CN115012061A - Preparation method of high-strength high-toughness graphene composite fiber - Google Patents
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Abstract
The invention discloses a preparation method of a high-strength high-toughness graphene composite fiber. By adding the ultra-high molecular weight polyethylene oxide and combining the optimization of the process conditions of the stretching ratio and the coagulation bath temperature in wet spinning, the graphene composite fiber with both strength and toughness is prepared. According to the method, the orientation degree of graphene sheets in the fibers is improved, meanwhile, an ultra-high molecular weight polymer long molecular chain is introduced between graphene layers, and the strength and toughness of the composite fibers are improved by utilizing hydrogen bonds between single-layer graphene oxide sheets and the long molecular chain and the high entanglement density of the long molecular chain.
Description
Technical Field
The invention relates to the field of graphene composite materials, in particular to a preparation method of high-strength high-toughness graphene composite fibers.
Background
Graphene is a carbonaceous material having a two-dimensional periodic honeycomb lattice structure composed of carbon six-membered rings, and generally exhibits 3 states of zero-dimensional fullerene, one-dimensional Carbon Nanotube (CNT) and three-dimensional graphite. Since its discovery in 2004, much research has been done on graphene. The monolithic graphene has the highest tensile strength (130GPa), the highest Young modulus (1TPa) and the highest carrier mobility (15000 cm) 2 ·V -1 ·S -1 ) And the fastest heat conduction and heat conduction speed (the heat conduction coefficient is 5000 W.m) -1 ·K -1 )。
In 2011, the continuous graphene fiber material is prepared by a liquid crystal wet spinning and thermal reduction method in the earthquake admission of Zhejiang university and the like, and has attracted wide attention. Graphene fibers are a novel one-dimensional carbonaceous material with an internal layered structure. Formed by graphene sheets or graphene oxide sheets crosslinked by physical action or chemical bonds between the sheets. The graphene fiber with certain flexibility and good conductivity shows excellent performance and potential application value in the fields of energy storage, wearable flexible devices, biomaterials, sensor materials, catalyst carriers and the like. However, the strength and flexibility of the current graphene fiber are relatively poor, and the requirement of large stretching deformation is difficult to meet.
At present, functional nanoparticles, polymers and the like are added into a spinning solution, and chemical bonds such as covalent bonds, ionic bonds, hydrogen bonds and the like are formed between the functional nanoparticles and graphene nanosheets to improve interaction force between graphene nanosheets and further improve fiber strength, but the flexibility of the fibers is usually sacrificedToughness is a cost, and actual requirements are difficult to meet. For example, 10, 12-pentacosadiyne-1-ol and divalent calcium ions are adopted by Beijing aviation Materials 2016,28(14),2834-2839 to simultaneously form covalent bonds and ionic bond crosslinking, so that the interaction between graphene layers is greatly increased, the strength of the graphene fibers reaches 842.6MPa, but the elongation at break is only 3.5%, and the toughness value is 15.8MJ/m 3 . Liu et al (Electrochimica Acta,2021,365.2020.137363) reacted poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), PEDOT: PSS is introduced into a graphene oxide matrix, and flexible (PEDOT: PSS/rGO) fibers (PGF) for a super capacitor are prepared through a hydrothermal restriction reaction. The elongation at break of the flexible composite fiber is as high as 13.9 percent, but the breaking strength is only about 100MPa, and the balance of strength and toughness cannot be realized.
Disclosure of Invention
The invention provides a preparation method of a high-strength high-toughness graphene composite fiber, aiming at solving the problem that the strength and the toughness cannot be balanced in the existing method.
The spinning solution can show excellent tensile property by adding the polymer with ultrahigh molecular weight, particularly selecting the polyethylene oxide (PEO) polymer; by combining a wet spinning process, the orientation of the graphene oxide sheet layer in the fiber can be greatly improved by optimizing the draw ratio in a gel silk state, so that the strength of the fiber is improved. Through optimizing coagulation bath temperature, promote the inside molecule diffusion motion of nascent fibre, do benefit to solvent and non-solvent and pass gelatinous fibrous epidermal layer in the coagulation bath, form more even fibre inner structure, promote the free volume grow of polymer simultaneously, macromolecule chain segment mobility reinforcing is favorable to stretching at the external world and readjusts the internal molecular chain arrangement orientation, reduces inside hole and defect.
