CN114395159B - Preparation method of flexible porous conductive material - Google Patents
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- 239000004020 conductor Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 153
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims description 91
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 75
- 239000012528 membrane Substances 0.000 claims description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011888 foil Substances 0.000 claims description 18
- 229920001690 polydopamine Polymers 0.000 claims description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 229920005610 lignin Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 230000006641 stabilisation Effects 0.000 claims description 9
- 238000011105 stabilization Methods 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000005021 flexible packaging material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
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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
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- H01G11/32—Carbon-based
- H01G11/40—Fibres
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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
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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Abstract
The invention provides a preparation method of a flexible porous conductive material, which comprises the following steps: uniformly mixing polydimethylsiloxane and a curing agent in a ratio of 10; adding the pretreated modified conductive fibers, and continuously stirring uniformly; putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process; slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp; heating in an oven to cure, and heating continuously after curing. The method adopts deionized water as the pore-foaming agent, the required material is simple, no complex operation is needed, and the porosity of the prepared porous sample is relatively controllable; the water contact angle of the flexible porous conductive material is reduced from 142.33 degrees to 0 degrees, and the improved wettability can promote the electrolyte to penetrate into the porous electrode, so that the capacitance is improved.
Description
Technical Field
The invention relates to the field of conductive materials, in particular to a preparation method of a flexible porous conductive material.
Background
Supercapacitors and batteries differ most fundamentally in their charge storage mechanism and in the material/structure of the electrodes. Generally, batteries are designed to store charge in the electrode material by undergoing a faradaic reaction to provide a higher energy density. However, supercapacitors store charge by a surface charge storage mechanism, which can provide higher power density. Supercapacitors are energy storage devices with good application prospects, attracting widespread academic and industrial attention over the past decades. Supercapacitors can provide higher energy density than conventional capacitors; compared to batteries, supercapacitors can provide higher power density and longer cycle life. At present, the super capacitor is widely applied to various aspects in life, such as fields of household appliances, transportation, military, aerospace, standby power supplies and the like, and plays a role in protecting, improving and replacing a battery.
Conventional supercapacitors are devices that are typically assembled from a diaphragm sandwiched between two electrodes and then packaged with a liquid electrolyte in a massive battery case, which has significant drawbacks in wearable applications due to its large and bulky size. For example, toxic liquid electrolytes require high-safety packaging materials and techniques to package in order to prevent leakage of the electrolyte during use. Moreover, the components of the super capacitor can only be assembled in specific shapes, such as button and spiral cylinder shapes, and are difficult to be combined with the circuit main board of other functional systems. To overcome these limitations, flexible all-solid-state supercapacitors have emerged as a new class of energy storage devices and have attracted considerable attention in recent years. The flexible all-solid-state supercapacitor is composed of flexible electrodes, solid electrolyte, a diaphragm and flexible packaging materials. The main advantage of this is the use of solid-state electrolytes and flexible electrodes, in contrast to conventional capacitors, which can be assembled into thin, light, small devices of any shape and size, thus increasing their potential for use in the flexible, wearable electronics industry.
The performance of a flexible all-solid-state supercapacitor depends to a large extent on the electrode material and the electrolyte. The assembly of the device is an important factor for determining the performance of the flexible all-solid-state supercapacitor. Therefore, flexible all-solid-state supercapacitors can be divided into two categories according to the way of assembling the electrode materials: a symmetrical flexible all-solid-state supercapacitor and an asymmetrical all-solid-state supercapacitor. Some materials, such as nanocarbon materials, transition metal oxides/hydroxides/sulfides, conductive polymers have been extensively studied as promising flexible electrode materials.
Disclosure of Invention
The technical problem to be solved is as follows: according to the invention, deionized water is used as a pore-foaming agent, the required material is simple, no complex operation is required, and the porosity of the prepared porous sample is relatively controllable; the water contact angle of the flexible porous conductive material is reduced from 142.33 degrees to 0 degrees, and the improved wettability can promote the electrolyte to penetrate into the porous electrode, so that the capacitance is improved.
