CN114551117B - Preparation method of fiber type super capacitor for flexible antibacterial electronic skin - Google Patents
Preparation method of fiber type super capacitor for flexible antibacterial electronic skin Download PDFInfo
- Publication number
- CN114551117B CN114551117B CN202210156479.2A CN202210156479A CN114551117B CN 114551117 B CN114551117 B CN 114551117B CN 202210156479 A CN202210156479 A CN 202210156479A CN 114551117 B CN114551117 B CN 114551117B
- Authority
- CN
- China
- Prior art keywords
- cnc
- pani
- solution
- stirring
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003990 capacitor Substances 0.000 title claims abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 7
- 229920000767 polyaniline Polymers 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 24
- 229920002678 cellulose Polymers 0.000 claims abstract description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000002195 synergetic effect Effects 0.000 claims abstract description 13
- 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 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 24
- 235000010980 cellulose Nutrition 0.000 claims description 23
- 238000009987 spinning Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 21
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 10
- 239000007864 aqueous solution Substances 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
- 239000008240 homogeneous mixture Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 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
- 239000003638 chemical reducing agent 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
- 238000001914 filtration 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
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 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
- 238000002156 mixing Methods 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
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 241000894006 Bacteria Species 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000000845 anti-microbial effect Effects 0.000 abstract description 2
- 230000002500 effect on skin Effects 0.000 abstract description 2
- 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
- 238000009954 braiding Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008204 material by function Substances 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
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000037315 hyperhidrosis Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of capacitors, and discloses a preparation method of a flexible antibacterial fibrous supercapacitor for electronic skin. The invention firstly prepares Cellulose Nanocrystalline (CNC) and large-diameter high-concentration graphene oxide, synthesizes CNC-PANI suspension, and prepares RGO/CNC-PANI/Fe based by wet spinning and reduction method 3+ A flexible antimicrobial electronic dermal fiber supercapacitor. The strength of the CNC base fiber can be enhanced through a synergistic effect between CNC and polyaniline; potassium chloride can increase the conductivity and strain sensitivity of the fiber, while the capacitor can be made by releasing Fe 3+ To eliminate bacteria.
Description
Technical Field
The invention relates to the field of capacitors, in particular to a preparation method of a flexible antibacterial fibrous supercapacitor for electronic skin.
Background
With the development of society and the progress of technology, wearable devices are getting more and more attention, and gradually change the lives of people. The wearable device mainly refers to an electronic device which can be directly worn on a person, and is an electronic product which can be integrated into clothing or similar clothing. Next generation wearable electronics require the system to be worn directly on the skin of a person covered with a highly extensible soft flex. However, most wearable products existing in the market at present are mainly worn, and mainly include smart watches, bracelets, glasses and the like, but products which can be worn directly are few. In order to obtain a smart textile, one approach is to attach functional materials to a planar fabric in a stacked manner to perform its function, however, this manner of stacking the functional materials on the fabric surface greatly reduces the inherent properties of softness, breathability, mechanical properties, etc. of the fabric. While fibers are a constituent of fabrics, research and preparation of flexible fibers with functionalization is of great importance for the development of wearable devices, since their soft, deformable, breathable, durable, wash-resistant properties have been manufactured and used by humans for thousands of years.
The fiber itself is lightweight, flexible and easily woven, and can be used for wearable applications by constructing flexible fibrous devices. Thus, fibrous flexible devices have been widely studied, mainly as energy devices such as fibrous solar cells, supercapacitors, lithium ion batteries, and the like. However, these energy devices are ultimately intended to provide energy to the corresponding wearable electronics for proper operation. Besides the strategy of constructing a fibrous flexible device to be woven on clothes to realize the wearing, the electronic skin can be directly attached to the skin of a human body due to the advantage of high flexibility and thinness, so that the wearing application of the electronic device is realized.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a fiber type super capacitor for flexible antibacterial electronic skin. The invention firstly prepares Cellulose Nanocrystalline (CNC) and large-diameter high-concentration graphene oxide, synthesizes CNC-PANI suspension, and prepares RGO/CNC-PANI/Fe based by wet spinning and reduction method 3+ A flexible antimicrobial electronic dermal fiber supercapacitor. The strength of the CNC base fiber can be enhanced through a synergistic effect between CNC and polyaniline; potassium chloride can increase the conductivity and strain sensitivity of the fiber, while the capacitor can be made by releasing Fe 3+ To eliminate bacteria.
The specific technical scheme of the invention is as follows: a preparation method of a fiber type super capacitor for flexible antibacterial 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 nanocrystalline from the circulating acid mixture, washing the cellulose nanocrystalline with water by centrifugation, dialyzing to remove the residual acid, and freeze-drying.
The strength of CNC base fiber can be obviously enhanced through multi-carboxylation.
Step 2: preparation of large-diameter high-concentration graphene oxide (LGO) solution: adding graphite nano-sheets into chromic acid washing liquid, performing ultrasonic dispersion, mechanically stirring, pouring water, performing suction filtration, washing with water, and washing with ethanol; baking and cooling to room temperature; centrifuging the resulting light orange solution to remove unoxidized graphite; and (3) obtaining large-diameter graphene oxide, adding the large-diameter graphene oxide into water, and stirring to obtain a large-diameter high-concentration graphene oxide solution.
