CN115101355B - Stretchable elastic conductive polymer-based full-gel fibrous supercapacitor and preparation method thereof - Google Patents
Stretchable elastic conductive polymer-based full-gel fibrous supercapacitor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 14
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- 229920000642 polymer Polymers 0.000 claims abstract description 13
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
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- 239000011530 conductive current collector Substances 0.000 claims abstract description 8
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- 239000000243 solution Substances 0.000 claims description 43
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004146 energy storage Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical group NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical group NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- 239000003990 capacitor Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a stretchable elastic conductive polymer-based all-gel fibrous supercapacitor and a preparation method thereof. The preparation method comprises the following steps: sputtering a conductive current collector on the surface of the hydrogel fiber, and assembling the hydrogel fiber sputtered by the conductive current collector by adopting a polyvinyl alcohol gel electrolyte; the hydrogel fiber is prepared by dissolving an elastic polymer matrix, a conductive polymer monomer, a crosslinking agent and an acid solution in deionized water, mixing with an initiator solution, injecting into a mold, freezing, and performing in-situ polymerization and crosslinking reaction. The hydrogel fiber has excellent conductivity, mechanical strength and elasticity; the all-gel fibrous supercapacitor has excellent electrochemical performance and intrinsic stretchability.
Description
Technical Field
The invention belongs to the technical field of flexible energy storage and wearable electronic devices, and particularly relates to a stretchable and elastic conductive polymer-based all-gel fibrous supercapacitor and a preparation method thereof.
Background
With the rise of flexible wearable equipment, the stretchable all-solid-state super capacitor has been widely focused in the field of flexible wearable energy storage devices due to the high power density, the electrochemical performance with high charge and discharge speed, and the excellent stretchability, stretching recovery and mechanical stability. Hydrogels are one of the most potential candidate materials for flexible wearable devices because of their excellent flexibility, elasticity, and ability to accommodate a variety of complex deformations. The conductive polymer is a functional material with excellent pseudo-capacitance energy storage performance, and the conductive polymer-based elastic hydrogel fiber has the excellent performances of the conductive polymer, such as electrical performance, high mechanical performance, easy preparation, processability and the like, has the advantages of biocompatibility, air permeability, braiding and the like of the hydrogel fiber, and has potential application value in the aspects of wearable sensing, energy storage, biomedical detection devices and the like.
High performance supercapacitor electrode materials can be obtained by polymerizing the conductive polymers in situ in the hydrogel elastic matrix and forming a continuous network, however the current materials are predominantly in the form of blocks or sheets. In addition, the existing preparation method of the conductive hydrogel fiber mainly comprises the steps that conductive particles are filled in a hydrogel matrix or grow in situ on the outer layer of the hydrogel, the prepared hydrogel fiber is difficult to meet the requirement of high conductivity under stretching, and a full-gel fibrous supercapacitor with intrinsic elasticity and stretchability has not been reported yet. Therefore, development of an all-gel fibrous supercapacitor with intrinsic elasticity is needed.
Chinese patent CN104282444a discloses a stretchable linear supercapacitor with a carbon nanotube/polyaniline composite material as a counter electrode and a method for preparing the same, wherein the method uses a stretchable polymer as a fiber substrate, and the carbon nanotube/polyaniline composite material formed under the condition of pre-stretching has a stretchability which is not intrinsic property of the material, and the polymer fiber substrate used has the disadvantages of reduced total capacity of the device and poor stability.
Document Advanced Materials,2018;30 (18) 1800124 reports a stretchable all-gel graphene/conductive polymer hydrogel fibrous supercapacitor whose stretchability stems from the wavy geometry of the device, and which is thus poor in tensile strength and stretch-rebound cycle life.
Disclosure of Invention
The invention aims to solve the technical problem of providing a stretchable and elastic conductive polymer-based all-gel fibrous supercapacitor and a preparation method thereof, so as to overcome the defects of low conductivity of hydrogel fibers, low capacity, weak mechanical property and the like of the stretchable fibrous supercapacitor in the prior art.
The invention provides a stretchable conductive polymer-based hydrogel fiber which is prepared by dissolving an elastic polymer matrix, a conductive polymer monomer, a crosslinking agent and an acid solution in deionized water to obtain a mixed solution, mixing the mixed solution with an initiator solution, injecting the mixed solution into a mold, freezing, performing in-situ polymerization and crosslinking reaction, removing the mold, purifying and freeze-drying.
