CN114551117A - Preparation method of flexible antibacterial fiber type supercapacitor for electronic skin - Google Patents
Preparation method of flexible antibacterial fiber type supercapacitor for electronic skin Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- 229920002678 cellulose Polymers 0.000 claims abstract description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002159 nanocrystal Substances 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 239000001103 potassium chloride Substances 0.000 claims abstract description 11
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 11
- 238000002166 wet spinning Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 43
- 238000005406 washing Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 29
- 235000010980 cellulose Nutrition 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 10
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 10
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 230000002195 synergetic effect Effects 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000008240 homogeneous mixture Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000010621 bar drawing Methods 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000002848 electrochemical method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 206010016936 Folliculitis Diseases 0.000 description 1
- 208000008454 Hyperhidrosis Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000191963 Staphylococcus epidermidis Species 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000037315 hyperhidrosis Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of capacitors, and discloses a preparation method of a flexible antibacterial fiber type supercapacitor for electronic skin. The preparation method comprises the steps of firstly preparing Cellulose Nanocrystals (CNC) and large-sheet-diameter high-concentration graphene oxide, synthesizing CNC-PANI suspension, and then preparing the graphene oxide based on RGO/CNC-PANI/Fe through a wet spinning and reduction method3+The flexible antibacterial fiber type super capacitor for electronic skin. CNC and polyaniline can be combined through cooperationEnhancing the strength of the CNC base fiber by the same effect; the potassium chloride can improve the conductivity and strain sensitivity of the fiber, and the capacitor can release Fe3+To eliminate bacteria.
Description
Technical Field
The invention relates to the field of capacitors, in particular to a preparation method of a flexible antibacterial fiber type supercapacitor for electronic skin.
Background
With the development of society and the advancement of science and technology, wearable devices are receiving more and more attention and gradually change the lives of people. Wearable devices mainly refer to electronic devices that can be worn directly on a person, and are electronic products that can be integrated into clothing or similar clothing. The next generation of wearable electronics requires the system to be worn directly on the body covered with highly expandable, soft, curved skin. However, most wearable products in the market are mainly worn, mainly including smart watches, bracelets, glasses and the like, and few products can be worn directly. In order to obtain intelligent textiles, one approach is to attach functional materials to a flat fabric in a stacked manner to perform their functions, however stacking the functional materials on the surface of the fabric greatly reduces the inherent properties of the fabric such as softness, air permeability, mechanical properties, etc. Since the fibers as the components of the fabric have been manufactured and used by human beings for thousands of years due to the characteristics of softness, deformability, air permeability, durability, water washing resistance, etc., the research and preparation of the functionalized flexible fibers have very important significance for the development of wearable devices.
The fiber itself has the characteristics of being light, flexible and easy to weave, and can be used for realizing wearable application by constructing a flexible fiber-shaped device. Fibrous flexible devices have therefore been extensively studied, mainly in the energy category of devices, such as fibrous solar cells, supercapacitors, lithium ion batteries, etc. However, these energy devices are ultimately intended to provide energy to the corresponding wearable electronic device for its proper operation. Besides the strategy of constructing a fibrous flexible device to be woven into clothes to realize the wearable effect, the electronic skin can be directly attached to the skin of a human body due to the advantages of high flexibility, lightness and thinness, so that the wearable application of the electronic device is realized.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a flexible antibacterial fiber type super capacitor for electronic skinThe preparation method is as follows. The preparation method comprises the steps of firstly preparing Cellulose Nanocrystals (CNC) and large-sheet-diameter high-concentration graphene oxide, synthesizing CNC-PANI suspension, and then preparing the graphene oxide based on RGO/CNC-PANI/Fe through a wet spinning and reduction method3+The flexible antibacterial fiber type super capacitor for electronic skin. The strength of the CNC-based fiber can be enhanced through a synergistic effect between the CNC and the polyaniline; the potassium chloride can improve the conductivity and strain sensitivity of the fiber, and the capacitor can release Fe3+To eliminate bacteria.
The specific technical scheme of the invention is as follows: a preparation method of a flexible antibacterial fiber type supercapacitor for electronic skin comprises the following steps:
step 1: preparation of Cellulose Nanocrystals (CNC): adding microcrystalline cellulose into the circulating acid mixture, and continuously stirring at 80-90 ℃; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the obtained functionalized cellulose nanocrystal and the circulating acid mixture, continuously centrifuging and washing the cellulose nanocrystal with water, dialyzing to remove the residual acid, and freeze-drying.
The strength of the CNC-based fiber can be obviously enhanced through the polycarboxylation.