The technical scheme is as follows: a preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent in a ratio of 10;
(2) Adding the pretreated modified conductive fibers, and continuously stirring uniformly;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
Preferably, the curing agent consists of a mixture of methylhydrogen copolymer chains and a platinum-based catalyst.
Preferably, the mass ratio of the polydimethylsiloxane to the modified conductive fibers is 100 (2-5).
Preferably, the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm.
Preferably, the pretreatment method of the modified conductive fiber comprises the following steps: dissolving the modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding a polydopamine solution, reacting for 1 hour, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5 hours, adjusting the pH value to 3-4 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber.
Preferably, the mass fraction of the polydopamine solution is 3-5%.
Preferably, the preparation method of the modified conductive fiber is as follows:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.1-1.0g of polyvinylpyrrolidone and 8mLN, and obtaining spinning solution A;
and 2, step: 0.5-1g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed evenly;
and step 3: adding the spinning solution A, and stirring for 12 hours at normal temperature to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, setting the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 injecting spinning solutions A of 1.0ml and 2 injecting spinning solutions B of 1.0ml respectively, spinning by adopting a 27G needle at the rotating speed of 3500r/min, adding materials every 2min, and spinning for 8min;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
step 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of the protective gas is 200mL/min in the process;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: and (3) after crushing, placing the obtained product in a direct-current pulse nitrogen normal-pressure plasma jet device for treatment, thus obtaining the modified conductive fiber. Preferably, the mass ratio of the lignin acetate to the polyvinylpyrrolidone in the spinning solution a is 5.
Preferably, the spinning temperature in the step (4) is 20-30 ℃, and the humidity is 25-35%.
The flexible porous conductive material prepared by the preparation method of the flexible porous conductive material is applied to a flexible supercapacitor electrode material.
Has the advantages that:
1. in the invention, because the polydimethylsiloxane has extremely strong hydrophobicity and is generally immiscible with water, the mixture can flow to the center under the action of inertia force through high-speed mechanical stirring, water drops can be thinned by the shearing force of the rotary cutter, so that the mixture is emulsified to form a stable water-in-oil system, and the water drops are uniformly dispersed in the polydimethylsiloxane.
2. The method adopts the deionized water as the pore-foaming agent, the required material is simple, the complex operation is not needed, and the porosity of the prepared porous sample is relatively controllable.
3. According to the invention, the modified carbon fiber is modified and modified by the polydopamine solution, and the polydopamine layer has abundant functional groups on the surface and can be used as an interface layer for post-modification, so that the modified carbon fiber can be better modified with polydimethylsiloxane.
4. After the modified carbon fiber is sintered, the modified carbon fiber still needs protection of Ar in the cooling process, and air is blown into the modified carbon fiber at 350 ℃, so that the surface part of the carbon fiber is oxidized to increase oxygen-containing functional groups, and the hydrophobicity of the carbon fiber is improved.
5. The water contact angle of the flexible porous conductive material is reduced to 0 degree from 142.33 degrees, and the improved wettability can promote the electrolyte to permeate into the porous electrode, so that the capacitance is improved.
Detailed Description
Example 1
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fiber, and continuously stirring uniformly, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by using a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 3 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 3%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.1g of polyvinylpyrrolidone and 8mLN, and obtaining a spinning solution A;
step 2: 0.5g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed evenly;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to be 12cm, setting the electrostatic voltage to be 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, setting 2 injection spinning solutions A to be 1.0ml respectively and 2 injection spinning solutions B to be 1.0ml respectively, spinning at 3500r/min by adopting a 27G needle head, adding materials every 2min, and spinning for 8min at the spinning temperature of 20 ℃ and the humidity of 25%;
and 5: removing the fiber film from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
and 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of the protective gas is 200mL/min in the process;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: crushing, and treating in a direct current pulse nitrogen normal pressure plasma jet device to obtain modified conductive fibers; the gas adopted is He and He/O 2 (99, 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma torch was 60 ℃.
Example 2
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fiber, and continuously and uniformly stirring, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 3.5 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 4%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.3g of polyvinylpyrrolidone and 8mLN, and obtaining a spinning solution A;
and 2, step: 0.6g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and evenly dispersed by ultrasonic;
and step 3: adding the spinning solution A, and stirring for 12 hours at normal temperature to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to be 12cm, setting the electrostatic voltage to be 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, setting 2 injection spinning solutions A to be 1.0ml respectively and 2 injection spinning solutions B to be 1.0ml respectively, spinning at 3500r/min by adopting a 27G needle head, adding materials every 2min, and spinning for 8min at the spinning temperature of 20 ℃ and the humidity of 25%;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
step 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane into an aqueous solution of cobalt acetate, refluxing for 24 hours at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, heating to 140 ℃ from normal temperature at the heating rate of 5 ℃/min, keeping for 30min, then heating to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the process of cooling, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: crushing, and treating in a direct current pulse nitrogen normal pressure plasma jet device to obtain modified conductive fibers; the gas adopted is He and He/O 2 (99, 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma torch was 60 ℃.
Example 3
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fiber, and continuously and uniformly stirring, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in an oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 4 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 5%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of lignin acetate, 0.5g of polyvinylpyrrolidone and 8mLN, and obtaining a spinning solution A;
step 2: 0.7g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed evenly;
and 3, step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to be 12cm, setting the electrostatic voltage to be 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, setting 2 injection spinning solutions A to be 1.0ml respectively and 2 injection spinning solutions B to be 1.0ml respectively, spinning at 3500r/min by adopting a 27G needle head, adding materials every 2min, and spinning for 8min at the spinning temperature of 25 ℃ and the humidity of 30%;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
step 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: crushing, and treating in a direct current pulse nitrogen normal pressure plasma jet device to obtain modified conductive fibers; the gas adopted is He and He/O 2 (99: 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma shower head was 60 ℃.
Example 4
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fiber, and continuously and uniformly stirring, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 3 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 3%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.7g of polyvinylpyrrolidone and 8mLN, and obtaining a spinning solution A;
step 2: 0.8g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed evenly;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 spinning solution A is injected into each spinning device by 1.0ml,2 spinning solution B is injected into each spinning device by 1.0ml, spinning is carried out by adopting a 27G needle head at the rotating speed of 3500r/min, materials are added every 2min, and spinning is carried out for 8min at the spinning temperature of 25 ℃ and the humidity of 30%;
and 5: removing the fiber film from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
step 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane into an aqueous solution of cobalt acetate, refluxing for 24 hours at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: crushing, and treating in a direct current pulse nitrogen normal pressure plasma jet device to obtain modified conductive fibers; the gas adopted is He and He/O 2 (99: 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma shower head was 60 ℃.
Example 5
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fiber, and continuously and uniformly stirring, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in an oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 3.5 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 4%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.9g of polyvinylpyrrolidone and 8mLN, and obtaining a spinning solution A;
step 2: 0.9g of nano tin dioxide powder and 8mLN of N-dimethylformamide solution are mixed and ultrasonically dispersed evenly;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 spinning solution A is injected into each spinning device by 1.0ml,2 spinning solution B is injected into each spinning device by 1.0ml, spinning is carried out by adopting a 27G needle head at the rotating speed of 3500r/min, materials are added every 2min, and spinning is carried out for 8min at the spinning temperature of 30 ℃ and the humidity of 35%;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
step 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and step 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: after being crushed, the mixture is placed in a direct-current pulse nitrogen normal-pressure plasma jet device for treatment, and modified conductive fibers are obtained; the gas adopted is He and He/O 2 (99: 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma shower head was 60 ℃.