The graphene oxide prepared by the method has rich carboxyl active sites on the surface, and meanwhile, the dispersibility of the solution is improved. The graphene sheets are gathered together by weak Van der Waals force, and only the graphene sheets with atom thickness have extremely large surface area and are attached to each other and arranged like scales on fish bodies after being pulled into fibers; if the fibers are knotted, the strength at the knot depends on the bending coefficient of the fibers, and the strength is higher because the bending coefficient of graphene oxide is very low, as if the knot were not present at all.
Step 3: preparation of CNC-PANI suspension: adding hydrochloric acid and aniline monomer into cellulose nanocrystalline aqueous suspension, and stirring in ice bath to obtain a uniform mixture to prevent agglomeration; ammonium sulfate is added into water, and the mixture is subjected to vigorous stirring and oxidation polymerization at 0-5 ℃ to obtain CNC-PANI suspension.
In this step, the strength of the fiber can be enhanced by a synergistic effect between CNC and polyaniline.
Step 4: GO/CNC-PANI/Fe 3+ Preparation of spinning solution: dripping potassium chloride solution and ferric chloride solution into CNC-PANI suspension successively, stirring, and mixing with K + And Fe (Fe) 3+ Form dynamic metal ion coordination bond and weak hydrogen bond; and (2) adding the large-diameter high-concentration graphene oxide solution prepared in the step (2) into the suspension, and stirring to obtain the GO/CNC-PANI/Fe with the synergistic soft-hard hierarchical structure 3+ The mixture was homogeneous.
The invention is based on weak hydrogen bond and Fe 3+ The synergistic effect of chelation, as well as potassium chloride, can increase the conductivity and strain sensitivity of the fiber, resulting in devices having excellent mechanical properties and excellent conductivity. Meanwhile, if the device is used for attaching skin and the wound part of the skin is infected, the Fe in the device can be promoted by high temperature caused by the infection part (when staphylococcus aureus, staphylococcus epidermidis and streptococcus are infected by skin tissues, the phenomena of scratching, friction, high temperature, humidity, hyperhidrosis and the like are caused easily due to acute, subacute and chronic skin folliculitis) 3+ Released, thereby playing a role in eliminating bacteria.
Step 5: wet spinning preparation of GO/CNC-PANI/Fe 3+ And (3) fibers: for GO/CNC-PANI/Fe 3+ Centrifuging the uniform mixture; the obtained GO/CNC-PANI/Fe 3+ Filling the spinning solution into an injector with a rotary nozzle, and then injecting the spinning solution into a calcium chloride ethanol water solution coagulation bath; after solidification, washing with water and ethanol; the resulting fibers were collected, dried at room temperature, and then dried in vacuo to completely eliminate the solvent from the fibers.
Step 6: preparation of RGO/CNC-PANI/Fe by reduction method 3+ And (3) fibers: carrying out chemical reduction treatment on the fiber obtained in the step 5 in HI aqueous solution, washing with absolute ethyl alcohol, and drying in vacuum; then carrying out thermal reduction, and reducing the fiber for 2.5-3h at 750-800 ℃ under Ar atmosphere, 1.5-2h at 950-1000 ℃ and 0.5-1h at 1150-1200 ℃.
The multi-step calcination of the invention can eliminate stress concentration in the fiber, improve the tensile strength of the fiber, prevent the fiber from overheat shrinkage and better maintain the original length.
Step 7: assembly of solid state capacitors: 2 polyethylene terephthalate sheets coated with a gold layer are used as a supporting substrate and a current collector, the fiber obtained in the step 5 is pre-woven and then is placed on the substrate to form 2 electrodes, and cellulose paper soaked by electrolyte is used as solid electrolyte and is placed between the two electrodes to form a sandwich type symmetrical capacitor.
Preferably, the step 1 specifically includes: adding 2-3g microcrystalline cellulose into 100-110ml of a 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 10-12h; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the obtained functionalized cellulose nanocrystalline from the circulating acid mixture according to a liquid-solid ratio of 20-22 ml:1g of cellulose nanocrystals were washed 3-5 times with water by centrifugation, dialyzed against a dialysis bag with mw=10000-15000 Da for 24-48h to remove the remaining acid, and freeze-dried.
Preferably, step 2 specifically includes: adding 500-600-mg graphite nano-sheets into 560-ml chromic acid washing liquid, performing ultrasonic dispersion for 30-40 min, mechanically stirring at 35-45 ℃ for 10-20 min, pouring 1-2 liters of water, performing suction filtration, washing 3-5 times, and washing with ethanol 2-3 times; baking at 110-120deg.C for 3-3.5, h, and cooling to room temperature; centrifuging the resulting light orange solution at 2000-3000rpm for 8-10min to remove unoxidized graphite; and (3) obtaining large-diameter graphene oxide with the transverse dimension of 0.5-6 mu m, adding 300-350mg of large-diameter graphene oxide into 10-12ml of water, and stirring for 3-4 hours at the temperature of 40-45 ℃ to obtain a large-diameter high-concentration graphene oxide solution.