Step 2: preparation of large-sheet-size high-concentration graphene oxide (LGO) solution: adding graphite nanosheets into chromic acid washing liquor for ultrasonic dispersion, then mechanically stirring, pouring water, performing suction filtration, washing with water and washing with ethanol; baking and cooling to room temperature; centrifuging the resulting pale orange solution to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide, adding the large-sheet-diameter graphene oxide into water, and stirring to obtain a large-sheet-diameter high-concentration graphene oxide solution.
The graphene oxide prepared by the method has rich carboxyl active sites on the surface, and the dispersibility of the solution is improved. The graphene sheets are gathered together by weak van der Waals force, only the graphene sheets with thick atoms have extremely large surface areas, and are arranged in an attached manner like scales on the fish body after being pulled into fibers; if the fiber is knotted, the strength of the knot is determined by the bending coefficient of the fiber, and the strength is higher because the bending coefficient of the graphene oxide is very low as if the knot does not exist at all.
And step 3: preparation of CNC-PANI suspension: adding hydrochloric acid and aniline monomer into cellulose nanocrystal aqueous suspension, and stirring in an ice bath to obtain a uniform mixture to prevent agglomeration; adding ammonium sulfate into water, and vigorously stirring for oxidative polymerization at 0-5 deg.C to obtain CNC-PANI suspension.
In this step, the strength of the fiber can be enhanced by a synergistic effect between the CNC and the polyaniline.
And 4, step 4: GO/CNC-PANI/Fe3+Preparing a spinning solution: sequentially dripping potassium chloride solution and ferric chloride solution into the CNC-PANI suspension, stirring, and adding K+And Fe3+The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding the large-sheet-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+The mixture was homogeneous.
The invention is based on weak hydrogen bonds and Fe3+The chelating synergy and the potassium chloride can improve the conductivity and the strain sensitivity of the fiber, so that the device has excellent mechanical property and excellent conductivity. Meanwhile, because the device is used for being attached to the skin, if the wound part of the skin is infected, the high temperature caused by the infected part (when skin tissues are infected by staphylococcus aureus, staphylococcus epidermidis and streptococcus, the phenomena of scratching, friction, high-temperature humidity and hyperhidrosis and the like caused by acute, subacute and chronic skin diseases and folliculitis easily caused by the skin tissues) can promote Fe in the device3+Releasing to eliminate bacteria.
And 5: preparation of GO/CNC-PANI/Fe by wet spinning3+Fiber: to GO/CNC-PANI/Fe3+Centrifuging the uniform mixture; mixing the obtained GO/CNC-PANI/Fe3+Filling the spinning solution into an injector with a rotary nozzle, and then injecting the spinning solution into a calcium chloride-ethanol aqueous solution coagulating bath; after solidification, washing with water and ethanol; the resulting fibers were collected, dried at room temperature and then dried under vacuum to completely eliminate the solvent from the fibers.
Step 6: preparation of RGO/CNC-PANI/Fe by reduction method3+Fiber: chemically reducing the fiber obtained in the step 5 in an HI aqueous solution, washing with absolute ethyl alcohol, and drying in vacuum; then, thermal reduction is carried out, the fiber is reduced for 2.5-3h at 750-800 ℃, 1.5-2h at 950-1000 ℃ and 0.5-1h at 1150-1200 ℃ under Ar atmosphere.
The invention can eliminate the stress concentration in the fiber by multi-step calcination, improve the tensile strength of the fiber, prevent the fiber from being shrunk by overheating, and better keep the original length.
And 7: assembling the solid capacitor: and (3) taking 2 polyethylene terephthalate sheets coated with gold layers as a supporting substrate and a current collector, pre-weaving the fibers obtained in the step (5) and then placing the fibers on the substrate to form 2 electrodes, and placing cellulose paper soaked by electrolyte as a solid electrolyte between the two electrodes to form the sandwich-type symmetrical capacitor.
Preferably, step 1 specifically comprises: adding 2-3g of microcrystalline cellulose into 100-110ml of circulating acid mixture consisting of citric acid and hydrochloric acid in a volume ratio of 8-10:1, and continuously stirring at 80-90 ℃ for 10-12 h; after completion, the resulting suspension was rapidly cooled to room temperature; and (3) filtering, separating the obtained functionalized cellulose nanocrystal and a circulating acid mixture, and mixing the cellulose nanocrystal and the circulating acid mixture according to a liquid-solid ratio of 20-22 ml: 1g of the cellulose nanocrystal is washed by water for 3-5 times through continuous centrifugation, dialyzed for 24-48h by a dialysis bag with Mw = 10000-.