Example 6
A preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to a ratio of 10;
(2) Adding the pretreated modified conductive fiber, and continuously and uniformly stirring, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fiber is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
The pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 4 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber; wherein the mass fraction of the polydopamine solution is 5%.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 1.0g of polyvinylpyrrolidone and 8mLN, and obtaining spinning solution A;
and 2, step: 1g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed uniformly;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 spinning solution A is injected into each spinning device by 1.0ml,2 spinning solution B is injected into each spinning device by 1.0ml, spinning is carried out by adopting a 27G needle head at the rotating speed of 3500r/min, materials are added every 2min, and spinning is carried out for 8min at the spinning temperature of 30 ℃ and the humidity of 35%;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
and 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: crushing, and treating in a direct current pulse nitrogen normal pressure plasma jet device to obtain modified conductive fibers; gas employedIs He and He/O 2 (99: 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma shower head was 60 ℃.
Comparative example 1
The difference between this example and example 6 is that the modified conductive fiber is not pretreated, specifically:
a preparation method of a flexible porous conductive material comprises the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding modified conductive fibers, and continuously stirring uniformly, wherein the mass ratio of the polydimethylsiloxane to the modified conductive fibers is 100; the diameter of the modified conductive fiber is 20-100nm, and the length is 1-3 μm;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in oven to 65 deg.C for curing, and heating for 3 hr.
The preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 1.0g of polyvinylpyrrolidone and 8mLN, and obtaining spinning solution A;
step 2: 1g of nano tin dioxide powder and 8mLN, N-dimethylformamide solution are mixed and ultrasonically dispersed uniformly;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 spinning solution A is injected into each spinning device by 1.0ml,2 spinning solution B is injected into each spinning device by 1.0ml, spinning is carried out by adopting a 27G needle head at the rotating speed of 3500r/min, materials are added every 2min, and spinning is carried out for 8min at the spinning temperature of 30 ℃ and the humidity of 35%;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
and 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane into an aqueous solution of cobalt acetate, refluxing for 24 hours at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, raising the temperature from normal temperature to 140 ℃ at the rate of 5 ℃/min, keeping for 30min, then raising the temperature to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: after being crushed, the mixture is placed in a direct-current pulse nitrogen normal-pressure plasma jet device for treatment, and modified conductive fibers are obtained; the gas adopted is He and He/O 2 (99: 1), the treatment power was 60W, the frequency was 13.56MHz, and the temperature of the plasma shower head was 60 ℃.
The contact angle test is used for researching the wettability of a sample, and an SDA 100 type video optical contact angle tester is adopted in the chapter for testing the contact angle.
TABLE 1 Properties of the different examples
As one application, a PVA/KCl gel electrolyte was prepared by dissolving 1g of PVA in 10 ml of 0.02M aqueous KCl solution and vigorously stirring at 85 ℃ until clear and transparent. Naturally cooling to 40 deg.C, pouring on a polytetrafluoroethylene dish, and drying in air to naturally volatilize excessive water. After curing at room temperature, the gel electrolyte is cut into a size matched with the electrode for later use. Two prepared materials of the invention and a piece of gel electrolyte are assembled into a super capacitor with a sandwich structure.