Preferably, the step 3 specifically includes: adding 20-22ml of 1M hydrochloric acid and 0.20-0.22g of aniline monomer into 8-12g of 1-3wt% cellulose nanocrystalline aqueous suspension, stirring in ice bath for 60-70min to obtain a uniform mixture, and preventing agglomeration; 0.41-0.43g of ammonium sulfate is added into 2-3ml of water, and the mixture is stirred vigorously at 0-5 ℃ for 2-2.5h for oxidative polymerization, thus obtaining CNC-PANI suspension.
Preferably, the step 4 specifically includes: dripping 2-2.5ml of 0.0018mol potassium chloride solution and 2-2.5ml of 0.0018mol ferric chloride solution into CNC-PANI suspension, stirring at 25-30deg.C for 1-1.5 hr, and adding K + And Fe (Fe) 3+ Form dynamic metal ion coordination bond and weak hydrogen bond; adding 1-1.5g of the large-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring for 2-3h at 25-30 ℃ to obtain the GO/CNC-PANI/Fe with the synergistic soft-hard hierarchical structure 3+ The mixture was homogeneous.
Preferably, the step 5 specifically includes: for GO/CNC-PANI/Fe 3+ Centrifuging the homogeneous mixture at 18000-20000 rpm; the obtained GO/CNC-PANI/Fe 3+ Spinning solution fillingIn 8-12ml plastic injector with rotary nozzle, the diameter of the spinneret orifice is 200-400 μm, and then the spinning solution is injected into 3-7wt% calcium chloride ethanol water solution coagulating bath, the corresponding injector speed is 40-60 μl min -1 Pull rod stretch speed v r1 =3.5-3.7 cm/s and pull rod collection speed v r2 =3.7-3.9 cm/s; after solidification for 30-35min, washing with water and ethanol for 3-5 times; the resulting fibers were collected, dried at room temperature for 10-12 hours, and then dried at 37-40 ℃ in vacuo for 20-24 hours to completely eliminate the solvent from the fibers.
Preferably, step 6 specifically includes: carrying out chemical reduction treatment on the fiber obtained in the step 5 in 40-47wt% HI aqueous solution at 80-85 ℃ for 9-10h, then continuously washing with absolute ethyl alcohol for 3-5 times, and carrying out vacuum drying at 40-50 ℃ for 10-12h; then carrying out thermal reduction, wherein the fiber is reduced for 2.5-3h at 750-800 ℃ under Ar atmosphere, is reduced for 1.5-2h at 950-1000 ℃ and is reduced for 0.5-1h at 1150-1200 ℃, and the reduction is carried out in a vacuum tube furnace.
Preferably, in step 7: the electrolyte is sodium sulfate electrolyte with the concentration of 0.8-1.2M.
Compared with the prior art, the invention has the following technical effects:
(1) The strength of CNC-based fibers is enhanced by the present invention through multi-carboxylation.
(2) The graphene oxide prepared by the method has rich carboxyl active sites on the surface, and meanwhile, the dispersibility of the solution is improved. The graphene sheets are gathered together by weak Van der Waals force, and only the graphene sheets with atom thickness have extremely large surface area and are attached to each other and arranged like scales on fish bodies after being pulled into fibers; if the fibers are knotted, the strength at the knot depends on the bending coefficient of the fibers, as graphene oxide is very low in bending coefficient, as if the knot were not present at all, and the strength is high.
(3) The strength of the fiber is enhanced by the synergistic effect between the CNC and the polyaniline.
(4) The invention is based on weak hydrogen bond and Fe 3+ The synergistic effect of chelation and potassium chloride can improve the conductivity and strain sensitivity of the fiber, so that the device has excellent mechanical property and excellent conductivity; at the same time due toThe device is used for attaching skin, if the wound part of the skin is infected, the high temperature caused by the infected part can promote Fe in the device 3+ Released, thereby playing a role in eliminating bacteria.
