CN115748234A - Preparation method of high-strength graphene material - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 239000000017 hydrogel Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000009987 spinning Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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Abstract
The invention discloses a method for obtaining a high-strength graphene material through ionic crosslinking. According to the invention, based on the coordination crosslinking action of metal ions and graphene oxide, the crosslinking between graphene oxide layers is enhanced, and stronger interlayer acting force is provided, so that the graphene oxide can bear larger tensile load to enable graphene oxide layers to be arranged straightly, thereby endowing the graphene material with excellent performances of high strength and high modulus, and having wide application prospects.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of a high-strength graphene material.
Background
In 2004, the physicists of the university of manchester, england, anderlich and consuding, norworth schloff, succeeded in separating graphene from graphite by micromechanical exfoliation. The graphene is a two-dimensional monoatomic layer honeycomb periodic lattice structure crystal consisting of carbon atoms in sp2 hybridized orbitals, and the thickness of the graphene is only 0.35nm. The graphene has excellent properties due to the unique structure, and has the advantages of excellent mechanical property, extremely large specific surface area, extremely large carrier mobility, extremely high thermal conductivity and the like. The graphene fiber is assembled by the graphene nanosheets, so that the excellent characteristics of the graphene in the nanoscale can be transferred to the macroscopic scale. With the gradual optimization of a material system and the gradual improvement of a preparation process, the graphene fiber is expected to be developed into a structure-function integrated fiber material and is applied to wider fields.
Graphene oxide, an important derivative of graphene, has attracted industrial attention because of its ease of mass production and unique solution processability. In 2011, a university of Zhejiang university Gaosuperior professor team prepares the graphene oxide fiber by a wet spinning method based on the lyotropic liquid crystal phenomenon of the graphene oxide. At present, the wet spinning method is the most commonly applied graphene fiber preparation method due to the characteristics of simple operation, high efficiency, large-scale application and the like. However, the nascent fiber obtained by liquid crystal wet spinning is not free from structural defects such as irregular wrinkles and the like in a solidification stage, large-size wrinkles in the fiber are easy to generate stress concentration in a stretching process, small-size wrinkles are large in quantity and different in size and are often difficult to regulate and control, the graphene oxide layer interval expansion is limited under a weak plasticizing system in the past, the deformation capability is weak under the stress action, and the micron-size wrinkles are difficult to completely eliminate. The structural defects exist in the fiber all the time, and are finally inherited to the graphene fiber after the processes of chemical reduction, heat treatment and the like, so that the comprehensive performance of the graphene fiber material is greatly influenced. In addition, for graphene oxide films, most of the existing methods are based on a blade coating method and a suction filtration method, and the two methods bring a large amount of wrinkles and pores to the surface and the inside of the film and damage the mechanical properties and the like of the film, which is a big problem of hindering the transfer of the excellent properties of two-dimensional graphene sheets to macroscopic materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a high-strength graphene material. According to the invention, based on the swelling of the graphene oxide by the metal ion solution and the coordination crosslinking effect, the acting force and the orientation degree between layers are greatly enhanced, and the highly oriented graphene oxide material with few folds is obtained; further, the high-performance graphene functional material with uniform folds is obtained through chemical reduction post-treatment.
The invention adopts the following technical scheme: a preparation method of a graphene oxide material comprises the following steps: placing the graphene oxide macroscopic material in a metal salt solution for soaking for 1-5 seconds and then stretching to obtain graphene oxide hydrogel; wherein the concentration of the metal salt is 0.2-2 mol/L, and the solvent of the metal salt can be water, acetic acid, ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, glycerol, triethylene glycol, tetraethylene glycol, pentaethylene glycol or other mixed solvents; the stretching rate is 40-60%, and the graphene oxide sheets are continuously stretched for 3-5s to keep the graphene oxide sheets in straight arrangement; in the step, uniform external force is kept, so that graphene sheets are kept in straight arrangement, the interlayer spacing is reduced, metal ions in a plasticizing bath can perform coordination crosslinking action on carboxyl functional groups at the upper edge of the graphene oxide sheets, a viscous sliding flow structure is converted into an elastic structure, interlayer sliding is greatly reduced, stronger interlayer acting force can be provided, and the graphene oxide sheets can bear larger load; and under the large-load stretching, unfolding the micro folds of the graphene sheet layers, arranging the graphene sheet layers in a straight manner, and drying to obtain the wrinkle-removed graphene oxide material.
Further, in the step (1), the metal salt is calcium chloride, magnesium chloride, copper sulfate, ferric chloride, aluminum chloride, or the like. The metal salt provides coordination crosslinking between graphene oxide sheets.
The graphene oxide macroscopic material is a graphene oxide fiber (not only a graphene oxide fiber monofilament, but also a graphene oxide fiber tow) and a graphene oxide film.
Further, the stretching bath is at least more polar than ethyl acetate, including but not limited to acetic acid, ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, glycerol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, or other mixed solvents.
Further, the method also comprises the step of carrying out reduction treatment on the de-wrinkled graphene oxide material. The reduction is chemical reduction, and reagents adopted by the chemical reduction are hydriodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride and the like.
The invention has the beneficial effects that: the method is characterized in that the graphene oxide hydrogel is subjected to plasticizing and stretching treatment in a plasticizing bath containing metal ions, and based on the characteristic of coordination and crosslinking between graphene oxide sheets by metal salts, the graphene oxide hydrogel can be subjected to coordination and crosslinking with carboxyl functional groups at the edges of the graphene oxide sheets, so that the acting force between the layers is enhanced, the inner sheets can bear large tensile load to enable the graphene oxide sheets to be arranged straightly, and a highly-oriented and regular micro-wrinkled structure is obtained, and therefore the graphene oxide hydrogel is endowed with excellent high modulus and high elasticity.
Drawings
Fig. 1 is SEM of the products of example 1 and comparative example 1 and a comparison of strength and modulus, a1 and a2 being the surface and cross section of the graphene fiber in example 1, respectively; b1 and b2 are the surface and the cross section of the graphene fiber in comparative example 1, respectively; the left dotted line in c represents the strength comparison of the graphene fibers of example 1 and comparative example 1, and the right dotted line in c represents the modulus comparison of the graphene fibers of example 1 and comparative example 1.
Fig. 2 is a SEM comparison of the products of example 2 and comparative example 2, a being the surface of the graphene fiber tow in example 2; b is the surface of the graphene fiber tow of comparative example 2.
Fig. 3 is a comparison of SEM and strength of the products of example 3 and comparative example 3, a1 and a2 being the surface and fracture surface of the graphene film in example 3, respectively; b1 and b2 are the surface and the fracture surface of the graphene film in comparative example 3 respectively; c is graphene film of example 3 (GP-Ca) 2+ ) Andstrength of graphene film (GP-Ethanol);
fig. 4 is a comparison of the maximum draw ratios of the ions in different plasticizing baths for the graphene oxide fibers of example 4, with the draw ratio on the ordinate.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example 1:
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide spinning solution of 8mg/g into a coagulating bath of ethyl acetate, and performing wet liquid crystal spinning to obtain a nascent graphene oxide fiber;
(2) Immersing the nascent graphene oxide fiber obtained in the step 1 in 1M CaCl 2 Plasticizing the graphene oxide film in a solution (the volume ratio of a solvent to ethanol is 1: 1) for 1s, and increasing the layer-to-layer spacing of graphene oxide sheets to 2.1nm at the stage;
(3) Stretching the graphene oxide fibers obtained in the step 2, wherein the stretching rate is 55%, and stretching is kept for 5s;
(4) Immersing the plasticized and stretched graphene oxide fiber in the step 3 into a water bath containing water and ethanol in a volume ratio of 3 2+ At this stage, the fiber needs to maintain the original tension;
(5) And (3) carrying out heat setting on the washed graphene oxide fibers in the step (4), and carrying out fumigation reduction treatment at 85 ℃ by using hydroiodic acid and acetic acid (1.
Through mechanical test, the strength of the graphene fiber reaches 1.82GPa.
Comparative example 1
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide spinning solution of 8mg/g into a coagulating bath of ethyl acetate, and performing wet liquid crystal spinning to obtain a nascent graphene oxide fiber;
(2) Immersing the nascent graphene oxide fiber in the step 1 into a solution with a volume ratio of water to ethanol of 1;
(3) Stretching the graphene oxide fibers obtained in the step 2, wherein the maximum stretching rate is 20%, and the stretching is kept for 5s;
(4) And (4) performing heat setting on the graphene oxide fiber in the step (3), and performing fumigation reduction treatment at 85 ℃ by using hydroiodic acid and acetic acid (1.
Through mechanical test, the strength of the graphene fiber reaches 0.78GPa.
The SEM of the products of example 1 and comparative example 1 are shown in fig. 1a and 1b, from which it can be seen that as the elongation increases, the fiber surface is more smoothly wrinkled, the cross-section is more dense and regular, and has a very excellent effect on mechanical conduction. The mechanical property diagrams are respectively shown in fig. 1c, and it can be seen from the diagrams that compared with the non-crosslinked graphene fiber, the strength of the graphene fiber subjected to ion crosslinking is improved by 133%, and the modulus is improved by 192%.
Example 2:
(1) Extruding 20mg/g DMF phase graphene oxide spinning solution into a coagulating bath of ethyl acetate through a spinneret plate with 100 holes and 120 micron apertures, and performing wet liquid crystal spinning to obtain a nascent graphene oxide fiber tow;
(2) Drawing the 100 graphene oxide fiber tows in the step 1 to 2M MgCl 2 Soaking the fiber tows in a solution (the volume ratio of water to ethanol is 1);
(3) Positively drafting the graphene oxide fiber tows in the step 2, wherein the stretching rate is 10%, and the stretching is kept for 5s;
(4) Drawing out the graphene oxide fiber tows in the step 3, and immersing the graphene oxide fiber tows into a water washing bath containing water and ethanol in a volume ratio of 3 2+ The fiber needs to keep the original tension at this stage;
(5) And (5) drying, collecting and chemically reducing the graphene oxide fiber tows in the step (4) to obtain uniformly oriented graphene fiber tows.
Comparative example 2:
(1) Extruding 20mg/g DMF (dimethyl formamide) phase graphene oxide spinning solution into a coagulating bath of ethyl acetate through a spinneret plate with 100 holes and 120 microns of pore diameter, and performing wet liquid crystal spinning to obtain nascent graphene oxide fiber tows;
(2) Drawing 100 graphene oxide fiber tows in the step 1 into a solution with a volume ratio of water to ethanol being 1;
(3) Carrying out positive drafting on the graphene oxide fiber tows in the step 2, wherein the stretching rate is 5%, and the stretching is kept for 5s;
(5) And (4) drying, collecting and chemically reducing the graphene oxide fiber tows in the step (3) to obtain the graphene fiber tows.
The SEM of the products of example 2 and comparative example 2 are shown in fig. 2a and 2b, and it can be seen that the surface of the cross-linked graphene fiber tow is more uniform, and the defects are less, so that the strength is more excellent.
Example 3:
(1) Obtaining a graphene oxide film by a film laying and drying method, and cutting the graphene oxide film into a strip shape with the length of 10mm and the width of 4 mm;
(2) Immersing the graphene oxide film obtained in the step 1 into 2M AlCl 3 Soaking the graphene oxide film in a solution (the volume ratio of the solvent to the water to the ethanol is 1) for 2s, so that the solution can fully penetrate into the interlayer of the graphene oxide macroscopic film;
(3) Applying axial tension to two ends of the graphene oxide film swelled in the step 2, wherein the graphene oxide macroscopic film material has a stretching rate of 13% under the action of the plasticizing stretching bath;
(4) Fixing the stretched graphene oxide macroscopic membrane material in the step 3, and carrying out washing bath on the membrane surface Al with the volume ratio of water to ethanol being 3 3+ In the process, the film is always in a tight state, then natural drying is carried out, and in the drying process, external force is applied to keep the current length;
(5) The film of step 4 was subjected to chemical reduction of hydroiodic acid and ethanol (1.
Through mechanical property tests, the strength of the crosslinked graphene film reaches 843MPa.
Comparative example 3:
(1) Obtaining a graphene oxide film by a film laying and drying method, and cutting the graphene oxide film into a strip shape with the length of 10mm and the width of 4 mm;
(2) Immersing the graphene oxide film obtained in the step 1 into a plasticizing and stretching bath of a solution with the volume ratio of water to ethanol being 1;
(3) Applying axial tension to two ends of the graphene oxide film swelled in the step 2, wherein the graphene oxide macroscopic film material has a stretching ratio of 7% under the action of the plasticizing stretching bath;
(4) And (3) carrying out chemical reduction on the stretched graphene oxide macroscopic membrane material in the step (3) by using hydroiodic acid and ethanol (1.
Through mechanical property test, the strength of the crosslinked graphene film reaches 468MPa.
The SEM of the products of example 3 and comparative example 3 are shown in fig. 3a and 3b, from which it can be seen that as the stretching ratio increases, random wrinkles of the graphene film surface are further eliminated and have two important features of plastic fracture, i.e., fibrous plastic orientation, near 45 ° shear deformation, having very excellent effects on mechanical conduction. The mechanical property diagrams are respectively shown in fig. 3c, and it can be seen that the strength of the graphene film subjected to ion crosslinking is improved by 80% compared with that of the graphene film not subjected to crosslinking.
Example 4:
(1) Extruding a DMF (dimethyl formamide) phase graphene oxide spinning solution of 8mg/g into a coagulating bath of ethyl acetate, and performing wet liquid crystal spinning to obtain nascent graphene oxide fibers;
(2) Respectively immersing the nascent graphene oxide fibers obtained in the step 1 into 0.2M FeCl 3 1M AlCl in solution (the volume ratio of the solvent to the ethanol is 1 3 In the solution (the volume ratio of the solvent to the ethanol is 1), 0.5M CuSO 4 In the solution (the volume ratio of the solvent to the ethanol is 1 2 In the solution (the volume ratio of the solvent to the ethanol is 1), 1M CaCl 2 Plasticizing the solution for 1s (the volume ratio of the solvent to the ethanol is 1).
(3) Stretching the graphene oxide fibers in different plasticizing baths in the step 2, wherein the maximum stretching rates respectively reach 20%, 30%, 33%, 35% and 55%, and keeping the stretching for 5s;
(4) Immersing the plasticized and stretched graphene oxide fiber in the step 3 into a water washing bath containing water and ethanol in a volume ratio of 3;
(5) And (3) carrying out heat setting on the washed graphene oxide fibers in the step (4), and carrying out fumigation reduction treatment at 85 ℃ by using hydroiodic acid and acetic acid (1.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a high-strength graphene material is characterized by comprising the following steps:
(1) Placing the graphene oxide macroscopic material in a metal salt solution for soaking for 1-5 seconds and then stretching to obtain graphene oxide hydrogel; wherein the concentration of the metal salt is 0.2-2 mol/L, and the solvent of the metal salt is a polar solvent; the stretching rate is 20-60%, and the stretching is continued for 3-5s to keep the graphene oxide sheet layers in straight arrangement;
(2) And drying to obtain the wrinkle-removed graphene oxide material.
2. The method according to claim 1, wherein in the step (1), the metal is presentThe salt is Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 3+ 、Al 3+ A salt.
3. The preparation method according to claim 1, wherein the graphene oxide macroscopic material is a graphene oxide fiber or a graphene oxide film.
4. The method according to claim 1, wherein the metal salt solution is prepared using a solvent selected from the group consisting of: acetic acid, ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, glycerol, triethylene glycol, tetraethylene glycol, pentaethylene glycol or other mixed solvents.
5. The method according to any one of claims 1 to 4, further comprising subjecting the de-wrinkled graphene oxide material to a reduction treatment.
6. The method according to claim 5, wherein the reduction is chemical reduction using reagents such as hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, and the like.
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