TABLE 2 capacitor Performance for various examples
| Area specific capacitance at 10mV/s (mF/cm) 2 ) | Capacity retention after 10000 cycles (%) | |
| Example 1 | 2033 | 88.3 |
| Example 2 | 2097 | 88.5 |
| Example 3 | 2146 | 88.9 |
| Example 4 | 2183 | 89.0 |
| Example 5 | 2204 | 89.6 |
| Example 6 | 2193 | 90.0 |
| Comparative example 1 | 1975 | 80.1 |
Claims (8)
1. A preparation method of a flexible porous conductive material is characterized by comprising the following steps:
(1) Uniformly mixing polydimethylsiloxane and a curing agent according to the proportion of 10;
(2) Adding the pretreated modified conductive fibers, and continuously stirring uniformly; the pretreatment method of the modified conductive fiber comprises the following steps: dissolving modified conductive fiber in ethanol, performing ultrasonic dispersion and electromagnetic stirring to be uniform, dropwise adding polydopamine solution, reacting for 1h, cooling to room temperature, stirring in a 60 ℃ constant-temperature water bath at 1000r/min for 1.5h, adjusting the pH value to 3-4 with acetic acid, dehydrating with ethanol, and vacuum drying at 80 ℃ to obtain the modified conductive fiber;
(3) Putting the mixture into a vacuum drying oven, and vacuumizing for 2h to remove bubbles generated in the stirring process;
(4) Slowly pouring the mixture into a mold, covering an aluminum plate after the mold is filled with the mixture, and vertically placing for 0.5h by fixing with a clamp;
(5) Heating in an oven to 65 deg.C for curing, and heating for 3 hr;
the preparation method of the modified conductive fiber comprises the following steps:
step 1: uniformly mixing 2.0g of acetic acid lignin, 0.1-1.0g of polyvinylpyrrolidone and 8mL of N, N-dimethylformamide solution to obtain a spinning solution A;
step 2: mixing 0.5-1g of nano tin dioxide powder and 8mL of N, N-dimethylformamide solution, and uniformly dispersing by ultrasonic;
and step 3: adding the spinning solution A, and stirring at normal temperature for 12h to obtain spinning solution B;
and 4, step 4: preparing a fiber membrane: adjusting the receiving distance to 12cm, setting the static voltage to 10kV, adhering aluminum foil paper on a collecting plate for receiving fibers, in four spinning devices, 2 injecting spinning solutions A of 1.0ml and 2 injecting spinning solutions B of 1.0ml respectively, spinning by adopting a 27G needle at the rotating speed of 3500r/min, adding materials every 2min, and spinning for 8min;
and 5: removing the fiber membrane from the aluminum foil paper, washing in a water bath kettle at 60 ℃, and continuously washing for 3d;
and 6: dissolving 3.0g of acetic acid drill into 150mL of distilled water, soaking the fiber membrane in a cobalt acetate aqueous solution, refluxing for 24h at 60 ℃, taking out the fiber membrane after the reaction is finished, and then putting the fiber membrane into an oven for drying;
and 7: carrying out oxidation stabilization treatment on the fiber membrane in an aerobic atmosphere, heating to 140 ℃ from normal temperature at the heating rate of 5 ℃/min, keeping for 30min, then heating to 280 ℃ and staying for 1h, cooling to room temperature and taking out to obtain a pre-oxidized fiber membrane;
and 8: placing the pre-oxidized fiber membrane into a tubular furnace, sealing, introducing Ar for protection, raising the temperature from 25 ℃ to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 30min, wherein the flow of protective gas in the process is 200mL/min;
and step 9: in the cooling process, ar is still introduced until the temperature is reduced to 350 ℃, and air is blown until the temperature is normal;
step 10: and (3) crushing the mixture, and then placing the crushed mixture in a direct-current pulse nitrogen normal-pressure plasma jet device for treatment to obtain the modified conductive fiber.
2. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: the curing agent consists of a mixture of methylhydrogen-silicon copolymer chains and a platinum-based catalyst.
3. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: the mass ratio of the polydimethylsiloxane to the modified conductive fibers is 100 (2-5).
4. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: the diameter of the modified conductive fiber is 20-100nm, and the length of the modified conductive fiber is 1-3 mu m.
5. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: the mass fraction of the polydopamine solution is 3-5%.
6. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: the mass ratio of the lignin acetate to the polyvinylpyrrolidone in the spinning solution A is 5.
7. The method for preparing a flexible porous conductive material according to claim 1, wherein the method comprises the following steps: in the step (4), the spinning temperature is 20-30 ℃, and the humidity is 25-35%.
8. The flexible porous conductive material prepared by the preparation method of the flexible porous conductive material according to any one of claims 1 to 7 is applied to a flexible supercapacitor electrode material.
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