(5) The multi-step calcination of the invention can eliminate stress concentration in the fiber, improve the tensile strength of the fiber, prevent the fiber from overheat shrinkage and better maintain the original length.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Step 1: preparation of Cellulose Nanocrystals (CNC): 2g of microcrystalline cellulose (MCC) was added to 100ml of a circulating acid mixture (volume ratio: citric acid: hydrochloric acid=9:1) and stirred continuously for 10h at 80 ℃; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and circulating acid mixture, adding deionized water into CNC (liquid-solid ratio 20 ml:1 g), and continuously centrifugally 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-diameter high-concentration graphene oxide (LGO) solution: adding the 500 mg graphite nano-sheets into 560 ml chromic acid washing liquid, and performing ultrasonic dispersion for 30 min; then mechanically stirring for 10min at 40 ℃, pouring 1 liter of deionized water, carrying out suction filtration, washing 3 times with water and 2 times with ethanol; baking at 110 ℃ for 3 hours, and cooling to room temperature for standby; centrifuging the light orange solution at 2000rpm for 8min to remove unoxidized graphite; obtaining large-diameter graphene oxide (LGO) with the transverse dimension of 0.5 mu m, adding 300mg of large-diameter graphene oxide into 10ml of water, and stirring at 40 ℃ for 3 hours to obtain a high-concentration LGO solution for later use;
step 3: preparation of CNC-PANI suspension: hydrochloric acid (20 ml, 1M) and aniline monomer (0.20 g) were then added to CNC aqueous suspension (10 g,2 wt%) and stirred in an ice bath for 60min to give a homogeneous mixture, preventing agglomeration; adding 0.41g of ammonium sulfate into 2ml of deionized water, and vigorously stirring at about 1 ℃ for 2 hours for oxidative polymerization to obtain CNC-PANI suspension;
step 4: GO/CNC-PANI/Fe 3+ Preparation of spinning solution:potassium chloride solution (2 ml,0.134g,0.0018 mol) and ferric chloride solution (2 ml, 0.292g,0.0018 mol) were added dropwise to the CNC-PANI suspension, and stirred at 25℃for 1h, followed by the different metal ions (K + And Fe (Fe) 3+ ) Form dynamic metal ion coordination bond and weak hydrogen bond; adding 1g of LGO solution prepared in the step 2 into the suspension, and stirring for 2h at 25 ℃ to obtain the GO/CNC-PANI/Fe with a synergistic soft-hard hierarchical structure 3+ Uniformly mixing the materials for later use;
step 5: wet spinning preparation of GO/CNC-PANI/Fe 3+ And (3) fibers: GO/CNC-PANI/Fe 3+ Centrifuging the homogeneous mixture at 18000 rpm; GO/CNC-PANI/Fe 3+ The spinning solution was fed into a 10ml plastic syringe with a rotating nozzle, the diameter size of the spinning orifice was 300. Mu.m, and then the spinning solution was injected into a coagulation bath of 5wt% calcium chloride ethanol aqueous solution (1:3 v/v), the corresponding syringe speed was 40. Mu.l min -1 Pull rod stretch speed v r1 =3.5 cm/s and pull rod collection speed v r2 =3.7 cm/s; after solidification for 30min, washing with water and ethanol for 3 times in sequence; the collected fibers were dried at room temperature for 10 hours and then dried at 37 ℃ in vacuo for 20 hours to completely eliminate the solvent from the fibers;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method 3+ And (3) fibers: the fiber obtained in the step 5 is subjected to chemical reduction treatment for 9 hours at 80 ℃ in HI (40%) aqueous solution, and then is continuously washed for 3 times by absolute ethyl alcohol, and is dried for 10 hours at 40 ℃; then carrying out thermal reduction, namely reducing the fiber for 2.5 hours at 750 ℃ under Ar atmosphere, reducing the fiber for 1.5 hours at 950 ℃ and reducing the fiber for 0.5 hour at 1150 ℃, wherein the reduction is carried out in a vacuum tube furnace;
step 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as counter electrode and mercury/mercury as reference electrode. Measurements were made in 1M sodium sulfate aqueous electrolyte at room temperature. Electrochemical performance was characterized using the CHI660B electrochemical workstation (Shanghai CH instruments); CV reactions were carried out between 0 and 1V at different scan rates of 10 mV/s. Measuring a gas electrostatic charge-discharge curve within a potential range of 0-1V under different currents of 20 mu A; EIS measurements are made at open circuit potential over a frequency range of 100kHz to 0.01HzThe ac disturbance is 5mV; according to experimental data, calculating mass specific capacitance, wherein the mass specific capacitance calculation formula of the supercapacitor electrode is C m =i×Δt/(m×Δv), wherein: i is constant current, deltat is discharge time, m is total mass added by the electrode, deltaV is potential difference in the discharge process;
step 8: assembly of solid state capacitors: 2 polyethylene terephthalate sheets (2 cm. Times.4 cm) coated with a gold layer were used as a supporting substrate and a current collector, 2 fibers (2 cm. Times.4 cm) obtained by simply braiding 2 steps 6 were placed on the substrate to form 2 electrodes, and cellulose paper soaked with 1M sodium sulfate electrolyte was placed between the two electrodes as a solid electrolyte 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 cycles of acid mixture (volume ratio: citric acid: hydrochloric acid=9:1) and stirred continuously for 11h at 85 ℃; after completion, the suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and circulating acid mixture, adding deionized water into CNC (liquid-solid ratio 21 ml:1 g), and continuously centrifugally washing for 4 times; dialyzing with dialysis bag (Mw cut-off 12000 Da) for 36 hr to remove residual acid, and freeze drying;