Preferably, step 2 specifically comprises: adding 500-600 mg of graphite nanosheets into 560 ml of chromic acid washing liquid for ultrasonic dispersion for 30-40 min, then mechanically stirring for 10-20 min at 35-45 ℃, pouring 1-2 liters of water, performing suction filtration, washing for 3-5 times with water, and washing for 2-3 times with ethanol; baking at the temperature of 110-120 ℃ for 3-3.5 h, and cooling to room temperature; centrifuging the obtained light orange solution at the speed of 2000-3000rpm for 8-10min to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide with the transverse dimension of 0.5-6 mu m, adding 300-350mg of the large-sheet-diameter graphene oxide into 10-12ml of water, and stirring for 3-4h at 40-45 ℃ to obtain a large-sheet-diameter high-concentration graphene oxide solution.
Preferably, step 3 specifically comprises: adding 20-22ml of 1M hydrochloric acid and 0.20-0.22g of aniline monomer into 8-12g of 1-3wt% cellulose nanocrystal aqueous suspension, and stirring in an ice bath for 60-70min to obtain a uniform mixture to prevent agglomeration; adding 0.41-0.43g ammonium sulfate into 2-3ml water, and vigorously stirring at 0-5 deg.C for 2-2.5h to obtain CNC-PANI suspension.
Preferably, step 4 specifically comprises: dripping 2-2.5ml of 0.0018mol potassium chloride solution and 2-2.5ml of 0.0018mol ferric chloride solution into the CNC-PANI suspension, stirring at 25-30 ℃ for 1-1.5h, and adding K+And Fe3+The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding 1-1.5g of the large-sheet-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring for 2-3h at 25-30 ℃ to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+The mixture was homogeneous.
Preferably, step 5 specifically comprises: for GO/CNC-PANI/Fe3+The homogeneous mixture was centrifuged at 18000 and 20000 rpm; mixing the obtained GO/CNC-PANI/Fe3+The spinning solution is filled into an 8-12ml plastic injector with a rotary nozzle, the diameter of a spinneret orifice is 200--1And the draw-bar drawing speed vr1=3.5-3.7cm/s and pull rod collection speed vr2=3.7-3.9 cm/s; after solidification for 30-35min, washing with water and ethanol for 3-5 times in sequence; collecting the obtained fiber, drying at room temperature for 10-12h, and vacuum drying at 37-40 deg.C for 20-24h to completely eliminate solvent in the fiber.
Preferably, step 6 specifically comprises: chemically reducing the fiber obtained in the step 5 in a 40-47wt% HI water solution at 80-85 ℃ for 9-10h, then continuously washing with absolute ethyl alcohol for 3-5 times, and vacuum drying at 40-50 ℃ for 10-12 h; then, thermal reduction is carried out, the fiber is reduced for 2.5-3h at 750-800 ℃, 1.5-2h at 950-1000 ℃ and 0.5-1h at 1150-1200 ℃ in Ar atmosphere, and the reduction is carried out in a vacuum tube furnace.
Preferably, in step 7: the electrolyte is 0.8-1.2M sodium sulfate electrolyte.
Compared with the prior art, the invention has the following technical effects:
(1) the strength of the CNC-based fiber is enhanced through polycarboxylation.
(2) The graphene oxide prepared by the method has rich carboxyl active sites on the surface, and the dispersibility of the solution is improved. The graphene sheets are gathered together by weak van der Waals force, only the graphene sheets with thick atoms have extremely large surface areas, and are arranged in an attached manner like scales on the fish body after being pulled into fibers; if the fiber is knotted, the strength of the knot is determined by the bending coefficient of the fiber, and the strength is higher as if the knot does not exist at all because the bending coefficient of the graphene oxide is very low.
(3) The strength of the fiber is enhanced by the synergy between the CNC and the polyaniline.
(4) The invention is based on weak hydrogen bonds and Fe3+The chelating synergistic effect and the potassium chloride can improve the conductivity and the strain sensitivity of the fiber, so that the device has excellent mechanical property and excellent conductivity; meanwhile, because the device is used for being attached to the skin, if the wound part of the skin is infected, the high temperature caused by the infected part can promote Fe in the device3+Releasing to eliminate bacteria.