In order to solve the background problem and achieve the purpose of the invention, the invention provides a preparation method of a high-strength high-toughness graphene composite fiber, which specifically comprises the following steps:
1) preparing 5-30mg/ml Graphene Oxide (GO) dispersion liquid;
2) preparing 0.1-2 wt% ultra high molecular weight polyethylene oxide (PEO) polymer solution;
3) preparing a composite spinning solution: mixing the graphene oxide dispersion liquid obtained in the step 1) with the polyethylene oxide solution obtained in the step 2) to obtain a composite spinning solution; in the composite spinning solution, the mass ratio of polyethylene oxide (PEO) to graphene oxide is 1:10 to 10: 1;
4) extruding the composite spinning solution prepared in the step 3) through a spinning head, adding the composite spinning solution into a first-stage solidification solution to generate nascent fiber, then adding the nascent fiber into a second-stage solidification solution, winding the nascent fiber on a scroll, and naturally drying the nascent fiber to obtain graphene oxide composite fiber; respectively stretching the fibers in the first-stage solidification liquid and the second-stage solidification liquid;
first-stage solidification liquid: the volume ratio of the ethyl acetate to the ethanol is 1:5 to 5:1, the stretching ratio is 5-10, and the temperature is 45-65 ℃;
and (3) secondary solidification liquid: the volume ratio of the deionized water to the ethanol is 1:3 to 3:1, the stretching ratio is 1.5-3, and the temperature is 25-50 ℃;
in the first-stage coagulating bath, the motion deformability of polymer molecular chains is regulated and controlled by temperature, so that high tensile property is obtained, partial molecular chains in the fiber are arranged in parallel in an oriented manner, and the structure is regular and compact. After primary stretching, in a secondary coagulating bath, regular and ordered molecular conformation is fixed, and the stable order of the internal structure of the fiber is ensured.
And (3) reducing the graphene oxide composite fiber in a reducing atmosphere to obtain the graphene composite fiber.
Further, the solvent of the Graphene Oxide (GO) dispersion liquid and the polyethylene oxide (PEO) polymer solution is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethanol, glycerol and the like, which are mixed according to any proportion.
Further, the aperture of the spinning head in the step 4) is 100-200 um.
Further, the reducing atmosphere in the step 5) is one or more of hydrazine hydrate steam, hydrogen iodide solution, vitamin C solution and thermal reduction.
Further, the reduction temperature in the step 5) is 80-95 ℃, and the reduction time is 12-24 h.
Further, the diameter of the graphene composite fiber in the step 5) is 5-50 um.
As a conventional choice for dispersing and removing impurities, when preparing a Graphene Oxide (GO) dispersion solution, firstly dissolving a graphene oxide raw material in a solvent, performing ultrasonic dispersion treatment to prepare a graphene oxide dilute solution, and then centrifuging and concentrating the graphene oxide dilute solution at a high speed to remove impurities to obtain a graphene oxide dispersion solution of 5-30 mg/ml;
as a conventional choice for fully dissolving the ultrahigh molecular weight polyethylene oxide, when preparing the ultrahigh molecular weight polyethylene oxide polymer solution, 0.1 to 2 parts by weight of the ultrahigh molecular weight polyethylene oxide raw material is added into 100 parts by weight of the solvent, heated and stirred for fully dissolving to obtain 0.1 to 2 weight percent of polyethylene oxide polymer solution;
as a conventional choice for fully mixing the composite spinning solution, the graphene oxide dispersion solution and the ultrahigh molecular weight polyethylene oxide solution are magnetically stirred for a certain time at a speed of 100-700 rpm when being mixed;
the invention has the beneficial effects that:
1. the ductility of the ultra-high molecular weight polymer is utilized, and an optimized wet spinning process is combined, so that an extremely high draw ratio is obtained, the orientation degree of the graphene sheet layer in the fiber is improved, the strength of the composite fiber is improved, the tensile strength of the fiber can reach 1211.4MPa, and the high toughness is maintained: the elongation at break reaches 5.1 percent, and the toughness is 38.7MJ/m 3;
2. the composite fiber obtained by the method has a shell-like structure which is alternated layer by layer, the interaction force between single-layer graphene oxide sheets is greatly increased due to the existence of a high polymer at the interface between the layers, and the rich hydrogen bond action force between the two graphene sheets enables the relative sliding and drawing between the sheets to be realized only by absorbing higher energy when the graphene sheets are subjected to external stretching action force; meanwhile, polyethylene oxide with high entanglement density and ultrahigh molecular weight is introduced between graphene layers, so that when fibers bear external tensile acting force, more energy is absorbed through disentanglement, slippage, deviation and fracture of molecular chains, the toughness of the material is further improved, and the inertial conflict between two performance indexes is solved;
3. the preparation method provided by the invention is simple, low in cost, short in period and high in efficiency.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene composite fiber prepared by the invention, and the scale is 20 micrometers.