step 2: preparation of large-diameter high-concentration graphene oxide (LGO) solution: adding 550 mg graphite nano-sheets into 560 ml chromic acid washing liquid, and performing ultrasonic dispersion for 35 min; then mechanically stirring for 15 min at 40 ℃, pouring 1.5 liters of deionized water, carrying out suction filtration, washing for 4 times, and washing with ethanol for 2 times; baking at 115 ℃ for 3h, and cooling to room temperature for later use; centrifuging the light orange solution at 2000rpm for 9min to remove unoxidized graphite; obtaining large-diameter graphene oxide (LGO) with the transverse dimension of 0.5-6 mu m, adding 330mg of large-diameter graphene oxide into 11ml of water, and stirring at 40 ℃ for 3 hours to obtain a high-concentration LGO solution for later use;
step 3: preparation of CNC-PANI suspension: hydrochloric acid (21 ml, 1M) and aniline monomer (0.21 g) were then added to 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 vigorously stirring at about 3 ℃ for 2 hours for oxidative polymerization to obtain CNC-PANI suspension;
step 4: GO/CNC-PANI/Fe 3+ Preparation of spinning solution: potassium chloride solution (2 ml,0.134g,0.0018 mol) and ferric chloride solution (2 ml, 0.292g,0.0018 mol) were added dropwise to the CNC-PANI suspension, and stirred at 28℃for 1h, followed by different metal ions (K + And Fe (Fe) 3+ ) Form dynamic metal ion coordination bond and weak hydrogen bond; adding 1g of LGO solution prepared in the step 2 into the suspension, and stirring for 2.5h at 25 ℃ to obtain the GO/CNC-PANI/Fe with a synergistic soft-hard hierarchical structure 3+ Uniformly mixing the materials for later use;
step 5: wet spinning preparation of GO/CNC-PANI/Fe 3+ And (3) fibers: GO/CNC-PANI/Fe 3+ The homogeneous mixture was centrifuged at 19000 rpm; GO/CNC-PANI/Fe 3+ The spinning solution was fed into a 10ml plastic syringe with a rotating nozzle, the diameter size of the spinning orifice was 300. Mu.m, and then the spinning solution was injected into a coagulation bath of 5wt% calcium chloride ethanol aqueous solution (1:3 v/v), the corresponding syringe speed was 50. Mu.l min -1 Pull rod stretch speed v r1 =3.6 cm/s and pull rod collection speed v r2 =3.8 cm/s; after solidification for 30min, washing with water and ethanol for 4 times in sequence; the collected fibers were dried at room temperature for 11 hours and then dried at 37 ℃ in vacuo for 22 hours to completely eliminate the solvent from the fibers;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method 3+ And (3) fibers: the fiber obtained in the step 5 is subjected to chemical reduction treatment for 9.5 hours at 80 ℃ in HI (44%) aqueous solution, and then is continuously washed for 4 times by absolute ethyl alcohol, and is dried for 11 hours at 45 ℃ in vacuum; then carrying out thermal reduction, namely reducing the fiber for 2.5 hours at 775 ℃ under Ar atmosphere, reducing for 1.5 hours at 950 ℃ and reducing for 0.8 hour at 1175 ℃, wherein the reduction is carried out in a vacuum tube furnace;
step 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as counter electrode and mercury/mercury as reference electrode. Measurements were made in 1M sodium sulfate aqueous electrolyte at room temperature. Electrochemical performance was characterized using the CHI660B electrochemical workstation (Shanghai CH instruments); CV reaction between 0 and 1V at different scan rates of 500mV/sAnd (3) row. Measuring a gas electrostatic charge-discharge curve within a potential range of 0-1V under different currents of 50 mu A; EIS measurements were performed at open circuit potential at a frequency range of 100kHz to 0.01Hz with an alternating current disturbance of 5mV; according to experimental data, calculating mass specific capacitance, wherein the mass specific capacitance calculation formula of the supercapacitor electrode is C m =i×Δt/(m×Δv), wherein: i is constant current, deltat is discharge time, m is total mass added by the electrode, deltaV is potential difference in the discharge process;
step 8: assembly of solid state capacitors: 2 polyethylene terephthalate sheets (2 cm. Times.4 cm) coated with a gold layer were used as a supporting substrate and a current collector, 2 fibers (2 cm. Times.4 cm) obtained by simply braiding 2 steps 6 were placed on the substrate to form 2 electrodes, and cellulose paper soaked with 1M sodium sulfate electrolyte was placed between the two electrodes as a solid electrolyte 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 for 12h at 90 ℃; after completion, the suspension was rapidly cooled to room temperature; filtering, separating the functionalized CNC and circulating acid mixture, adding deionized water into CNC (liquid-solid ratio 22 ml:1 g), and continuously centrifugally 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-diameter high-concentration graphene oxide (LGO) solution: adding 600 mg graphite nano-sheets into 560 ml chromic acid washing liquid, and performing ultrasonic dispersion 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 120deg.C for 3.5 and h, and cooling to room temperature for use; centrifuging the light orange solution at 3000rpm for 10min to remove unoxidized graphite; obtaining large-diameter graphene oxide (LGO) with the transverse dimension of 0.5-6 mu m, adding 350mg of large-diameter graphene oxide into 12ml of water, and stirring at 45 ℃ for 4 hours to obtain a high-concentration LGO solution for later use;