Preferably, in the hydrogel fiber, the elastic polymer matrix is a polymer containing polyhydroxy, and the polymer containing polyhydroxy includes one or more of polyvinyl alcohol, polyacrylamide, polyacrylic acid and polyethylene glycol.
Preferably, in the hydrogel fiber, the conductive polymer monomer includes one or more of aniline, pyrrole and thiophene.
Preferably, in the hydrogel fiber, the cross-linking agent is 3-aminophenylboronic acid ABA.
Preferably, in the hydrogel fiber, the acid solution comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid solutions of 0.1-6 mol/L.
Preferably, in the hydrogel fiber, the initiator comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide.
The invention also provides a preparation method of the stretchable conductive polymer-based hydrogel fiber, which comprises the following steps:
(1) Dissolving an elastic polymer matrix, a conductive polymer monomer, a cross-linking agent and an acid solution in deionized water to obtain a mixed solution, and dissolving an initiator in the deionized water to obtain an initiator solution;
(2) Mixing the mixed solution obtained in the step (1) with an initiator solution, injecting the mixture into a mold, freezing, performing in-situ polymerization and crosslinking reaction, removing the mold, purifying, and freeze-drying to obtain the hydrogel fiber.
Preferably, in the above method, the concentration of the elastic polymer matrix in the mixed solution in the step (1) is 1 to 20wt% and the concentration of the conductive polymer monomer is 0.025 to 1mol/L.
Preferably, in the above method, the molar ratio of the initiator in the step (2) to the conductive polymer monomer in the mixed solution is 0.5-2.
Preferably, in the above method, the mixing in the step (2) is performed at 0 to 5 ℃; freezing is as follows: the solution was rapidly placed in a liquid nitrogen bath or dry ice bath and frozen instantaneously.
Preferably, in the above method, the die in the step (2) is a tetrafluoro tube with a diameter of 0.1-2 mm.
Preferably, in the above method, the temperature of the in-situ polymerization and crosslinking reaction in the step (2) is 0 to-80 ℃ for 6 to 96 hours.
Preferably, in the above method, the purifying in step (2) is: water and ethanol are used to remove inorganic salts, unreacted substances and oligomers in the fiber.
The invention also provides a stretchable and elastic conductive polymer-based all-gel fibrous supercapacitor, which comprises the hydrogel fiber.
The invention also provides a preparation method of the stretchable and elastic conductive polymer-based all-gel fibrous supercapacitor, which comprises the following steps:
and sputtering the conductive current collector on the surface of the hydrogel fiber, and assembling the hydrogel fiber sputtered by the conductive current collector into the full-gel fibrous supercapacitor by adopting the polyvinyl alcohol gel electrolyte.
Preferably, in the above method, the conductive substance sputtered by the conductive current collector includes one or more of gold, silver, platinum and carbon.
Preferably, in the above method, the polyvinyl alcohol gel electrolyte is one or several of phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid aqueous solutions of polyvinyl alcohol, the concentration of polyvinyl alcohol is 1-10wt%, and the concentration of phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid is 0.1-10wt%, more preferably, the polyvinyl alcohol gel electrolyte is: sulfuric acid/polyvinyl alcohol and phosphoric acid/polyvinyl alcohol gel electrolyte.
The invention also provides application of the stretchable and elastic conductive polymer-based full-gel fibrous supercapacitor in a flexible wearable energy storage device.
The invention firstly adopts a die method and an ice template method to prepare the stretchable conductive polymer-based hydrogel fiber, and a conductive current collector is sputtered on the surface of the stretchable conductive polymer-based hydrogel fiber to prepare a fibrous hydrogel electrode, and then the fibrous electrode is assembled into the stretchable full-gel fibrous supercapacitor by adopting a gel electrolyte.
Advantageous effects
(1) The invention adopts a mould method and an ice template method, takes 3-aminophenylboric acid as a cross-linking agent, and prepares the hydrogel fiber with excellent conductivity, good mechanical strength and elasticity by in-situ polymerization of an elastic matrix and cross-linking of conductive polymer and the elastic matrix by borate bonds.