Fig. 2 is a mechanical curve of graphene composite fibers (rGO @ PEO) prepared by the present invention. .
Detailed Description
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.
Example 1
1) Dissolving 1 part by weight of graphene oxide raw material in 1000 parts by weight of N, N-Dimethylacetamide (DMAC), and performing ultrasonic dispersion treatment to obtain a graphene oxide solution;
2) concentrating the graphene oxide solution to remove impurities to obtain 5mg/ml graphene oxide dispersion liquid;
3) dissolving 1 weight part of ultra-high molecular weight polyethylene oxide raw material in 100 weight parts of N, N-Dimethylacetamide (DMAC), heating and stirring uniformly to obtain a polyethylene oxide polymer solution with the mass fraction of 1 wt%.
4) And (3) stirring the graphene oxide dispersion liquid obtained in the step 2 and the polyethylene oxide solution obtained in the step 3 according to the mass ratio of MGO to MPEO (multi-stage polyethylene oxide) of 1:10 for a certain time at the stirring speed of 100rpm to obtain a composite spinning solution for later use.
5) Extruding the composite spinning solution prepared in the step 4 into a coagulating liquid through a spinning head with the aperture of 100um of an injector, wherein a first-stage coagulating bath consists of ethyl acetate and ethanol, the volume ratio of the ethyl acetate to the ethanol is V-ethanol is 5:1, the temperature of the coagulating bath is 45 ℃, and the stretching ratio is 10; the second-stage coagulating bath consists of deionized water and ethanol, the volume ratio of the deionized water to the ethanol is 3:1, the temperature of the coagulating bath is 25 ℃, and the stretching ratio is 4. And naturally drying to obtain the graphene oxide composite fiber.
6) And (3) placing the graphene oxide composite fiber in a reducing atmosphere, and reducing for 12h at 85 ℃ to obtain the reduced graphene oxide composite fiber. The reducing atmosphere is hydrazine hydrate vapor.
7) And (3) repeatedly soaking and cleaning the reduced graphene oxide composite fiber obtained in the step (6) by using absolute ethyl alcohol and deionized water in sequence. And (3) drying in a 60 ℃ drying oven to obtain the high-strength and high-toughness graphene composite fiber.
8) The mechanical test of the graphene fiber is carried out on a Keysight nano stretching instrument, the stretching instrument is high in precision, the mechanical property of the nano fiber can be accurately tested, the stretching speed is 5mm/min, and the sample gauge length is 5 mm. Firstly cutting a 5 x 5mm paper frame, then fixing fibers on the paper frame by using epoxy resin, after the epoxy resin is cured, fixing the paper frame on a Keysight nano extensometer clamp, carefully cutting paper sheets by using scissors, and starting software to perform mechanical test at the moment. The cross section of the fiber is obtained by shooting the morphology of a fiber fracture through a scanning electron microscope and calculating the cross section of the fiber by using software.
9) The resulting fiber had a tensile strength of 1211.4MPa, an elongation at break of 5.1% and a tenacity of 38.7MJ/m 3.
Example 2
1) Dissolving 1 part by weight of graphene oxide raw material in 1000 parts by weight of N, N-Dimethylacetamide (DMAC), and performing ultrasonic dispersion treatment to obtain a graphene oxide solution;
2) concentrating the graphene oxide solution to remove impurities to obtain 10mg/ml graphene oxide dispersion liquid;
3) dissolving 1 weight part of ultra-high molecular weight polyethylene oxide raw material in 100 weight parts of N, N-Dimethylacetamide (DMAC), heating and stirring uniformly to obtain a polyethylene oxide polymer solution with the mass fraction of 0.1 wt%.
4) And (3) stirring the graphene oxide dispersion liquid obtained in the step 2 and the polyethylene oxide solution obtained in the step 3 according to the mass ratio of MGO to MPEO (multi-stage polyethylene oxide) of 1:5 for a certain time at the stirring speed of 500rpm to obtain a composite spinning solution for later use.
5) Extruding the composite spinning solution prepared in the step 4 into a coagulating liquid through a spinning head with the aperture of 100um of an injector, wherein a first-stage coagulating bath consists of ethyl acetate and ethanol, the volume ratio of the ethyl acetate to the ethanol is V-1: 5, the temperature of the coagulating bath is 65 ℃, and the stretching ratio is 6; the second-stage coagulating bath consists of deionized water and ethanol in a volume ratio of V deionized water to V ethanol of 1:3, the temperature of the coagulating bath is 50 ℃, and the stretching ratio is 3. And naturally drying to obtain the graphene oxide composite fiber.
6) And (3) placing the graphene oxide composite fiber in a reducing atmosphere, and reducing for 24h at the temperature of 95 ℃ to obtain the reduced graphene oxide composite fiber. The reducing atmosphere is hydrogen iodide vapor.
7) And (3) repeatedly soaking and cleaning the reduced graphene oxide composite fiber obtained in the step (6) by using absolute ethyl alcohol and deionized water in sequence. And (3) drying in a 60 ℃ drying oven to obtain the high-strength and high-toughness graphene composite fiber.
8) The mechanical test of the graphene fiber is carried out on a Keysight nanometer stretching instrument, the stretching instrument is high in precision, the mechanical property of the nanometer fiber can be accurately tested, the stretching speed is 5mm/min, and the sample gauge length is 5 mm. Firstly cutting a 5 x 5mm paper frame, then fixing fibers on the paper frame by using epoxy resin, after the epoxy resin is cured, fixing the paper frame on a Keysight nano extensometer clamp, carefully cutting paper sheets by using scissors, and starting software to perform mechanical test at the moment. The cross-sectional area of the fiber was obtained by taking the morphology of the fiber fracture by scanning electron microscopy and calculating the cross-sectional area of the fiber using software.
9) The resulting fiber had a tensile strength of 1172.4MPa, an elongation at break of 4.7%, and a tenacity of 28.1MJ/m 3.
Example 3
1) Dissolving 1 part by weight of graphene oxide raw material in 1000 parts by weight of N, N-Dimethylacetamide (DMAC), and performing ultrasonic dispersion treatment to obtain a graphene oxide solution;
2) concentrating the graphene oxide solution to remove impurities to obtain 20mg/ml graphene oxide dispersion liquid;
3) dissolving 1 weight part of ultra-high molecular weight polyethylene oxide raw material in 100 weight parts of N, N-Dimethylacetamide (DMAC), heating and stirring uniformly to obtain a polyethylene oxide polymer solution with the mass fraction of 1.5 wt%.
4) And (3) stirring the graphene oxide dispersion liquid obtained in the step 2 and the polyethylene oxide solution obtained in the step 3 according to the mass ratio of MGO to MPEO (multi-stage polyethylene oxide) of 1:1 for a certain time at the stirring speed of 600rpm to obtain a composite spinning solution for later use.
5) Extruding the composite spinning solution prepared in the step 4 into a coagulating liquid through a spinning head with the caliber of 150um of an injector, wherein a first-stage coagulating bath consists of ethyl acetate and ethanol, the volume ratio of the ethyl acetate to the ethanol is V-1: 1, the temperature of the coagulating bath is 55 ℃, and the stretching ratio is 4; the second-stage coagulating bath consists of deionized water and ethanol in a volume ratio of V deionized water to V ethanol of 1:1, the temperature of the coagulating bath is 45 ℃, and the stretching ratio is 2. And naturally drying to obtain the graphene oxide composite fiber.