step 3: preparation of CNC-PANI suspension: hydrochloric acid (22 ml, 1M) and aniline monomer (0.22 g) were then added to 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 vigorously stirring at about 5 ℃ for 2.5 hours for oxidative polymerization to obtain CNC-PANI suspension;
step 4: GO/CNC-PANI/Fe 3+ Preparation of spinning solution: potassium chloride solution (2.5 ml,0.134g,0.0018 mol) and ferric chloride solution (2.5 ml, 0.292g,0.0018 mol) were added dropwise to the CNC-PANI suspension, and stirred at 30deg.C for 1.5h, followed by different metal ions (K + And Fe (Fe) 3+ ) Form dynamic metal ion coordination bond and weak hydrogen bond; adding 1.5g of LGO solution prepared in the step 2 into the suspension, and stirring for 3 hours at 30 ℃ to obtain the GO/CNC-PANI/Fe with a synergistic soft-hard hierarchical structure 3+ Uniformly mixing the materials for later use;
step 5: wet spinning preparation of GO/CNC-PANI/Fe 3+ And (3) fibers: GO/CNC-PANI/Fe 3+ Centrifuging the homogeneous mixture at a speed of 20000 rpm; GO/CNC-PANI/Fe 3+ The spinning solution was fed into a 10ml plastic syringe with a rotating nozzle, the diameter size of the spinning orifice was 300. Mu.m, and then the spinning solution was injected into a coagulation bath of 5wt% calcium chloride ethanol aqueous solution (1:3 v/v), the corresponding syringe speed was 60. Mu.l min -1 Pull rod stretch speed v r1 =3.7 cm/s and pull rod collection speed v r2 =3.9 cm/s; after solidification for 35min, washing with water and ethanol for 5 times in sequence; the collected fibers were dried at room temperature for 12 hours and then dried at 40 ℃ in vacuo for 24 hours to completely eliminate the solvent from the fibers;
step 6: preparation of RGO/CNC-PANI/Fe by reduction method 3+ And (3) fibers: the fiber obtained in the step 5 is subjected to chemical reduction treatment in HI (47%) aqueous solution at 85 ℃ for 10 hours, and then is washed with absolute ethyl alcohol for 5 times continuously, and is dried in vacuum at 50 ℃ for 12 hours; then carrying out thermal reduction, wherein the fiber is reduced for 3 hours at 800 ℃ and 2 hours at 1000 ℃ and 1 hour at 1200 ℃ in Ar atmosphere, and all the steps are carried out in a vacuum tube furnace;
step 7: electrochemical measurement: all electrochemical measurements were performed in a standard three-electrode system with platinum as counter electrode and mercury/mercury as reference electrode. Measurement of 1M sodium sulfate aqueous electrolyte at room temperatureIs performed in the middle (a). Electrochemical performance was characterized using the CHI660B electrochemical workstation (Shanghai CH instruments); CV reactions were carried out between 0 and 1V at different scan rates of 1000 mV/s. Under different currents of 80 mu A, measuring a gas electrostatic charge-discharge curve within a potential range of 0-1V; EIS measurements were performed at open circuit potential at a frequency range of 100kHz to 0.01Hz with an alternating current disturbance of 5mV; according to experimental data, calculating mass specific capacitance, wherein the mass specific capacitance calculation formula of the supercapacitor electrode is C m =i×Δt/(m×Δv), wherein: i is constant current, deltat is discharge time, m is total mass added by the electrode, deltaV is potential difference in the discharge process;
step 8: assembly of solid state capacitors: 2 polyethylene terephthalate sheets (2 cm. Times.4 cm) coated with a gold layer were used as a supporting substrate and a current collector, 2 fibers (2 cm. Times.4 cm) obtained by simply braiding 2 steps 6 were placed on the substrate to form 2 electrodes, and cellulose paper soaked with 1M sodium sulfate electrolyte was placed between the two electrodes as a solid electrolyte 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 unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a fiber type super capacitor for flexible antibacterial electronic skin is characterized by comprising the following steps of: the method comprises the following steps:
step 1: preparation of 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 nanocrystalline from the circulating acid mixture, continuously centrifuging and washing the cellulose nanocrystalline with water, dialyzing to remove the residual acid, and freeze-drying;
step 2: preparation of large-diameter high-concentration graphene oxide solution: adding graphite nano-sheets into chromic acid washing liquid, performing ultrasonic dispersion, mechanically stirring, pouring water, performing suction filtration, washing with water, and washing with ethanol; baking and cooling to room temperature; centrifuging the resulting light orange solution to remove unoxidized graphite; the preparation method comprises the steps of obtaining large-diameter graphene oxide, adding the large-diameter graphene oxide into water, and stirring to obtain a large-diameter high-concentration graphene oxide solution;