(5) The invention can eliminate the stress concentration in the fiber by multi-step calcination, improve the tensile strength of the fiber, prevent the fiber from being shrunk by overheating, and better keep the original length.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Step 1: preparation of Cellulose Nanocrystals (CNC): 2g microcrystalline cellulose (MCC) was added to 100ml of a circulating acid mixture (volume ratio: citric acid: hydrochloric acid = 9: 1) and stirred continuously at 80 ℃ for 10 h; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and the circulating acid mixture, adding deionized water into the CNC (liquid-solid ratio is 20 ml: 1g), and continuously centrifuging and washing for 3 times; dialyzing with dialysis bag (Mw cut-off 12000 Da) for 24 hr to remove residual acid, and freeze drying;
step 2: preparation of large-sheet-size high-concentration graphene oxide (LGO) solution: adding 500 mg of graphite nanosheets into 560 ml of chromic acid washing liquor, and ultrasonically dispersing for 30 min; then mechanically stirring for 10min at 40 ℃, pouring 1L of deionized water, carrying out suction filtration, washing with water for 3 times, and washing with ethanol for 2 times; baking at 110 deg.C for 3h, and cooling to room temperature; centrifuging the light orange solution at 2000rpm for 8min to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide (LGO) with the transverse dimension of 0.5 mu m, adding 300mg of the large-sheet-diameter graphene oxide into 10ml of water, and stirring for 3 hours at 40 ℃ to obtain a high-concentration LGO solution for later use;
and step 3: preparation of CNC-PANI suspension: then hydrochloric acid (20ml, 1M) and aniline monomer (0.20 g) were added to CNC aqueous suspension (10 g, 2 wt%), and stirred in an ice bath for 60min to obtain a homogeneous mixture, preventing agglomeration; adding 0.41g of ammonium sulfate into 2ml of deionized water, and violently stirring at about 1 ℃ for 2h for oxidative polymerization to obtain a CNC-PANI suspension;
and 4, step 4: GO/CNC-PANI/Fe3+Preparing a spinning solution: dripping potassium chloride solution (2ml, 0.134g, 0.0018mol) and ferric chloride solution (2ml, 0.292g, 0.0018mol) into CNC-PANI suspension, stirring at 25 deg.C for 1h with different metal ions (K)+And Fe3+) The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding 1g of LGO solution prepared in the step 2 into the suspension, and stirring for 2h at 25 ℃ to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+Mixing the mixture evenly for later use;
and 5: preparation of GO/CNC-PANI/Fe by wet spinning3+Fiber: GO/CNC-PANI/Fe3+The homogeneous mixture was centrifuged at 18000 rpm; mixing GO/CNC-PANI/Fe3+The spinning dope was filled into a 10ml plastic syringe with a rotating nozzle having a diameter size of 300 μm, and then the spinning dope was injected into a coagulating bath of 5wt% calcium chloride in ethanol (1: 3 v/v) at a corresponding syringe speed of 40 μ l min-1And the draw-bar drawing speed vr1=3.5cm/s and pull rod collection speed vr2=3.7 cm/s; after solidification for 30min, washing with water and ethanol sequentially for 3 times; the collected fibers were dried at room temperature for 10h and then dried at 37 deg.C under vacuum for 20h to completely eliminate the solvent from the fibers；
Step 6: preparation of RGO/CNC-PANI/Fe by reduction method3+Fiber: carrying out chemical reduction treatment on the fiber obtained in the step 5 in HI (40%) aqueous solution at 80 ℃ for 9h, then continuously washing with absolute ethyl alcohol for 3 times, and carrying out vacuum drying at 40 ℃ for 10 h; then carrying out thermal reduction, reducing the fiber at 750 ℃ for 2.5h, at 950 ℃ for 1.5h and at 1150 ℃ for 0.5h in Ar atmosphere, and carrying out the reduction in a vacuum tube furnace;
and 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as the counter electrode and mercury/mercury as the reference electrode. Measurements were made at room temperature in 1M sodium sulfate aqueous electrolyte. The electrochemical performance of the sample was characterized by using CHI660B electrochemical workstation (Shanghai CH instruments Co.); CV reactions were performed at different scan rates of 10mV/s, between 0 and 1V. Measuring a gas static charge-discharge curve within a potential range of 0-1V under different currents of 20 muA; EIS measurements were performed at open circuit potential with 5mV AC perturbation over the frequency range of 100kHz to 0.01 Hz; calculating the mass specific capacitance according to experimental data, wherein the mass specific capacitance calculation formula of the super capacitor electrode is Cm= I × Δ t/(m × Δ V), wherein: i is constant current, delta t is discharge time, m is total mass added by the electrode, and delta V is potential difference in the discharge process;
and 8: assembling the solid capacitor: 2 gold-coated polyethylene terephthalate sheets (2 cm × 4 cm) were used as a support substrate and a current collector, 2 fibers (2 cm × 4 cm) obtained in step 6 were simply woven on the substrate to form 2 electrodes, and a cellulose paper soaked with 1M sodium sulfate electrolyte was used as a solid electrolyte between the two electrodes to form a sandwich-type symmetrical capacitor.
Example 2
Step 1: preparation of Cellulose Nanocrystals (CNC): 2g of microcrystalline cellulose (MCC) was added to 105 ml of a circulating acid mixture (volume ratio: citric acid: hydrochloric acid = 9: 1) and stirred continuously at 85 ℃ for 11 h; after completion, the suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and the circulating acid mixture, adding deionized water into the CNC (liquid-solid ratio of 21 ml: 1g), and continuously centrifuging and washing for 4 times; dialyzing with dialysis bag (Mw cut-off 12000 Da) for 36h to remove residual acid, and freeze drying;
step 2: preparing a large-sheet-diameter high-concentration graphene oxide (LGO) solution: adding 550 mg of graphite nanosheets into 560 ml of chromic acid washing liquor, and ultrasonically dispersing for 35 min; then mechanically stirring for 15 min at 40 ℃, pouring 1.5 liters of deionized water, filtering, washing with water for 4 times and washing with ethanol for 2 times; baking at 115 deg.C for 3h, and cooling to room temperature; the light orange solution was centrifuged at 2000rpm for 9min to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide (LGO) with the transverse dimension of 0.5-6 mu m, adding 330mg of the large-sheet-diameter graphene oxide into 11ml of water, and stirring for 3 hours at 40 ℃ to obtain a high-concentration LGO solution for later use;
and step 3: preparation of CNC-PANI suspension: hydrochloric acid (21 ml, 1M) and aniline monomer (0.21 g) were then added to the CNC aqueous suspension (10 g, 2 wt%), and stirred in an ice bath for 65min to give a homogeneous mixture, preventing agglomeration; adding 0.42g of ammonium sulfate into 2.5ml of deionized water, and violently stirring at about 3 ℃ for 2h for oxidative polymerization to obtain CNC-PANI suspension;
and 4, step 4: GO/CNC-PANI/Fe3+Preparing a spinning solution: dripping potassium chloride solution (2ml, 0.134g, 0.0018mol) and ferric chloride solution (2ml, 0.292g, 0.0018mol) into CNC-PANI suspension, stirring at 28 deg.C for 1h, and adding different metal ions (K)+And Fe3+) The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding 1g of LGO solution prepared in the step 2 into the suspension, and stirring for 2.5h at 25 ℃ to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+Mixing the mixture evenly for later use;
and 5: preparation of GO/CNC-PANI/Fe by wet spinning3+Fiber: GO/CNC-PANI/Fe3+The homogeneous mixture was centrifuged at 19000 rpm; mixing GO/CNC-PANI/Fe3+The spinning dope was filled into a 10ml plastic syringe with a rotating nozzle having a diameter size of 300 μm, and then the spinning dope was injected into a coagulating bath of 5wt% calcium chloride in ethanol (1: 3 v/v) at a corresponding syringe speed of 50 μ l min-1And the draw-bar drawing speed vr1=3.6cm/s and pull rod collection speed vr2=3.8 cm/s; after 30min of coagulation, water was usedAnd ethanol were washed 4 times in sequence; collecting fiber, drying at room temperature for 11h, and vacuum drying at 37 deg.C for 22h to completely eliminate solvent in fiber;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method3+Fiber: chemically reducing the fiber obtained in the step 5 in HI (44%) water solution at 80 ℃ for 9.5h, then continuously washing with absolute ethyl alcohol for 4 times, and vacuum-drying at 45 ℃ for 11 h; then carrying out thermal reduction, reducing the fiber for 2.5h at 775 ℃, 1.5h at 950 ℃ and 0.8h at 1175 ℃ in Ar atmosphere, and carrying out the reduction in a vacuum tube furnace;
and 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as the counter electrode and mercury/mercury as the reference electrode. Measurements were performed at room temperature in 1M sodium sulfate aqueous electrolyte. The electrochemical performance of the sample was characterized by using CHI660B electrochemical workstation (Shanghai CH instruments Co.); CV reactions were performed at various scan rates of 500mV/s, between 0 and 1V. Measuring a gas static charge-discharge curve within a potential range of 0-1V under different currents of 50 muA; EIS measurements were performed at open circuit potential with 5mV AC perturbation over the frequency range of 100kHz to 0.01 Hz; calculating the mass specific capacitance according to experimental data, wherein the mass specific capacitance calculation formula of the super capacitor electrode is Cm= I × Δ t/(m × Δ V), wherein: i is constant current, delta t is discharge time, m is total mass added by the electrode, and delta V is potential difference in the discharge process;
and 8: assembling the solid capacitor: 2 gold-coated polyethylene terephthalate sheets (2 cm × 4 cm) were used as a support substrate and a current collector, 2 fibers (2 cm × 4 cm) obtained in step 6 were simply woven on the substrate to form 2 electrodes, and a cellulose paper soaked with 1M sodium sulfate electrolyte was used as a solid electrolyte between the two electrodes to form a sandwich-type symmetrical capacitor.
Example 3
Step 1: preparation of Cellulose Nanocrystals (CNC): 3g of microcrystalline cellulose (MCC) was added to 110ml of a circulating acid mixture (volume ratio: citric acid: hydrochloric acid = 9: 1) and stirred continuously at 90 ℃ for 12 h; after completion, the suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and the circulating acid mixture, adding deionized water into the CNC (liquid-solid ratio is 22 ml: 1g), and continuously centrifuging and washing for 5 times; dialyzing with dialysis bag (Mw cut-off 12000 Da) for 48 hr to remove residual acid, and freeze drying;
step 2: preparation of large-sheet-size high-concentration graphene oxide (LGO) solution: adding 600 mg of graphite nanosheets into 560 ml of chromic acid washing liquor, and ultrasonically dispersing for 40 min; then mechanically stirring for 20 min at 40 ℃, pouring 2 liters of deionized water, carrying out suction filtration, washing with water for 5 times and washing with ethanol for 3 times; baking at 120 deg.C for 3.5 h, and cooling to room temperature; centrifuging the light orange solution at 3000rpm for 10min to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide (LGO) with the transverse dimension of 0.5-6 mu m, adding 350mg of the large-sheet-diameter graphene oxide into 12ml of water, and stirring for 4 hours at 45 ℃ to obtain a high-concentration LGO solution for later use;
and step 3: preparation of CNC-PANI suspension: hydrochloric acid (22ml, 1M) and aniline monomer (0.22 g) were then added to the CNC aqueous suspension (10 g, 2 wt%), and stirred in an ice bath for 70min to give a homogeneous mixture, preventing agglomeration; adding 0.43g of ammonium sulfate into 3ml of deionized water, and violently stirring at about 5 ℃ for 2.5h for oxidative polymerization to obtain a CNC-PANI suspension;
and 4, step 4: GO/CNC-PANI/Fe3+Preparing a spinning solution: dripping potassium chloride solution (2.5ml, 0.134g, 0.0018mol) and ferric chloride solution (2.5ml, 0.292g, 0.0018mol) into the CNC-PANI suspension, stirring at 30 deg.C for 1.5h, and adding different metal ions (K)+And Fe3+) The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding 1.5g of LGO solution prepared in the step 2 into the suspension, and stirring for 3h at 30 ℃ to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+Mixing the mixture evenly for later use;
and 5: preparation of GO/CNC-PANI/Fe by wet spinning3+Fiber: GO/CNC-PANI/Fe3+The homogeneous mixture was centrifuged at 20000 rpm; mixing GO/CNC-PANI/Fe3+The spinning solution was filled into a 10ml plastic syringe with a rotating nozzle, the diameter of the orifice of which was 300 μm, and then the spinning solution was injected into a coagulating bath of 5wt% aqueous calcium chloride ethanol (1: 3 v/v) at a corresponding syringe speedThe concentration is 60 μ l min-1And the draw-bar drawing speed vr1=3.7cm/s and pull rod collection speed vr2=3.9 cm/s; after 35min of solidification, washing with water and ethanol sequentially for 5 times; collecting fiber, drying at room temperature for 12h, and vacuum drying at 40 deg.C for 24h to completely eliminate solvent in fiber;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method3+Fiber: chemically reducing the fiber obtained in the step 5 in HI (47%) water solution at 85 ℃ for 10h, then continuously washing with absolute ethyl alcohol for 5 times, and vacuum-drying at 50 ℃ for 12 h; then carrying out thermal reduction, reducing the fiber at 800 ℃ for 3h, 1000 ℃ for 2h and 1200 ℃ for 1h in Ar atmosphere, and carrying out the reduction in a vacuum tube furnace;
and 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as the counter electrode and mercury/mercury as the reference electrode. Measurements were performed at room temperature in 1M sodium sulfate aqueous electrolyte. The electrochemical performance of the sample was characterized by using CHI660B electrochemical workstation (Shanghai CH instruments Co.); CV reactions were performed at different scan rates of 1000mV/s, between 0 and 1V. Measuring a gas static charge-discharge curve within a potential range of 0-1V under different currents of 80 muA; EIS measurements were performed at open circuit potential with 5mV AC perturbation over the frequency range of 100kHz to 0.01 Hz; calculating the mass specific capacitance according to experimental data, wherein the mass specific capacitance calculation formula of the super capacitor electrode is Cm= I × Δ t/(m × Δ V), wherein: i is constant current, delta t is discharge time, m is total mass added by the electrode, and delta V is potential difference in the discharge process;
and 8: assembling the solid capacitor: 2 gold-coated polyethylene terephthalate sheets (2 cm × 4 cm) were used as a support substrate and a current collector, 2 fibers (2 cm × 4 cm) obtained in step 6 were simply woven on the substrate to form 2 electrodes, and a cellulose paper soaked with 1M sodium sulfate electrolyte was used as a solid electrolyte between the two electrodes to form a sandwich-type symmetrical capacitor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a flexible antibacterial fiber type supercapacitor for electronic skin is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparing cellulose nanocrystals: adding microcrystalline cellulose into the circulating acid mixture, and continuously stirring at 80-90 ℃; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the obtained functionalized cellulose nanocrystal and a circulating acid mixture, continuously centrifuging and washing the cellulose nanocrystal with water, dialyzing to remove the residual acid, and freeze-drying;
step 2: preparing a large-sheet-diameter high-concentration graphene oxide solution: adding graphite nanosheets into chromic acid washing liquor for ultrasonic dispersion, then mechanically stirring, pouring water, performing suction filtration, washing with water and washing with ethanol; baking and cooling to room temperature; centrifuging the resulting pale orange solution to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide, adding the large-sheet-diameter graphene oxide into water, and stirring to obtain a large-sheet-diameter high-concentration graphene oxide solution;
and step 3: preparation of CNC-PANI suspension: adding hydrochloric acid and aniline monomer into cellulose nanocrystal aqueous suspension, and stirring in an ice bath to obtain a uniform mixture to prevent agglomeration; adding ammonium sulfate into water, and vigorously stirring at 0-5 deg.C for oxidative polymerization to obtain CNC-PANI suspension;
and 4, step 4: GO/CNC-PANI/Fe3+Preparing a spinning solution: sequentially dripping potassium chloride solution and ferric chloride solution into CNC-PANI suspension, stirring with K+And Fe3+The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding the large-sheet-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring to obtain GO/CNC-PANI/Fe with a synergetic soft-hard hierarchical structure3+Mixing the mixture evenly;
and 5: preparation of GO/CNC-PANI/Fe by wet spinning3+Fiber: to GO/CNC-PANI/Fe3+Centrifuging the uniform mixture; mixing the obtained GO/CNC-PANI/Fe3+Filling the spinning solution into an injector with a rotary nozzle, and then injecting the spinning solution into a calcium chloride ethanol water solution coagulating bath; after solidification, washing with water and ethanol; collecting the obtained fiber, drying at room temperature, and then drying in vacuum to completely eliminate the solvent in the fiber;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method3+Fiber: chemically reducing the fiber obtained in the step 5 in an HI aqueous solution, washing with absolute ethyl alcohol, and drying in vacuum; then carrying out thermal reduction, wherein the fiber is reduced for 2.5-3h at 750-800 ℃, for 1.5-2h at 950-1000 ℃ and for 0.5-1h at 1150-1200 ℃ in Ar atmosphere;
and 7: assembling the solid capacitor: and (3) taking 2 polyethylene terephthalate sheets coated with gold layers as a supporting substrate and a current collector, pre-weaving the fibers obtained in the step (5) and then placing the fibers on the substrate to form 2 electrodes, and placing cellulose paper soaked by electrolyte as a solid electrolyte between the two electrodes to form the sandwich-type symmetrical capacitor.
2. The method of claim 1, wherein: the step 1 specifically comprises the following steps: adding 2-3g of microcrystalline cellulose into 100-110ml of circulating acid mixture consisting of citric acid and hydrochloric acid in a volume ratio of 8-10:1, and continuously stirring at 80-90 ℃ for 10-12 h; after completion, the resulting suspension was rapidly cooled to room temperature; and (3) filtering, separating the obtained functionalized cellulose nanocrystal and a circulating acid mixture, and mixing the cellulose nanocrystal and the circulating acid mixture according to a liquid-solid ratio of 20-22 ml: 1g of the cellulose nanocrystal is washed by water for 3-5 times through continuous centrifugation, dialyzed for 24-48h by a dialysis bag with Mw = 10000-.
3. The method of claim 1, wherein: the step 2 specifically comprises the following steps: adding 500-600 mg of graphite nanosheets into 560 ml of chromic acid washing liquid for ultrasonic dispersion for 30-40 min, then mechanically stirring for 10-20 min at 35-45 ℃, pouring 1-2 liters of water, performing suction filtration, washing for 3-5 times with water, and washing for 2-3 times with ethanol; baking at the temperature of 110-120 ℃ for 3-3.5 h, and cooling to room temperature; centrifuging the obtained light orange solution at 2000-3000rpm for 8-10min to remove unoxidized graphite; obtaining large-sheet-diameter graphene oxide with the transverse dimension of 0.5-6 mu m, adding 300-350mg of the large-sheet-diameter graphene oxide into 10-12ml of water, and stirring for 3-4h at 40-45 ℃ to obtain a large-sheet-diameter high-concentration graphene oxide solution.
4. The method of claim 1, wherein: the step 3 specifically comprises the following steps: adding 20-22ml of 1M hydrochloric acid and 0.20-0.22g of aniline monomer into 8-12g of 1-3wt% cellulose nanocrystal aqueous suspension, and stirring in an ice bath for 60-70min to obtain a uniform mixture to prevent agglomeration; adding 0.41-0.43g ammonium sulfate into 2-3ml water, and vigorously stirring at 0-5 deg.C for 2-2.5h to obtain CNC-PANI suspension.
5. The method of claim 1, wherein: the step 4 specifically comprises the following steps: dripping 2-2.5ml of 0.0018mol potassium chloride solution and 2-2.5ml of 0.0018mol ferric chloride solution into the CNC-PANI suspension, stirring at 25-30 ℃ for 1-1.5h, and adding K+And Fe3+The dynamic metal ion coordination bond and the weak hydrogen bond are formed; adding 1-1.5g of the large-sheet-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring at 25-30 ℃ for 2-3h to obtain GO/CNC-PANI/Fe with a synergistic soft-hard hierarchical structure3+The mixture was homogeneous.
6. The method of claim 1, wherein: the step 5 specifically comprises the following steps: to GO/CNC-PANI/Fe3+The homogeneous mixture was centrifuged at 18000 and 20000 rpm; mixing the obtained GO/CNC-PANI/Fe3+The spinning solution is filled into an 8-12ml plastic injector with a rotary nozzle, the diameter of a spinneret orifice is 200--1And the draw-bar drawing speed vr1=3.5-3.7cm/s and pull rod collection speed vr2=37-3.9 cm/s; after solidification for 30-35min, washing with water and ethanol for 3-5 times in sequence; collecting the obtained fiber, drying at room temperature for 10-12h, and vacuum drying at 37-40 deg.C for 20-24h to completely eliminate solvent in the fiber.
7. The method of claim 1, wherein: the step 6 specifically comprises the following steps: chemically reducing the fiber obtained in the step 5 in a 40-47wt% HI water solution at 80-85 ℃ for 9-10h, then continuously washing with absolute ethyl alcohol for 3-5 times, and vacuum drying at 40-50 ℃ for 10-12 h; then, thermal reduction is carried out, the fiber is reduced for 2.5-3h at 750-800 ℃, 1.5-2h at 950-1000 ℃ and 0.5-1h at 1150-1200 ℃ in Ar atmosphere, and the reduction is carried out in a vacuum tube furnace.
8. The method of claim 1, wherein: in step 7: the electrolyte is 0.8-1.2M sodium sulfate electrolyte.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101530823B1 (en) * | 2014-07-07 | 2015-06-25 | 서울대학교산학협력단 | Fabrication of three-dimensional graphene structures decorated with carbon-layer coated metal-oxide nanofiber for flexible supercapacitor electrode |
| CN105675182A (en) * | 2015-11-30 | 2016-06-15 | 重庆大学 | Preparation method of cellulose-based flexible stress-strain sensitive material |
| CN107464697A (en) * | 2017-07-28 | 2017-12-12 | 浙江理工大学 | A kind of fibrous type electrode of super capacitor and preparation method thereof |
| CN111101377A (en) * | 2019-12-26 | 2020-05-05 | 浙江理工大学 | Preparation method of flexible high-strength textile-based conductive composite material |
| CN111799097A (en) * | 2020-07-10 | 2020-10-20 | 西北工业大学 | Preparation method of graphene/MXene composite fiber flexible electrode material based on solid electrolyte and braided super capacitor |
| CN113764201A (en) * | 2021-07-06 | 2021-12-07 | 深圳大学 | Super capacitor, preparation method thereof, implantation method thereof and implantable electronic medical device |
-
2022
- 2022-02-21 CN CN202210156479.2A patent/CN114551117B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101530823B1 (en) * | 2014-07-07 | 2015-06-25 | 서울대학교산학협력단 | Fabrication of three-dimensional graphene structures decorated with carbon-layer coated metal-oxide nanofiber for flexible supercapacitor electrode |
| CN105675182A (en) * | 2015-11-30 | 2016-06-15 | 重庆大学 | Preparation method of cellulose-based flexible stress-strain sensitive material |
| CN107464697A (en) * | 2017-07-28 | 2017-12-12 | 浙江理工大学 | A kind of fibrous type electrode of super capacitor and preparation method thereof |
| CN111101377A (en) * | 2019-12-26 | 2020-05-05 | 浙江理工大学 | Preparation method of flexible high-strength textile-based conductive composite material |
| CN111799097A (en) * | 2020-07-10 | 2020-10-20 | 西北工业大学 | Preparation method of graphene/MXene composite fiber flexible electrode material based on solid electrolyte and braided super capacitor |
| CN113764201A (en) * | 2021-07-06 | 2021-12-07 | 深圳大学 | Super capacitor, preparation method thereof, implantation method thereof and implantable electronic medical device |
Non-Patent Citations (1)
| Title |
|---|
| 凌新龙;阳辰峰;宁军霞;: "纤维素的改性及应用研究进展", 纺织科学与工程学报, no. 03, pages 60 - 85 * |
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