6) And (3) placing the graphene oxide composite fiber in a reducing atmosphere, and reducing for 20h at 90 ℃ to obtain the reduced graphene oxide composite fiber. The reducing agent is a vitamin C solution.
7) And (3) repeatedly soaking and cleaning the reduced graphene oxide composite fiber obtained in the step (6) by using absolute ethyl alcohol and deionized water in sequence. And (3) drying in a 60 ℃ drying oven to obtain the high-strength and high-toughness graphene composite fiber.
8) The mechanical test of the graphene fiber is carried out on a Keysight nano stretching instrument, the stretching instrument is high in precision, the mechanical property of the nano fiber can be accurately tested, the stretching speed is 5mm/min, and the sample gauge length is 5 mm. Firstly cutting a 5 x 5mm paper frame, then fixing fibers on the paper frame by using epoxy resin, after the epoxy resin is cured, fixing the paper frame on a Keysight nano extensometer clamp, carefully cutting paper sheets by using scissors, and starting software to perform mechanical test at the moment. The cross-sectional area of the fiber was obtained by taking the morphology of the fiber fracture by scanning electron microscopy and calculating the cross-sectional area of the fiber using software.
9) The resulting fiber had a tensile strength of 929.8MPa, an elongation at break of 2.59%, and a tenacity of 11MJ/m 3.
Example 4
1) Dissolving 1 part by weight of graphene oxide raw material in 1000 parts by weight of N, N-Dimethylacetamide (DMAC), and performing ultrasonic dispersion treatment to obtain a graphene oxide solution;
2) concentrating the graphene oxide solution to remove impurities to obtain 30mg/ml graphene oxide dispersion liquid;
3) dissolving 1 weight part of ultra-high molecular weight polyethylene oxide raw material in 100 weight parts of N, N-Dimethylacetamide (DMAC), heating and stirring uniformly to obtain a polyethylene oxide polymer solution with the mass fraction of 2 wt%.
4) And (3) stirring the graphene oxide dispersion liquid obtained in the step 2 and the polyethylene oxide solution obtained in the step 3 according to the mass ratio of MGO to MPEO of 10:1 for a certain time at the stirring speed of 700rpm to obtain a composite spinning solution for later use.
5) Extruding the composite spinning solution prepared in the step 4 into a coagulating liquid through a spinning head with the caliber of 200um of an injector, wherein a first-stage coagulating bath consists of ethyl acetate and ethanol, the volume ratio of the ethyl acetate to the ethanol is V to 2:1, the temperature of the coagulating bath is 45 ℃, and the stretching ratio is 2; the second-stage coagulating bath consists of deionized water and ethanol in a volume ratio of V deionized water to V ethanol of 2:1, the temperature of the coagulating bath is 40 ℃, and the stretching ratio is 1.5. And naturally drying to obtain the graphene oxide composite fiber.
6) And (3) placing the graphene oxide composite fiber in a vacuum atmosphere, and reducing for 24h at the temperature of 95 ℃ to obtain the reduced graphene oxide composite fiber.
7) And (3) repeatedly soaking and cleaning the reduced graphene oxide composite fiber obtained in the step (6) by using absolute ethyl alcohol and deionized water in sequence. And (3) drying in a 60 ℃ drying oven to obtain the high-strength and high-toughness graphene composite fiber.
8) The mechanical test of the graphene fiber is carried out on a Keysight nano stretching instrument, the stretching instrument is high in precision, the mechanical property of the nano fiber can be accurately tested, the stretching speed is 5mm/min, and the sample gauge length is 5 mm. Firstly cutting a 5 x 5mm paper frame, then fixing fibers on the paper frame by using epoxy resin, after the epoxy resin is cured, fixing the paper frame on a Keysight nano extensometer clamp, carefully cutting paper sheets by using scissors, and starting software to perform mechanical test at the moment. The cross-sectional area of the fiber was obtained by taking the morphology of the fiber fracture by scanning electron microscopy and calculating the cross-sectional area of the fiber using software.
9) The tensile strength of the obtained fiber is 802.9MPa, the elongation at break is 2.2%, and the toughness is 6.32MJ/m 3.
Comparative example 1
The graphene oxide dispersion and the polyethylene oxide solution were mixed at a mass ratio MGO: MPEO of 1:15 as compared to example 1, and under the same conditions, the fiber obtained had a tensile strength of 719.51MPa, an elongation at break of 6.4%, and a toughness of 27.47MJ/m 3. It can be seen that the more the ultra-high molecular weight polyethylene oxide is added, the better the ultra-high molecular weight polyethylene oxide is added, and the excessive amount can reduce the tensile strength and toughness of the composite fiber.
Comparative example 2
Compared with the example 3, the temperature of the primary coagulation bath is 25 ℃, the temperature of the secondary coagulation bath is 20 ℃, and other conditions are the same, so that the tensile strength of the obtained fiber is 478.07MPa, the elongation at break is 2.6%, and the toughness is 5.55MJ/m 3. Therefore, the strength and the toughness of the composite fiber are obviously influenced by the temperature of the coagulation bath, and the strength and the toughness of the composite fiber are obviously reduced only by reducing the temperature of the primary coagulation bath and the temperature of the secondary coagulation bath.
Comparative example 3
Compared with example 4, the first stage coagulation bath temperature is 25 ℃, the draw ratio is 1.2, the second stage coagulation bath temperature is 15 ℃, the draw ratio is 0.8, and the tensile strength of the obtained fiber is 468.64MPa, the elongation at break is 1.3%, and the toughness is 3.51MJ/m3 under the same conditions. Therefore, the solidification bath temperature has obvious influence on both the strength and the toughness of the composite fiber, the first-stage and second-stage solidification bath temperatures are reduced, and the stretching ratio is influenced, so that the strength and the toughness of the composite fiber are obviously reduced.
Claims (6)
1. A preparation method of a high-strength high-toughness graphene composite fiber is characterized by comprising the following steps:
1) preparing 5-30mg/ml Graphene Oxide (GO) dispersion liquid;
2) preparing 0.1-2 wt% ultra high molecular weight polyethylene oxide (PEO) polymer solution;
3) preparing a composite spinning solution: mixing the graphene oxide dispersion liquid obtained in the step 1) with the polyethylene oxide solution obtained in the step 2) to obtain a composite spinning solution; in the composite spinning solution, the mass ratio of polyoxyethylene to graphene oxide is 1:10 to 10: 1;
4) extruding the composite spinning solution prepared in the step 3) through a spinning head, adding the composite spinning solution into a first-stage solidification solution to generate nascent fiber, then adding the nascent fiber into a second-stage solidification solution, winding the nascent fiber on a scroll, and naturally drying the nascent fiber to obtain graphene oxide composite fiber; respectively stretching the fibers in the first-stage solidification liquid and the second-stage solidification liquid;
first-stage solidification liquid: the volume ratio of the ethyl acetate to the ethanol is 1:5 to 5:1, the stretching ratio is 5-10, and the temperature is 45-65 ℃;
and (3) secondary solidification liquid: the volume ratio of the deionized water to the ethanol is 1:3 to 3:1, the stretching ratio is 1.5-3, and the temperature is 25-50 ℃;
5) and (3) reducing the graphene oxide composite fiber in a reducing atmosphere to obtain the graphene composite fiber.
2. The preparation method according to claim 1, wherein the solvent of the graphene oxide dispersion liquid and the polyethylene oxide polymer solution is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacethyl (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethanol, glycerol and the like, and the solvent is mixed according to any proportion.
3. The preparation method according to claim 1, wherein the spinneret orifice in step 4) is 100-200 um; the temperature of the first-stage coagulation bath is 45-65 ℃, and the temperature of the second-stage coagulation bath is 25-50 ℃.
4. The method according to claim 1, wherein the reducing atmosphere in step 5) is one or more of hydrazine hydrate vapor, a hydrogen iodide solution, a vitamin C solution, and thermal reduction.
5. The preparation method according to claim 1, wherein the reduction temperature in the step 5) is 80-95 ℃ and the reduction time is 12-24 h.
6. The preparation method according to claim 1, wherein the diameter of the graphene composite fiber obtained in step 5) is 5-50 um.
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