CN114318583B - Reduced graphene oxide composite fiber and preparation method and application thereof - Google Patents
Reduced graphene oxide composite fiber 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 90
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- 239000000835 fiber Substances 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims abstract description 79
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims abstract description 79
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 75
- 238000006722 reduction reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002166 wet spinning Methods 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims description 33
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
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- 238000006116 polymerization reaction Methods 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 8
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- 150000002505 iron Chemical class 0.000 claims description 4
- 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 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 2
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- 239000000243 solution Substances 0.000 description 63
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 9
- 239000012362 glacial acetic acid Substances 0.000 description 9
- 230000007547 defect Effects 0.000 description 6
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- 238000005345 coagulation Methods 0.000 description 5
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Abstract
The invention belongs to the technical field of functional fiber material preparation, and provides a reduced graphene oxide composite material, and a preparation method and application thereof. According to the invention, poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS) is added into graphene oxide, and the obtained PEDOT/PSS and graphene oxide mixed solution are subjected to wet spinning and reduction reaction to obtain the high-performance graphene fiber. PEDOT is conjugated with graphene oxide pi-pi, so that a conjugated system is increased, and the conductivity of the fiber is enhanced; PSS increases the spacing between graphene sheets through electrostatic repulsion, so that wrinkling of the graphene sheets is reduced, meanwhile PSS spans the sheets and forms pi-pi conjugation with graphene to connect the graphene sheets, and the fiber stretch resistance is enhanced. The method not only improves the conductivity of the graphene fiber, but also improves the mechanical property of the graphene fiber, greatly widens the application range of the graphene, and has great significance for continuous industrial production of the graphene fiber.
Description
Technical Field
The invention relates to the technical field of functional fiber material preparation, in particular to a reduced graphene oxide composite fiber, and a preparation method and application thereof.
Background
With the advent of industry 4.0, smart wearable devices became a popular research. The intelligent wearable device needs to work under the condition of not affecting normal activities of human bodies, and higher requirements are put on flexibility, stretching resistance, bending property and light miniaturization of each component part of the intelligent wearable device. Fibrous supercapacitor as a flexible energy storage device has important application in power supply modules in intelligent wearable devices.
The graphene fiber prepared from the graphene has certain flexibility and conductivity, and is an ideal electrode material of a fibrous supercapacitor. The Reduced Graphene Oxide (RGO) fiber is generally prepared by chemically reducing Graphene Oxide (GO). When the reduced graphene oxide fiber composite material is prepared by wet spinning, graphene sheets are easily stacked again in the chemical reduction GO process, so that the specific surface area of the reduced graphene oxide fiber is reduced, and the reduced graphene oxide fiber composite material is difficult to reach ideal conductivity; and the stacking direction of the reduced graphene oxide sheets is disordered, and the shrinkage in a coagulating bath is uneven, so that lattice defects and stress concentration can be caused, the reduced graphene oxide fiber is fragile and easy to break, and the reduced graphene oxide fiber composite material has poor toughness.
Disclosure of Invention
In view of the above, the present invention aims to provide a reduced graphene oxide composite material, and a preparation method and application thereof. The reduced graphene oxide composite material obtained by the preparation method has excellent toughness; at the same time, it has excellent conductivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a reduced graphene oxide composite fiber, which comprises the following steps:
mixing 3, 4-ethylenedioxythiophene monomer, polystyrene sulfonic acid, oxidant and water, and performing chemical polymerization reaction to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution;
mixing the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution and graphene oxide aqueous dispersion to obtain spinning solution;
carrying out wet spinning on the spinning solution to obtain a composite fiber precursor;
and carrying out a reduction reaction on the composite fiber precursor to obtain the reduced graphene oxide composite fiber.
Preferably, the ratio of the amounts of the 3, 4-ethylenedioxythiophene monomer and polystyrene sulfonic acid species is 1: (0.1-10).
