and assembling the sheets under a high-humidity environment to bond the sheets into a whole, wherein the number of the assembled sheets is more than or equal to 2, so that a sample (1 mm) with a certain thickness is obtained;
(2) Then compressing the assembled graphene oxide foam by using a special fixture, and controlling the compression ratio to be 90%;
(3) Fixing the compressed and assembled graphene oxide foam by using a clamp, then carrying out flame complete combustion, taking off the clamp, and carrying out heat treatment on a sample at 800 ℃ for 1h in an inert atmosphere or a vacuum environment to obtain the graphene foam material with high elastic modulus (2 MPa) and high elasticity (reversible compressive strain of 50%).
Example 2
The difference from example 1 is that the compression ratio in step (2) is 70%, the elastic modulus of the obtained graphene foam material is 1.0MPa, and the reversible compression strain is 70%.
Example 3
The difference from example 1 is that the compression ratio in step (2) is 50%, the elastic modulus of the obtained graphene foam material is 0.1MPa, and the reversible compression strain is 90%.
Example 4
The difference from example 1 is that the heat treatment conditions in step (3) were: and treating at 1200 ℃ for 1 hour. The elastic modulus of the obtained graphene foam material is 1.8MPa, and the reversible compression strain is 60%.
Example 5
The difference from example 1 is that the heat treatment conditions in step (3) were: treated at 1600 ℃ for 0.5 hour. The elastic modulus of the obtained graphene foam material is 1.7MPa, and the reversible compression strain is 65%.
The above examples show that when the compression ratio is controlled to be 50-90%, the heat treatment conditions are 800-1600 ℃, and the treatment time is 0.5-1 h, the elastic modulus of the obtained composite material is more than or equal to 0.1MPa, and the reversible compression strain is 50-90%.
The above examples show that when the compression ratio is controlled to be 70-90%, the heat treatment conditions are 800-1600 ℃, and the treatment time is 0.5-1 h, the elastic modulus of the obtained composite material is more than or equal to 1MPa, and the reversible compression strain is 50-70%.
Comparative example 1
The difference from example 1 is that the graphene oxide foam assembled in step (1) is directly subjected to combustion in step (3) by using a fixture without compression in step (2), and the elastic modulus of the obtained graphene foam material is 0.05MPa.
Comparative example 2
The difference from the embodiment 1 is that in the step (3), the flame is directly and completely combusted without being fixed by a clamp, the sample is violently expanded, the thickness direction is obviously increased, and the elastic modulus of the obtained graphene foam material is 0.08MPa.
In conclusion, the elastic modulus of the material obtained by the invention is remarkably improved to 0.1-20 MPa, even 1-20 MPa, and compared with the existing high-strength graphene foam material, the elastic modulus can be improved by more than 100 times; the modulus of elasticity of the material is generally below 0.1MPa if not compressed (comparative example 1) or clamped (comparative example 2).
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a high-modulus and high-elasticity graphene foam material is characterized by comprising the following steps:
fixing the compressed graphene oxide foam material by using a clamp, and completely burning the flame; taking down the clamp, and carrying out heat treatment on the product after combustion for more than 0.1h in an inert atmosphere or vacuum environment to prepare a high-modulus and high-elasticity graphene foam material;
the compressed graphene oxide foam material is a compressed product of the graphene oxide foam material with the compression ratio of 50% -95% controlled.
2. The preparation method according to claim 1, wherein the complete flame combustion means that all areas of a sample are subjected to flame combustion once, so that oxygen-containing groups in graphene oxide are rapidly removed and reduced to obtain graphene;
and/or the heat treatment temperature is 200-3000 ℃; optionally 400 to 2000 ℃, optionally 800 to 1600 ℃, optionally 800 ℃;
and/or the clamp is a flat plate clamp;
and/or the heat treatment time is more than 0.5h, optionally 0.5h to 15h, optionally 0.5h to 5h, optionally 0.5h to 3h, optionally 0.5h to 2h, optionally 0.5h to 1h, optionally 1h.
3. The method of claim 1 or 2, wherein the compression ratio is controlled at 50% to 95%, optionally 70% to 90%.
4. The method according to any one of claims 1 to 3, wherein the graphene oxide foam is compressed by a method comprising: bonding and assembling a plurality of graphene oxide foam sheets in a high humidity environment, and then compressing the graphene oxide foam sheets by using a flat plate clamp;
optionally, the plurality of graphene oxide foam sheets comprises at least two sheets.
5. The method according to any one of claims 1 to 4, wherein the method for preparing the graphene oxide foam sheet comprises: mixing the graphene oxide aqueous dispersion, a surfactant and a flame retardant under the stirring condition, foaming to 1.5-3 times, tiling, and drying to obtain a graphene oxide foam sheet; optionally, the graphene oxide foam sheet has a thickness of 2 to 8mm.
6. The preparation method according to claim 5, wherein the weight ratio of the graphene oxide to the surfactant to the flame retardant is (8-20): (2-16): (0.8-4), optionally (12-20): (3-8): (1.2-4), optionally (16-20): (4-8): (1.6-3), optionally 16:4:2.4;
optionally, the surfactant is a nonionic surfactant and/or an anionic surfactant; optionally the surfactant is selected from sodium dodecylbenzene sulphonate, and/or an alkyl glycoside, and/or tween 20;
optionally, the flame retardant is selected from a phosphorus-based, nitrogen-based, and/or bromine-based flame retardant; optionally, the flame retardant is ammonium polyphosphate, and/or melamine, and/or decabromodiphenyl ether;
optionally, the concentration of the graphene oxide aqueous dispersion is 8-20 mg/mL, optionally 12-20 mg/mL, optionally 16mg/mL.