(2) The invention adopts the ion sputtering instrument to sputter the conductive current collector on the surface of the gel fiber after freeze drying, further improves the conductivity of the hydrogel fiber, and the assembled symmetrical full-gel fibrous supercapacitor has excellent electrochemical performance and intrinsic stretchability.
Drawings
FIG. 1 is a graph showing the mechanical properties of the different hydrogel fibers of example 1.
FIG. 2 is an SEM image of an ABA crosslinked PANI-ABA-PVA hydrogel fiber containing in example 1.
Fig. 3 is an assembled and stretched view of the fully gel symmetrical fibrous supercapacitor of example 1.
Fig. 4 is an ac impedance spectrum of the hydrogel fibers in example 1, example 2, and example 3.
Fig. 5 is a constant current charge-discharge diagram of the assembled full gel supercapacitor of example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The main reagent sources are as follows: polyvinyl alcohol 124 (alcoholysis 98-99.8%), aniline, pyrrole, hydrochloric acid, sulfuric acid, phosphoric acid, potassium persulfate, ammonium persulfate are all purchased from national pharmaceutical group chemical reagent Co., ltd, 3-aminophenylboronic acid (ABA) is purchased from Shaoshan long-distance chemical technology (Shanghai) Co., ltd, and ethanol is purchased from Shanghai Taitan technology Co., ltd. The raw materials and equipment used in the present invention are all commonly used raw materials and equipment unless otherwise specified.
The tensile property testing method comprises the following steps: the mechanical properties of the prepared hydrogel fibers were tested at 23℃under 60% humidity using an MTS E42 stretcher, with a 20mm clamp spacing and a 10mm stretching rate -1 The number of samples was 5, the diameter of the hydrogel fiber was calculated by a microscope before the tensile test, and the relationship between the elongation at break and the tensile strength of the sample was obtained by the tensile test.
Electrochemical testing: the electrochemical workstation adopted in the electrochemical test is Interface1000E of Gamry electrochemical instrument company in the United states, and the experimental temperature is room temperature. Direct current charge and Discharge test (Galvanostatic Charge/Discharge, GCD): the voltage ranges from 0 to 1V, and the current densities are respectively 0.5, 1, 2 and 5A g -1 . Ac impedance spectroscopy test (Electrochemical Impedance Spectroscopy, EIS): the frequency range is 0.01HZ-10 5 HZ, voltage disturbance was 5mV.
Example 1
First, 10g of polyvinyl alcohol (PVA) was dissolved in 90ml of water at 95℃to prepare a 10wt% PVA aqueous solution. Preparation of solution A by weighing 0.0163g of 3-aminophenylboronic acid and adding 833. Mu.L of 6mol/L hydrochloric acid solution thereto, completely dissolving 3-aminophenylboronic acid by ultrasound, adding 140. Mu.L of aniline and stirring to obtain a homogeneous solution; subsequently, 3.5ml of PVA solution was added thereto and stirred into a homogeneous solution. Preparation of solution B0.411 g of potassium persulfate was weighed and dissolved in 1ml of water. Cooling the solution A, B in a refrigerator for 30min, cooling to 5 ℃, mixing the solution A, B, and degassing bubbles after uniform mixing. The mixed solution was injected into a tetrafluoro tube fiber mold having a diameter of 1mm using a syringe and rapidly frozen in a liquid nitrogen freezing bath, followed by transferring to a freezer for reaction at-20 ℃ for 24 hours.
After the reaction, the hydrogel fiber with the mold is taken out, thawed and removed, the hydrogel fiber is soaked in deionized water and ethanol for 24 hours to remove unreacted monomers and oligomers, and then the hydrogel fiber is freeze-dried. And (3) sputtering gold on the surface of the freeze-dried fiber by adopting an ion sputtering instrument (sputtering for 360s under vacuum) to obtain the fiber electrode material. A sulfuric acid (10 wt%) solution of PVA (10 wt%) was formulated for use as the inner layer gel electrolyte and a phosphoric acid (10 wt%) solution of PVA (10 wt%) was formulated for use as the outer layer gel electrolyte. Firstly, a 1mol/L sulfuric acid solution is used for soaking a gel fiber electrode, and after the fiber is completely absorbed in water and swelled, a layer of sulfuric acid electrolyte solution of PVA is used for coating the outer layer of the fiber. And after drying, assembling the two hydrogel fiber electrodes, coating a layer of PVA phosphoric acid electrolyte on the outer layer, and drying at room temperature to obtain the full gel fibrous supercapacitor.
Firstly, it is verified that 3-aminophenylboric acid in the hydrogel can improve the mechanical properties of hydrogel fibers, as shown in figure 1, the mechanical properties of the PANI-ABA-PVA hydrogel fibers containing ABA crosslinking are obviously higher than those of pure PVA hydrogel fibers and are also higher than those of PANI-PVA hydrogel fibers without ABA (except that no ABA is added in the preparation method, the preparation method is the same as that of the PANI-ABA-PVA hydrogel fibers containing ABA crosslinking, as shown in figure 2, the prepared hydrogel fibers have obvious network structure, the assembled form is shown in figure 3 and have certain tensile properties, alternating impedance (EIS) test is carried out for obtaining the conductivity of the hydrogel fibers, as shown in figure 4, the conductivity of the hydrogel fibers in example 1 is 11S/cm., and figure 5 is the electrochemical performance test of the symmetrical all-gel fibrous supercapacitor, and the electrochemical performance test is carried out at 0.5 mAcm -2 Shows 254mF cm at a current density of (C) -2 Is a specific capacitance of (a).
Example 2
10g of polyvinyl alcohol (PVA) was dissolved in 90ml of water at 95℃to prepare a 10wt% PVA aqueous solution. First, preparing a solution A: 0.0217g ABA is weighed and dissolved in 833 mu L of 6mol/L hydrochloric acid, 667 mu L deionized water is added into the solution, and after the solution is stirred uniformly, 170 mu L pyrrole and 2.5ml PVA solution are added into the solution; preparing a solution B: 0.548g of ammonium persulfate was dissolved in 1ml of deionized water. The solution A, B is placed in a refrigerator to be cooled for 30min, the solution A, B is mixed after the temperature reaches 5 ℃, bubbles are removed after the mixture is uniform, the uniformly mixed solution is injected into a tetrafluoro tube fiber mold with the diameter of 1.5mm by using a syringe and is transferred to dry ice to be quickly frozen, and then the mixture is transferred to the refrigerator to be reacted for 12h at the temperature of minus 20 ℃.
After the reaction is finished, taking out the hydrogel fiber with the mould, thawing, removing the mould, soaking the hydrogel fiber for 24 hours by using deionized water and ethanol, and removing impurities such as unreacted monomers, oligomers and the like; the hydrogel fibers were then freeze-dried. The hydrogel fiber of example 2 had a conductivity of 3S/cm as measured by EIS, as shown in FIG. 4. And (3) sputtering platinum on the surface of the freeze-dried fiber by adopting an ion sputtering instrument (sputtering for 180 seconds under vacuum) to obtain the fiber electrode. A sulfuric acid (10 wt%) solution of PVA (10 wt%) was formulated for use as the inner layer gel electrolyte and a phosphoric acid (10 wt%) solution of PVA (10 wt%) was formulated for use as the outer layer gel electrolyte. Firstly, a 1mol/L sulfuric acid solution is used for soaking a gel fiber electrode, and after the fiber is completely absorbed in water and swelled, a layer of sulfuric acid electrolyte solution of PVA is used for coating the outer layer of the fiber. And after drying, assembling the two hydrogel fiber electrodes, coating a layer of PVA phosphoric acid electrolyte on the outer layer, and drying at room temperature to obtain the full gel fibrous supercapacitor. The hydrogel fibers in this example had an elongation at break of 400% and a strength of 300KPa.
Example 3
10g of polyvinyl alcohol (PVA) was dissolved in 90ml of water at 95℃to prepare a 10wt% PVA aqueous solution. Firstly, preparing a solution A, weighing 0.0266g of ABA, dissolving in 833 mu L of 6mol/L hydrochloric acid, adding 667 mu L deionized water, adding 212 mu L aniline into the solution A after the solution A is completely dissolved, and adding 2.5ml of PVA (10 wt percent aqueous solution); solution B:0.6846g ammonium persulfate was dissolved in 1ml deionized water. The solution A, B is placed in a refrigerator to be cooled for 30min, the solution A, B is mixed after the temperature reaches 5 ℃, bubbles are removed after the mixture is uniform, the uniformly mixed solution is injected into a tetrafluoro tube fiber mold with the diameter of 0.5mm by using a syringe and is transferred to dry ice to be quickly frozen, and then the mixture is transferred to the refrigerator to be reacted for 48h at the temperature of minus 20 ℃.
After the reaction is finished, taking out the hydrogel fiber with the mould, thawing, removing the mould, soaking the hydrogel fiber for 24 hours by using deionized water and ethanol, and removing impurities such as unreacted monomers, oligomers and the like; the hydrogel fibers were then freeze-dried. The hydrogel fiber of example 3 had a conductivity of 6S/cm as measured by EIS, as shown in FIG. 4. And (3) sputtering platinum on the surface of the freeze-dried fiber by adopting an ion sputtering instrument (sputtering for 180 seconds under vacuum) to obtain the fiber electrode. A sulfuric acid (10 wt%) solution of PVA (5 wt%) was formulated for use as the inner layer gel electrolyte and a phosphoric acid (10 wt%) solution of PVA (5 wt%) was formulated for use as the outer layer gel electrolyte. Firstly, a 1mol/L sulfuric acid solution is used for soaking a gel fiber electrode, and after the fiber is completely absorbed in water and swelled, a layer of sulfuric acid electrolyte solution of PVA is used for coating the outer layer of the fiber. And after drying, assembling the two hydrogel fiber electrodes, coating a layer of PVA phosphoric acid electrolyte on the outer layer, and drying at room temperature to obtain the full gel fibrous supercapacitor. The hydrogel fibers in this example had an elongation at break of 550% and a strength of 500KPa.
Claims (8)
1. A method of making a hydrogel fiber comprising:
(1) Dissolving an elastic polymer matrix, a conductive polymer monomer, a cross-linking agent and an acid solution in deionized water to obtain a mixed solution, and dissolving an initiator in the deionized water to obtain an initiator solution; wherein the concentration of the elastic polymer matrix in the mixed solution in the step (1) is 1-20 wt%, and the concentration of the conductive polymer monomer is 0.025-1 mol/L; wherein the elastic polymer matrix is a polymer containing polyhydroxy, and the polymer containing polyhydroxy comprises one or two of polyvinyl alcohol and polyethylene glycol; the conductive polymer monomer comprises one or more of aniline, pyrrole and thiophene; the cross-linking agent is 3-aminophenylboric acid ABA;
(2) Mixing the mixed solution obtained in the step (1) with an initiator solution, injecting the mixture into a mold, freezing, performing in-situ polymerization and crosslinking reaction, removing the mold, purifying, and freeze-drying to obtain hydrogel fibers; the temperature of the in-situ polymerization and crosslinking reaction is 0 to 80 ℃ below zero, and the time is 6 to 96 h; wherein the molar ratio of the initiator to the conductive polymer monomer in the mixed solution is 0.5-2.
2. The method of claim 1, wherein the mixing in step (2) is performed at 0-5 ℃; freezing is as follows: the solution was rapidly placed in a liquid nitrogen bath or dry ice bath and frozen instantaneously.
3. The hydrogel fiber according to claim 1, wherein the acid solution in step (1) comprises one or more of 0.1 to 6mol/L of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid solutions; the initiator in the step (2) comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide.
4. A hydrogel fiber made by the method of claim 1.
5. An all gel state fibrous supercapacitor comprising the hydrogel fiber of claim 4.
6. A preparation method of an all-gel fibrous supercapacitor comprises the following steps:
conducting current collector sputtering on the surface of the hydrogel fiber according to claim 4, and assembling the hydrogel fiber sputtered by the conducting current collector into a full gel state fibrous supercapacitor by adopting a polyvinyl alcohol gel electrolyte.
7. The method according to claim 6, wherein the conductive material sputtered by the conductive current collector comprises one or more of gold, silver, platinum, and carbon; the polyvinyl alcohol gel electrolyte is one or more of phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid aqueous solutions of polyvinyl alcohol, the concentration of the polyvinyl alcohol is 1-10wt%, and the concentration of the phosphoric acid, the sulfuric acid, the hydrochloric acid or the nitric acid is 0.1-10wt%.
8. Use of the all-gel fibrous supercapacitor of claim 5 in a flexible wearable energy storage device.
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