Preferably, the oxidizing agent comprises a soluble ferric salt comprising FeCl and/or a monovalent cation persulfate salt 3 And/or Fe 2 (SO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The monovalent cation persulfate comprises Na 2 S 2 O 8 、K 2 S 2 O 8 And (NH) 4 ) 2 S 2 O 8 One or more of the following.
Preferably, when the oxidizing agent is a mixture of a soluble ferric salt and a monovalent cation persulfate, the mass ratio of the 3, 4-ethylenedioxythiophene monomer, the soluble ferric salt and the monovalent cation persulfate is 1: (0.1-1): (1-10).
Preferably, the graphene oxide in the graphene oxide aqueous dispersion has a sheet diameter of 30 to 50 μm.
Preferably, in the spinning solution, the mass ratio of poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid to graphene oxide is (1-99): (99-1).
Preferably, the reduction reaction mode comprises chemical reduction, irradiation reduction or high-temperature reduction;
the reducing agent for chemical reduction comprises one or more of hydroiodic acid, hydrazine hydrate, sodium citrate and ascorbic acid, and the volume ratio of the spinning solution to the reducing agent for chemical reduction is 1: (10-100);
the irradiation reduction conditions include: the light source comprises Co 60 Gamma rays with irradiation dose of 0.1-1000 kGy;
the high-temperature reduction temperature is 800-2800 ℃ and the high-temperature reduction time is 30 min-8 h.
Preferably, the temperature of the chemical reduction is 15-30 ℃ and the time is 8-14 h.
The invention also provides the reduced graphene oxide composite material obtained by the preparation method.
The invention also provides application of the reduced graphene oxide composite material in wearable equipment.
The invention provides a preparation method of a reduced graphene oxide composite fiber, which comprises the following steps: mixing 3, 4-ethylenedioxythiophene monomer, polystyrene sulfonic acid, oxidant and water, and performing chemical polymerization reaction to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution; mixing the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution and graphene oxide aqueous dispersion to obtain spinning solution; carrying out wet spinning on the spinning solution to obtain a composite fiber precursor; and carrying out a reduction reaction on the composite fiber precursor to obtain the reduced graphene oxide composite fiber.
Poly (3, 4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS) are added as conductive adhesives, wherein the poly (3, 4-ethylenedioxythiophene) is conjugated with graphene oxide pi-pi, so that a conjugated system is increased, and the conductivity of the composite material is enhanced; PSS increases the spacing between graphene sheets through electrostatic repulsion, so that wrinkling of the graphene sheets is reduced, meanwhile PSS spans the sheets and forms pi-pi conjugation with graphene to bridge the graphene sheets, and the stretching resistance of the composite material is enhanced. In addition, the poly (3, 4-ethylenedioxythiophene)/poly-p-styrenesulfonic acid solution and the graphene oxide aqueous dispersion are prepared respectively, and then the poly (3, 4-ethylenedioxythiophene)/poly-p-styrenesulfonic acid aqueous dispersion solution and the graphene oxide aqueous dispersion solution are mixed, so that the doping amount of the poly (3, 4-ethylenedioxythiophene)/poly-p-styrenesulfonic acid can be accurately controlled, and the industrial continuous production operation is more convenient. Compared with pure RGO fibers, the reduced graphene oxide composite material prepared by the preparation method provided by the invention has higher fiber conductivity and tensile resistance.
Drawings
FIG. 1 is an infrared spectrum of PEDOT: PSS obtained in example 1;
FIG. 2 is a Raman spectrum of RGO fibers and the reduced graphene oxide composite material obtained in example 1;
FIG. 3 is a scanning electron micrograph of RGO fibers;
FIG. 4 is a scanning electron micrograph of the reduced graphene oxide composite material obtained in example 1;
FIG. 5 is a graph of electrical conductivity of RGO fibers and reduced graphene oxide composites obtained in examples 1-4;
fig. 6 is a graph of fiber break strength versus elongation at break for RGO fibers and the reduced graphene oxide composite material obtained in example 1.
Detailed Description
The invention provides a preparation method of a reduced graphene oxide composite fiber, which comprises the following steps:
mixing 3, 4-ethylenedioxythiophene monomer, polystyrene sulfonic acid, oxidant and water, and performing chemical polymerization reaction to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution;
mixing the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution and graphene oxide aqueous dispersion to obtain spinning solution;
carrying out wet spinning on the spinning solution to obtain a composite fiber precursor;
and carrying out a reduction reaction on the composite fiber precursor to obtain the reduced graphene oxide composite fiber.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, 3, 4-Ethylenedioxythiophene (EDOT) monomer, polystyrene sulfonic acid (PSS), oxidant and water are mixed for chemical polymerization reaction, so as to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS) solution.
In the present invention, the oxidizing agent preferably comprises a soluble trivalent iron salt and/or monovalent cation persulfate salt, and further preferably comprises a mixture of a soluble trivalent iron salt and monovalent cation persulfate salt.
In the present invention, the soluble trivalentThe ferric salt preferably comprises FeCl 3 And/or Fe 2 (SO 4 ) 3 Further preferably FeCl 3 。
In the present invention, the monovalent cation persulfate preferably comprises Na 2 S 2 O 8 、K 2 S 2 O 8 And (NH) 4 ) 2 S 2 O 8 One or more of them, more preferably Na 2 S 2 O 8 。
In the present invention, the oxidizing agent is preferably FeCl 3 And Na (Na) 2 S 2 O 8 Is a mixture of (a) and (b); the FeCl 3 And Na (Na) 2 S 2 O 8 FeCl in the mixture of (2) 3 And Na (Na) 2 S 2 O 8 The ratio of the amounts of the substances is preferably (0.1 to 1): (1 to 10), more preferably (0.2 to 0.8): (1-5).
In the present invention, the water is preferably deionized water.
In the present invention, the ratio of the amounts of the 3, 4-ethylenedioxythiophene monomer and polystyrene sulfonic acid is preferably 1: (0.1 to 10), more preferably 1: (0.3 to 5), more preferably 1: (1-4).
In the present invention, the ratio of the amounts of the 3, 4-ethylenedioxythiophene monomer and the oxidant is preferably 1: (1.1 to 11), more preferably 1: (1.2-5.8).
In the present invention, when the oxidizing agent is preferably FeCl 3 And Na (Na) 2 S 2 O 8 The 3, 4-ethylenedioxythiophene monomer and FeCl 3 The ratio of the amounts of substances is preferably 1: (0.1 to 1), more preferably 1: (0.2-0.8); the 3, 4-ethylenedioxythiophene monomer and Na 2 S 2 O 8 The ratio of the amounts of substances is preferably 1: (1 to 10), more preferably 1: (1-5).
In the present invention, the ratio of the amounts of the 3, 4-ethylenedioxythiophene monomer and water is preferably 1: (1000-10000).
In the present invention, the oxidizing agent is preferably used in the form of an oxidizing agent solution; the solvent of the oxidant solution is preferably waterThe water is preferably deionized water. In the present invention, the oxidizing agent is preferably FeCl 3 And Na (Na) 2 S 2 O 8 When a mixture of (2) is used; the FeCl 3 And Na (Na) 2 S 2 O 8 Respectively by FeCl 3 Solution and Na 2 S 2 O 8 The solution is used; the FeCl 3 The concentration of the solution is preferably 0.5 to 5mol/L, more preferably 1 to 3mol/L; the Na is 2 S 2 O 8 The concentration of the solution is preferably 0.5 to 5mol/L, more preferably 1 to 3mol/L.
In the present invention, the temperature of the chemical polymerization reaction is preferably 15 to 30 ℃, and the time is preferably 8 to 30 hours, and more preferably 10 to 24 hours; the chemical polymerization is preferably carried out under stirring, and the stirring speed is preferably 300-3000 rpm.
After the chemical polymerization reaction, the invention preferably further comprises the step of washing the obtained chemical polymerization reaction system with water to obtain the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution. In the present invention, the number of times of the water washing is preferably 3.
The invention preferably also includes determining the solids content of the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution. The method for determining the solid content of the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution is not particularly limited, and can be performed by adopting technical schemes well known to those skilled in the art.
After obtaining a poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution, the invention mixes the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution with graphene oxide aqueous dispersion to obtain spinning solution.
In the present invention, the concentration of the graphene oxide aqueous dispersion is preferably 15 to 20mg/mL.
After said mixing, the invention preferably further comprises concentrating the resulting mixed system, preferably by centrifugation.
In the present invention, in the spinning solution, the mass ratio of poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid to graphene oxide is preferably (1 to 99): (99 to 1), more preferably (2 to 50): (98-50); the concentration of the graphene oxide is preferably 15-20 mg/mL.
After the spinning solution is obtained, the invention carries out wet spinning on the spinning solution to obtain the precursor of the composite fiber.
In the present invention, the parameters of the wet spinning include: the coagulation bath preferably includes one or more of glacial acetic acid, ethyl acetate, an acetone-isopropyl alcohol-calcium chloride mixed solvent, and an acetone-isopropyl alcohol-lithium chloride mixed solvent.
After the composite fiber precursor is obtained, the composite fiber precursor is subjected to a reduction reaction, so that the reduced graphene oxide composite fiber is obtained.
In the present invention, the reduction reaction preferably includes chemical reduction, irradiation reduction and high-temperature reduction, and further preferably chemical reduction.
In the present invention, the reagent for chemical reduction preferably includes one or more of hydroiodic acid, hydrazine hydrate, sodium citrate and ascorbic acid; the concentration of the hydroiodic acid is preferably 30 to 55wt%. In the present invention, the volume ratio of the spinning solution to the chemically reduced reagent is preferably 1: (10-100). In the present invention, the temperature of the chemical reduction is preferably 15 to 30℃and the time is preferably 8 to 14 hours.
In the present invention, the irradiation reduction conditions preferably include: the light source preferably comprises Co 60 The irradiation dose of gamma rays is preferably 0.1-1000 kGy.
In the present invention, the high temperature reduction is preferably performed at 800 to 2800 ℃ for 30min to 8h.
After the reduction reaction, the method preferably further comprises the steps of washing, collecting and drying the obtained precursor of the reduced composite fiber to obtain the reduced graphene oxide composite fiber.
In the present invention, the washing preferably includes sequentially performing ethanol washing and water washing, and the parameters and operations of the ethanol washing and water washing are not particularly limited as long as the excessive impurities can be completely removed.
In the present invention, the collecting is preferably collecting the resulting washed fiber composite material onto a reel.
In the present invention, the temperature of the drying is preferably room temperature, i.e., neither additional heating nor additional cooling is required.
The invention also provides the reduced graphene oxide composite fiber obtained by the preparation method. The reduced graphene oxide composite fiber provided by the invention has excellent conductivity and stretching resistance.
The invention also provides application of the reduced graphene oxide composite fiber in wearable equipment. In the invention, the reduced graphene oxide composite fiber has excellent conductivity and stretching resistance, so that the reduced graphene oxide composite fiber can be applied to wearable equipment.
The reduced graphene oxide composite fiber, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
1) Dispersing 1 part by weight of EDOT and 0.6 part by weight of PSS in 130 parts by weight of deionized water, adding Na 2 S 2 O 8 Na at a concentration of 1mol/L in an amount of 2 parts by weight 2 S 2 O 8 Adding FeCl into the solution 3 FeCl with concentration of 1mol/L with content of 0.3 weight part 3 The solution was magnetically stirred for 24h to obtain a PEDOT/PSS stock solution.
2) And (3) centrifugally washing the obtained PEDOT/PSS original solution to obtain the PEDOT/PSS aqueous solution.
3) The solids content of the PEDOT/PSS aqueous solution was calculated by the weighing method to be 1.14%.
4) 1 part by weight of graphene oxide was dispersed in 56 parts by weight of water to prepare an aqueous GO dispersion of 18 mg/mL.
5) Uniformly mixing the GO aqueous dispersion and the PEDOT/PSS aqueous solution according to the mass ratio of 20:80 of the PEDOT/GO, and centrifugally concentrating to obtain the GO-PEDOT/PSS spinning solution.
6) Filling GO/PEDOT/PSS spinning solution into a needle cylinder, and injecting the spinning solution into glacial acetic acid coagulation bath at an injection speed of 0.200mL/min (the volume ratio of the spinning solution to the glacial acetic acid is 1: 60).
7) 47% by weight HI (volume ratio of dope to hydroiodic acid 1:30 Reducing at room temperature for 14h; and cleaning the fiber, collecting the fiber to a winding drum, and drying the fiber at room temperature to obtain the RGO/PEDOT/PSS composite fiber.
Example 2
1) Dispersing 1 part by weight of EDOT and 1.5 parts by weight of PSS in 500 parts by weight of deionized water, adding Na 2 S 2 O 8 Na at a concentration of 1mol/L in an amount of 4 parts by weight 2 S 2 O 8 Adding FeCl into the solution 3 FeCl with concentration of 1mol/L with content of 0.5 weight part 3 The solution was magnetically stirred for 24h to obtain a PEDOT/PSS stock solution.
2) And (3) centrifugally washing the obtained PEDOT/PSS original solution to obtain the PEDOT/PSS aqueous solution.
3) The solid content of the PEDOT/PSS aqueous solution was calculated by a weighing method and found to be 1.30%.
4) 1 part by weight of graphene oxide was dispersed in 56 parts by weight of water to prepare an aqueous GO dispersion of 18 mg/mL.
5) Uniformly mixing the GO aqueous dispersion and the PEDOT/PSS aqueous solution according to the mass ratio of PEDOT to GO of 10:90, and centrifugally concentrating to obtain the GO-PEDOT/PSS spinning solution.
6) Filling GO/PEDOT/PSS spinning solution into a needle cylinder, and injecting the spinning solution into glacial acetic acid coagulation bath at an injection speed of 0.200mL/min (the volume ratio of the spinning solution to the glacial acetic acid is 1: 30).
7) 45wt% HI (volume ratio of dope to hydroiodic acid 1:10 Reducing at room temperature for 10h; and cleaning the fiber, collecting the fiber to a winding drum, and drying the fiber at room temperature to obtain the RGO/PEDOT/PSS composite fiber.
Example 3
1) Dispersing 1 part by weight of EDOT and 3 parts by weight of PSS in 900 parts by weight of deionized water, adding Na 2 S 2 O 8 6 parts by weight of Na having a concentration of 1mol/L 2 S 2 O 8 Adding FeCl into the solution 3 FeCl with concentration of 1mol/L with content of 0.7 weight part 3 The solution was magnetically stirred for 24h to obtain a PEDOT/PSS stock solution.
2) And (3) centrifugally washing the obtained PEDOT/PSS original solution to obtain the PEDOT/PSS aqueous solution.
3) The solid content of the PEDOT/PSS aqueous solution was calculated by a weighing method and found to be 1.35%.
4) 1 part by weight of graphene oxide was dispersed in 56 parts by weight of water to prepare an aqueous GO dispersion of 18 mg/mL.
5) Uniformly mixing the GO aqueous dispersion and the PEDOT/PSS aqueous solution according to the mass ratio of PEDOT/GO of 15:85, and centrifugally concentrating to obtain the GO-PEDOT/PSS spinning solution.
6) Filling GO/PEDOT/PSS spinning solution into a needle cylinder, and injecting the spinning solution into glacial acetic acid coagulation bath at an injection speed of 0.200mL/min (the volume ratio of the spinning solution to the glacial acetic acid is 1: 30).
7) 47% by weight HI (volume ratio of dope to hydroiodic acid 1:30 Reducing at room temperature for 12h; and cleaning the fiber, collecting the fiber to a winding drum, and drying the fiber at room temperature to obtain the RGO/PEDOT/PSS composite fiber.
Example 4
1) Dispersing 1 part by weight of EDOT and 5 parts by weight of PSS in 1200 parts by weight of deionized water, adding Na 2 S 2 O 8 Na at a concentration of 1mol/L in an amount of 8 parts by weight 2 S 2 O 8 Adding FeCl into the solution 3 FeCl with concentration of 1mol/L with content of 0.9 weight part 3 The solution was magnetically stirred for 24h to obtain a PEDOT/PSS stock solution.
2) And (3) centrifugally washing the obtained PEDOT/PSS original solution to obtain the PEDOT/PSS aqueous solution.
3) The solid content of the PEDOT/PSS aqueous solution was calculated by the weighing method to be 1.39%.
4) 1 part by weight of graphene oxide was dispersed in 56 parts by weight of water to prepare an aqueous GO dispersion of 18 mg/mL.
5) Uniformly mixing the GO aqueous dispersion and the PEDOT/PSS aqueous solution according to the mass ratio of PEDOT to GO of 25:75, and centrifugally concentrating to obtain the GO-PEDOT/PSS spinning solution.
6) Filling GO/PEDOT/PSS spinning solution into a needle cylinder, and injecting the spinning solution into glacial acetic acid coagulation bath at an injection speed of 0.200mL/min (the volume ratio of the spinning solution to the glacial acetic acid is 1: 60).
7) 55wt% HI (volume ratio of dope to hydroiodic acid 1:30 Reducing for 8 hours at room temperature; and cleaning the fiber, collecting the fiber to a winding drum, and drying the fiber at room temperature to obtain the RGO/PEDOT/PSS composite fiber.
The electrical conductivity of the composite fibers obtained in examples 1 to 4 was measured by a four-probe method, and the breaking strength and breaking elongation of the composite fibers obtained in examples 1 to 4 were measured by an electronic universal material strength tester. The results are shown in Table 1.
Table 1 results of Performance test of the composite fibers obtained in examples 1 to 4
As can be seen from table 1: the prepared RGO is PEDOT/PSS composite fiber with the conductivity of 30-38S/cm, the breaking strength of 200-400 MPa and the breaking elongation of 2-5%.
FIG. 1 is an infrared spectrum of PEDOT: PSS obtained in example 1; as can be seen from fig. 1: the PEDOT/PSS has C= C, C-O-C, C-O, C-S, S =O and other absorption peaks, which shows that the PEDOT/PSS is successfully prepared.
FIG. 2 is a Raman spectrum of RGO fibers and the reduced graphene oxide composite material obtained in example 1; as can be seen from fig. 2: the Raman spectrum of the reduced graphene oxide composite material has characteristic peaks of functional groups contained in PEDOT/PSS and RGO, which shows that RGO-PEDOT/PSS composite fiber is successfully prepared. The ratio of the D peak to the G peak in the RGO Raman spectrum represents the defect of RGO, I D /I G The larger the C atom lattice defect degree is, the larger the C atom lattice defect degree is. The inclusion of PEDOT/PSS increases the extent of RGO defects, but because of the PEDOT/PSS as a conductive adhesive, the interlayer acting force of the sheet is increased, so that the breaking strength of the fiber is improved; meanwhile, the defect degree of the reduced graphene oxide composite fiber is improved, and the electrode material prepared from the reduced graphene oxide composite fiber has better electrochemical performance.
Fig. 3 is a scanning electron micrograph of RGO fiber, and fig. 4 is a scanning electron micrograph of the reduced graphene oxide composite material obtained in example 1. As can be seen from fig. 3 to 4: after the graphene oxide is compounded with PEDOT/PSS, fiber wrinkles are obviously reduced, the surface is smoother, and the orientation degree is improved.
FIG. 5 is a graph of electrical conductivity of RGO fibers and reduced graphene oxide composites obtained in examples 1-4; as can be seen from fig. 5: after graphene oxide is compounded with PEDOT/PSS, the fiber conductivity is improved along with the increase of the content of PEDOT/PSS.
Fig. 6 is a graph of fiber break strength versus elongation at break for RGO fibers and the reduced graphene oxide composite material obtained in example 1. As can be seen from fig. 6: the breaking strength of the reduced graphene oxide composite material is improved by 2-3 times compared with RGO, and the breaking elongation is not greatly different.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the reduced graphene oxide composite fiber is characterized by comprising the following steps:
mixing 3, 4-ethylenedioxythiophene monomer, polystyrene sulfonic acid, oxidant and water, and performing chemical polymerization reaction to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution;
mixing the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution and graphene oxide aqueous dispersion to obtain spinning solution;
carrying out wet spinning on the spinning solution to obtain a composite fiber precursor;
carrying out a reduction reaction on the composite fiber precursor to obtain the reduced graphene oxide composite fiber;
the ratio of the amounts of the 3, 4-ethylenedioxythiophene monomer and polystyrene sulfonic acid is 1: (0.1 to 0.46);
the solid content of the poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid solution was 1.14%, 1.30%, 1.35% and 1.39%;
the sheet diameter of the graphene oxide in the graphene oxide aqueous dispersion liquid is 30-50 mu m;
the concentration of the graphene oxide aqueous dispersion liquid is 15-20 mg/mL;
in the spinning solution, the mass ratio of poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid to graphene oxide is (1-99): (99-1).
2. The method of claim 1, wherein the oxidizing agent comprises a soluble ferric salt and/or a monovalent cation persulfate salt, the soluble ferric salt comprising feci 3 And/or Fe 2 (SO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The monovalent cation persulfate comprises Na 2 S 2 O 8 、K 2 S 2 O 8 And (NH) 4 ) 2 S 2 O 8 One or more of the following.
3. The method according to claim 2, wherein when the oxidizing agent is a mixture of a soluble trivalent iron salt and a monovalent cation persulfate, the mass ratio of the 3, 4-ethylenedioxythiophene monomer, the soluble trivalent iron salt and the monovalent cation persulfate is 1: (0.1-1): (1-10).
4. The method according to claim 1, wherein the reduction reaction comprises chemical reduction, irradiation reduction or high temperature reduction;
the reducing agent for chemical reduction comprises one or more of hydroiodic acid, hydrazine hydrate, sodium citrate and ascorbic acid, and the volume ratio of the spinning solution to the reducing agent for chemical reduction is 1: (10-100);
the irradiation reduction conditions include: the light source comprises Co 60 Gamma rays with irradiation dose of 0.1-1000 kGy;
the high-temperature reduction temperature is 800-2800 ℃ and the high-temperature reduction time is 30 min-8 h.
5. The method according to claim 4, wherein the chemical reduction is carried out at a temperature of 15 to 30℃for a period of 8 to 14 hours.
6. The reduced graphene oxide composite material obtained by the production method according to any one of claims 1 to 5.
7. Use of the reduced graphene oxide composite material of claim 6 in a wearable device.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434770A (en) * | 2008-11-28 | 2009-05-20 | 华东理工大学 | Preparation of antistatic water solution |
| CN103289063A (en) * | 2013-06-14 | 2013-09-11 | 电子科技大学 | Method for preparing polythiophene-base graphene oxide reduced composite material |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434770A (en) * | 2008-11-28 | 2009-05-20 | 华东理工大学 | Preparation of antistatic water solution |
| CN103289063A (en) * | 2013-06-14 | 2013-09-11 | 电子科技大学 | Method for preparing polythiophene-base graphene oxide reduced composite material |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
Non-Patent Citations (3)
| Title |
|---|
| "Highly-wrinkled reduced graphene oxide-conductive polymer fibers for flexible fiber-shaped and interdigital-designed supercapacitors";Bo Li et al.;《Journal of Power Sources》;第117-124页 * |
| PEDOT/PSS的合成及在抗静电涂料中的应用;孙东成;孙德生;;高分子材料科学与工程(07);第111-113页 * |
| 高电导率聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸复合物的制备及表征;王兴平;杜鹃;罗艳;钟毅;;化工新型材料(04);第97-99页、第150页 * |
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