step 3: preparation of CNC-PANI suspension: adding hydrochloric acid and aniline monomer into cellulose nanocrystalline aqueous suspension, and stirring in ice bath to obtain a uniform mixture to prevent agglomeration; adding ammonium sulfate into water, and carrying out violent stirring oxidation polymerization at 0-5 ℃ to obtain CNC-PANI suspension;
step 4: GO/CNC-PANI/Fe 3+ Preparation of spinning solution: dripping potassium chloride solution and ferric chloride solution into CNC-PANI suspension successively, stirring, and mixing with K + And Fe (Fe) 3+ Form dynamic metal ion coordination bond and weak hydrogen bond; and (2) adding the large-diameter high-concentration graphene oxide solution prepared in the step (2) into the suspension, and stirring to obtain the GO/CNC-PANI/Fe with the synergistic soft-hard hierarchical structure 3+ A homogeneous mixture;
step 5: wet spinning preparation of GO/CNC-PANI/Fe 3+ And (3) fibers: for GO/CNC-PANI/Fe 3+ Centrifuging the uniform mixture; the obtained GO/CNC-PANI/Fe 3+ Filling the spinning solution into an injector with a rotary nozzle, and then injecting the spinning solution into a calcium chloride ethanol water solution coagulation 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 method 3+ And (3) fibers: carrying out chemical reduction treatment on the fiber obtained in the step 5 in HI aqueous solution, washing with absolute ethyl alcohol, and drying in vacuum; then carrying out thermal reduction, and reducing the fiber for 2.5-3h at 750-800 ℃ under Ar atmosphere, 1.5-2h at 950-1000 ℃ and 0.5-1h at 1150-1200 ℃;
step 7: assembly of solid state capacitors: 2 polyethylene terephthalate sheets coated with a gold layer are used as a supporting substrate and a current collector, the fiber obtained in the step 5 is pre-woven and then is placed on the substrate to form 2 electrodes, and cellulose paper soaked by electrolyte is used as solid electrolyte and is placed between the two electrodes to form a sandwich type symmetrical capacitor.
2. The method of manufacturing according to claim 1, wherein: the step 1 specifically comprises the following steps: adding 2-3g microcrystalline cellulose into 100-110ml of a 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 10-12h; after completion, the resulting suspension was rapidly cooled to room temperature; filtering, separating the obtained functionalized cellulose nanocrystalline from the circulating acid mixture according to a liquid-solid ratio of 20-22 ml:1g of cellulose nanocrystals were washed 3-5 times with water by centrifugation, dialyzed against a dialysis bag with mw=10000-15000 Da for 24-48h to remove the remaining acid, and freeze-dried.
3. The method of manufacturing according to claim 1, wherein: the step 2 specifically comprises the following steps: adding 500-600-mg graphite nano-sheets into 560-ml chromic acid washing liquid, performing ultrasonic dispersion for 30-40 min, mechanically stirring at 35-45 ℃ for 10-20 min, pouring 1-2 liters of water, performing suction filtration, washing 3-5 times, and washing with ethanol 2-3 times; baking at 110-120deg.C for 3-3.5, h, and cooling to room temperature; centrifuging the resulting light orange solution at 2000-3000rpm for 8-10min to remove unoxidized graphite; and (3) obtaining large-diameter graphene oxide with the transverse dimension of 0.5-6 mu m, adding 300-350mg of large-diameter graphene oxide into 10-12ml of water, and stirring for 3-4 hours at the temperature of 40-45 ℃ to obtain a large-diameter high-concentration graphene oxide solution.
4. The method of manufacturing according to 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 nanocrystalline aqueous suspension, stirring in ice bath for 60-70min to obtain a uniform mixture, and preventing agglomeration; 0.41-0.43g of ammonium sulfate is added into 2-3ml of water, and the mixture is stirred vigorously at 0-5 ℃ for 2-2.5h for oxidative polymerization, thus obtaining CNC-PANI suspension.
5. The method of manufacturing according to 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 CNC-PANI suspension, stirring at 25-30deg.C for 1-1.5 hr, and adding K + And Fe (Fe) 3+ Form dynamic metal ion coordination bond and weak hydrogen bond; adding 1-1.5g of the large-diameter high-concentration graphene oxide solution prepared in the step 2 into the suspension, and stirring for 2-3h at 25-30 ℃ to obtain the GO/CNC-PANI/Fe with the synergistic soft-hard hierarchical structure 3+ The mixture was homogeneous.
6. The method of manufacturing according to claim 1, wherein: the step 5 specifically comprises the following steps: for GO/CNC-PANI/Fe 3+ Centrifuging the homogeneous mixture at 18000-20000 rpm; the obtained GO/CNC-PANI/Fe 3+ The spinning solution is filled into 8-12ml plastic injector with rotary nozzle, the diameter of the spinning hole is 200-400 μm, and then the spinning solution is injected into 3-7wt% calcium chloride ethanol water solution coagulating bath, the corresponding injector speed is 40-60 μl min -1 Pull rod stretch speed v r1 =3.5-3.7 cm/s and pull rod collection speed v r2 =3.7-3.9 cm/s; after solidification for 30-35min, washing with water and ethanol for 3-5 times; the resulting fibers were collected, dried at room temperature for 10-12 hours, and then dried at 37-40 ℃ in vacuo for 20-24 hours to completely eliminate the solvent from the fibers.