7. The preparation method according to any one of claims 1 to 6, wherein in the preparation of the graphene oxide foam sheet, the expansion ratio is controlled to be 1.5 to 2.0 times, optionally 2.0 to 2.5 times, optionally 2.0 times;
and/or the drying temperature is between room temperature and 100 ℃, optionally between 30 and 80 ℃, optionally between 50 and 70 ℃, optionally 60 ℃.
8. The preparation method of any one of claims 1 to 7, wherein the high modulus, high elasticity graphene foam material has an elastic modulus of 0.1 to 20MPa and a reversible compressive strain of 10 to 90%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 10-70%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 50-70%; optionally the elastic modulus is 2-20 MPa, and the reversible compression strain is 10% -50%;
and/or the high-modulus and high-elasticity graphene foam material is provided with elastic grids with the hole wall thickness of 10nm or below 10nm and the hole diameter size of 10 nm-50 mu m.
9. A high modulus and high elasticity graphene foam material is characterized in that the material is provided with elastic grids with the hole wall thickness of 10nm or below 10nm and the hole diameter size of 10 nm-50 mu m;
optionally, the high-modulus and high-elasticity graphene foam material has an elastic modulus of 0.1-20 MPa and a reversible compressive strain of 10% -90%; optionally the elastic modulus is 1-20 MPa, and the reversible compression strain is 10-70%; optionally, the elastic modulus is 2-20 MPa, and the reversible compressive strain is 10% -50%;
optionally, the raw materials in the following weight ratio are included: the weight ratio of the graphene oxide to the surfactant to the flame retardant is (8-20): (2-16): (0.8-4), optionally (12-20): (3-8): (1.2-4), optionally (16-20): (4-8): (1.6-3), optionally 16:4:2.4;
optionally, the surfactant is a nonionic surfactant and/or an anionic surfactant; optionally the surfactant is selected from sodium dodecylbenzene sulphonate, and/or an alkyl glycoside, and/or tween 20;
optionally, the flame retardant is selected from a phosphorus-based, nitrogen-based, and/or bromine-based flame retardant; optionally, the flame retardant is ammonium polyphosphate, and/or melamine, and/or decabromodiphenyl ether;
alternatively, it is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the high modulus, high elasticity graphene foam prepared by the preparation method of any one of claims 1 to 8 or the high modulus, high elasticity graphene foam of claim 9 in stretchable conductors, smart sensors or aerospace field.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150217538A1 (en) * | 2014-02-06 | 2015-08-06 | Aruna Zhamu | Highly oriented graphene structures and process for producing same |
| CN106967392A (en) * | 2017-04-28 | 2017-07-21 | 哈尔滨赫兹新材料科技有限公司 | The hot three-dimensional grapheme heat sink material of high-strength highly-conductive and its construction method |
| CN107010618A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | The preparation method and radiating film of a kind of high starch breeding alkene radiating film |
| CN108328596A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院物理研究所 | A kind of carbon sponge and preparation method thereof and pressure sensor |
| CN109095457A (en) * | 2018-09-12 | 2018-12-28 | 芦露华 | A method of quickly preparing reduced graphene and its composite material |
| CN109096526A (en) * | 2018-09-07 | 2018-12-28 | 青岛科技大学 | A kind of graphite oxide aerogel, redox graphene aeroge and its preparation method and application |
| CN109734076A (en) * | 2018-12-28 | 2019-05-10 | 北京理工大学 | A kind of preparation method of large area high intensity super-elasticity grapheme foam material |
| CN110155978A (en) * | 2018-02-14 | 2019-08-23 | 美利坚合众国（由农业部长代表） | Wooden base carbon foam and composite material and correlation technique |
| CN113120884A (en) * | 2021-04-16 | 2021-07-16 | 北京理工大学 | Graphene aerogel with sound absorption and audio recognition functions and application thereof |
-
2023
- 2023-02-10 CN CN202310108222.4A patent/CN115893388A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150217538A1 (en) * | 2014-02-06 | 2015-08-06 | Aruna Zhamu | Highly oriented graphene structures and process for producing same |
| CN108328596A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院物理研究所 | A kind of carbon sponge and preparation method thereof and pressure sensor |
| CN106967392A (en) * | 2017-04-28 | 2017-07-21 | 哈尔滨赫兹新材料科技有限公司 | The hot three-dimensional grapheme heat sink material of high-strength highly-conductive and its construction method |
| CN107010618A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | The preparation method and radiating film of a kind of high starch breeding alkene radiating film |
| CN110155978A (en) * | 2018-02-14 | 2019-08-23 | 美利坚合众国（由农业部长代表） | Wooden base carbon foam and composite material and correlation technique |
| CN109096526A (en) * | 2018-09-07 | 2018-12-28 | 青岛科技大学 | A kind of graphite oxide aerogel, redox graphene aeroge and its preparation method and application |
| CN109095457A (en) * | 2018-09-12 | 2018-12-28 | 芦露华 | A method of quickly preparing reduced graphene and its composite material |
| CN109734076A (en) * | 2018-12-28 | 2019-05-10 | 北京理工大学 | A kind of preparation method of large area high intensity super-elasticity grapheme foam material |
| CN113120884A (en) * | 2021-04-16 | 2021-07-16 | 北京理工大学 | Graphene aerogel with sound absorption and audio recognition functions and application thereof |
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