7. The method of manufacturing according to claim 1, wherein: the step 6 specifically comprises the following steps: carrying out chemical reduction treatment on the fiber obtained in the step 5 in 40-47wt% HI aqueous solution at 80-85 ℃ for 9-10h, then continuously washing with absolute ethyl alcohol for 3-5 times, and carrying out vacuum drying at 40-50 ℃ for 10-12h; then carrying out thermal reduction, wherein the fiber is reduced for 2.5-3h at 750-800 ℃ under Ar atmosphere, is reduced for 1.5-2h at 950-1000 ℃ and is reduced for 0.5-1h at 1150-1200 ℃, and the reduction is carried out in a vacuum tube furnace.
8. The method of manufacturing according to claim 1, wherein: in step 7: the electrolyte is sodium sulfate electrolyte with the concentration of 0.8-1.2M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210156479.2A CN114551117B (en) | 2022-02-21 | 2022-02-21 | Preparation method of fiber type super capacitor for flexible antibacterial electronic skin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210156479.2A CN114551117B (en) | 2022-02-21 | 2022-02-21 | Preparation method of fiber type super capacitor for flexible antibacterial electronic skin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114551117A CN114551117A (en) | 2022-05-27 |
| CN114551117B true CN114551117B (en) | 2023-10-03 |
Family
ID=81674660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210156479.2A Active CN114551117B (en) | 2022-02-21 | 2022-02-21 | Preparation method of fiber type super capacitor for flexible antibacterial electronic skin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114551117B (en) |
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 |
|---|
| 纤维素的改性及应用研究进展;凌新龙;阳辰峰;宁军霞;;纺织科学与工程学报(03);60-85 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114551117A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wei et al. | An all-solid-state yarn supercapacitor using cotton yarn electrodes coated with polypyrrole nanotubes | |
| Li et al. | Highly-wrinkled reduced graphene oxide-conductive polymer fibers for flexible fiber-shaped and interdigital-designed supercapacitors | |
| Sun et al. | Recent progress of fiber-shaped asymmetric supercapacitors | |
| Luo et al. | Constructing 3D bacterial cellulose/graphene/polyaniline nanocomposites by novel layer-by-layer in situ culture toward mechanically robust and highly flexible freestanding electrodes for supercapacitors | |
| Liang et al. | Continuous and integrated PEDOT@ Bacterial cellulose/CNT hybrid helical fiber with “reinforced cement-sand” structure for self-stretchable solid supercapacitor | |
| CN110379642B (en) | Stretchable nanofiber, application thereof, stretchable capacitor electrode comprising stretchable nanofiber and preparation method | |
| CN107574493A (en) | A kind of spiral winding structure flexible extensible strain transducer based on electrospinning | |
| Dong et al. | Matching electrode lengths enables the practical use of asymmetric fiber supercapacitors with a high energy density | |
| CN102779648B (en) | Preparation method for flexible electrode material for super capacitor | |
| Gopalsamy et al. | Wet-spun poly (ionic liquid)-graphene hybrid fibers for high performance all-solid-state flexible supercapacitors | |
| Zhao et al. | Utilizing human hair for solid-state flexible fiber-based asymmetric supercapacitors | |
| CN111944167A (en) | Conductive hydrogel and preparation method and application thereof | |
| Ramandi et al. | Self-supporting electrode for flexible supercapacitors: NiCo-layered double hydroxide derived from metal organic frameworks wrapped on graphene/polyaniline nanotubes@ cotton cloth | |
| Su et al. | Flexible two-ply yarn supercapacitors based on carbon nanotube/stainless steel core spun yarns decorated with Co3O4 nanoparticles and MnOx composites | |
| Cai et al. | High performance flexible silk fabric electrodes with antibacterial, flame retardant and UV resistance for supercapacitors and sensors | |
| CN105561403A (en) | Preparation method of alginate-graphene-nano cuprous oxide composite antibacterial film | |
| Wang et al. | Hierarchical core-shell polypyrrole@ NiCo layered double hydroxide arrays grown on stainless steel yarn with high flexibility for 1D symmetric yarn-shaped supercapacitors | |
| Nie et al. | Robust rope supercapacitor constructed by programmed graphene composite fibers with high and stable performance | |
| Jatoi et al. | Current applications of smart nanotextiles and future trends | |
| CN114551117B (en) | Preparation method of fiber type super capacitor for flexible antibacterial electronic skin | |
| Cai et al. | Preparation of sulfur-doped graphene fibers and their application in flexible fibriform micro-supercapacitors | |
| Dong et al. | Highly sensitive, scrub-resistant, robust breathable wearable silk yarn sensors via interfacial multiple covalent reactions for health management | |
| CN108396399A (en) | A kind of production method of graphene intelligent health-care underwear | |
| Lv et al. | Nanocellulose-based nanogenerators for sensor applications: A review | |
| Zhao et al. | Wet-spun PEDOT: PSS/ionic liquid composite fibers for wearable e-textiles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |