CN110164706B - Preparation method of bacterial cellulose-carbon nanotube/polyaniline composite microfiber and micro supercapacitor - Google Patents

Preparation method of bacterial cellulose-carbon nanotube/polyaniline composite microfiber and micro supercapacitor Download PDF

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CN110164706B
CN110164706B CN201910326433.9A CN201910326433A CN110164706B CN 110164706 B CN110164706 B CN 110164706B CN 201910326433 A CN201910326433 A CN 201910326433A CN 110164706 B CN110164706 B CN 110164706B
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bacterial cellulose
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CN110164706A (en
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韩景泉
李丽圭
王瑶
岳一莹
梅长彤
徐信武
朱赛玲
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Nanjing Forestry University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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

Abstract

The invention discloses a preparation method of bacterial cellulose-carbon nano tube/polyaniline composite microfiber, which is based on a microfluid spinning technology, and is characterized in that a BC-CNT gel fiber is formed by chelating with a dispersion of SA and BC-CNT as a core layer and calcium chloride as a sheath layer; then soaking the prepared BC-CNT fiber into aniline dispersion after coagulating bath, washing, thermal shrinkage and cooling, and adding ammonium persulfate solution for reaction; BC-CNT/PANI fibers were produced. Preparing a micro super capacitor, namely placing two composite microfibers on a PDMS substrate in parallel; the tail parts are respectively fixed with copper wires; and covering the gel electrolyte and the PDMS precursor. The specific surface area and the electrochemical performance are increased through the internal layered nuclear sheath and the porous structure of the composite microfiber, so that the supercapacitor has high energy density, high power density, good cycle retention capacity and bending capacity, and can be widely applied to portable and miniaturized electronic equipment.

Description

Preparation method of bacterial cellulose-carbon nanotube/polyaniline composite microfiber and micro supercapacitor
Technical Field
The invention relates to a bacterial cellulose-carbon nano tube/polyaniline composite microfiber, in particular to a preparation method of the bacterial cellulose-carbon nano tube/polyaniline composite microfiber and a preparation method of a micro super capacitor, and belongs to the technical field of polymer composite conductive materials.
Background
Carbon Nanotubes (CNTs) are a one-dimensional quantum nanomaterial with a special structure, with a diameter of the order of nanometers (1-100nm) and a length of the order of micrometers, and the two ends of the tube are generally sealed. The carbon nanotube is mainly composed of six-membered ring structure (carbon atom sp)2Hybrid) of a single or several layers of coaxial circular tubes with a layer spacing of about 0.34 nm. It is a widely used electrode material, and because carbon nanotubes have special physical and chemical properties, they can also be assembled into fibers by solid-state spinning or wet spinning techniques. Although the potential of carbon nanotubes is impressive, its practical application is limited due to its slow production rate, high cost, limited functionality and poor wettability.
Bacterial Cellulose (BC) is a highly crystalline three-dimensional network formed by products of metabolism of various bacteria, free of lignin, hemicellulose and other extractives. The structure enables the BC to have certain special characteristics, such as high purity, high crystallinity, larger mechanical strength, high water retention value, antibacterial property, nontoxicity, biocompatibility, biodegradability and the like, thereby being widely applied in a plurality of fields. It is known from research that bacterial cellulose can be used as a base layer of a conductive material due to its inherent mechanical strength and elasticity, thereby increasing the strength of the conductive material (e.g., PPy, PANI) and forming an independent electrode.
Polyaniline (PANI) is a typical conductive polymer, and has diversified structures, higher conductivity, unique doping mechanism, easily available raw materials, simple synthesis method and good environmental stability, so that the Polyaniline (PANI) becomes a hotspot of conductive polymer research and is widely applied to the fields of optics, electrics, magnetics and the like. However, PANI has a conjugated delocalized structure, which makes PANI insoluble in organic solvents, and has poor conductivity in neutral and alkaline environments, and thus, application is limited. PANI is easy to compound with other organic or inorganic materials, so that the function and the application of the PANI are more abundant and wider. Therefore, PANI has been a hot spot for conductive polymer research.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a bacterial cellulose-carbon nano tube/polyaniline composite microfiber and a micro supercapacitor.
In order to achieve the above object, the present invention adopts the following technical solutions:
a preparation method of bacterial cellulose-carbon nano tube/polyaniline composite microfiber comprises the following steps:
s1, chelating to form BC-CNT gel fibers by taking the dispersion of SA and BC-CNT as a core layer and calcium chloride as a sheath layer based on a microfluid spinning technology; then carrying out coagulating bath, washing, thermal shrinkage and cooling to obtain the BC-CNT fiber;
s2, immersing the BC-CNT fiber into aniline dispersion, and adding ammonium persulfate solution (N)ANI：NAPS1: 1.25) reacting, and forming a polyaniline layer on the surface of the BC-CNT fiber by adopting an in-situ polymerization method; and washing to obtain the BC-CNT/PANI fiber.
The microfluid spinning technology in the step S1 includes a reaction microchannel;
a core cavity is arranged in a tube cavity of the reaction microchannel, and the tube cavity outside the core cavity is a sheath cavity;
the inlet ends of the core cavity and the sheath cavity are respectively connected with the core tube and the sheath tube.
The preparation of the dispersion of SA and BC-CNT in step S1 above, comprising the steps of:
a1, mixing BC and CNTs in an aqueous solution according to a certain mass ratio, stirring and ultrasonically dispersing to prepare a BC-CNT dispersion liquid;
a2, adding SA into the BC-CNT dispersion liquid according to a certain mass ratio, and stirring to form dispersion
The mass ratio of BC to CNTs in the step A1 is 1:1-1: 2; the mass ratio of SA to BC in step a2 was 6: 1.
The coagulating bath in the step S1 is calcium chloride solution, washed to be deionized water, and then is heated and condensed to be dried for 2-3h in a vacuum oven at 100 ℃, and then is heated at the heating rate of 2.5 ℃/min and is maintained at 800-;
in step S2, the BC-CNT fiber is soaked in aniline dispersion at 0 ℃ for 1-2h
The reaction temperature is 0 ℃, and the reaction time is 10-12 h;
the washing solution comprises ethanol and water in sequence.
The aniline dispersion in step S2 is a dispersion obtained by dissolving aniline monomer in phosphoric acid and stirring.
Further, the concentration of the phosphoric acid is 1mol/l, and the mass of the aniline monomer is 0.5-0.8 g.
A miniature super capacitor comprises the following preparation steps:
b1, placing a bacterial cellulose-carbon nanotube/polyaniline composite microfiber as set forth in any one of claims 1 to 7 on a PDMS substrate in parallel;
b2, fixing copper wires at the tail parts of the BC-CNT/PANI fibers through conductive silver paste;
and B3, covering a gel electrolyte on the BC-CNT/PANI fiber, coating a PDMS precursor, and solidifying at 75-80 ℃ to obtain the super capacitor.
The gel electrolyte comprises: phosphoric acid/polyvinyl alcohol gel electrolyte; the preparation method comprises the following steps: dissolving phosphoric acid and polyvinyl alcohol in a mass ratio of 1:1 in water, and stirring at 90-95 ℃ until the mixture is clear.
The PDMS precursor was a PDMS substrate and Sylgard 184 silicone elastomer with a thickness of 10: 1, and mixing the components in a mass ratio.
The invention has the advantages that:
the BC-CNT/PANI fiber is subjected to thermal shrinkage and then is subjected to heat treatment at 800 ℃ in the manufacturing process, and the unique advantages of functional groups and nanometer size enable the BC and the CNT to have strong interaction (hydrogen bonds), so that a porous network with a compact structure is formed.
The core sheath and the porous structure layered inside significantly increase the specific surface area and also promote the migration of ions. The electrochemical performance of the bacterial cellulose-carbon nanotube fiber electrode is obviously improved, and the bacterial cellulose-carbon nanotube/polyaniline fiber electrode has high specific capacity. The prepared all-solid-state micro super capacitor has high energy density and high power density, and good cycle retention capacity (more than 2000 times) and bending capacity.
The flexible all-solid-state micro-integrated circuit realizes excellent electrochemical performance, is combined with a microfluid spinning technology, improves the fiber preparation efficiency, has feasibility of large-scale production in industry, can be applied to various portable, miniaturized and wearable electronic devices, is highly flexible, is easy to program, can be connected in series and parallel, can be edited, and has strong practicability and wide applicability.
Drawings
FIG. 1 is a schematic structural view of a reaction microchannel of the present invention;
FIG. 2 is a schematic structural diagram of a micro supercapacitor according to the present invention;
FIG. 3 is a Raman spectrum of all samples;
FIG. 4 is FTIR spectra of all samples;
FIG. 5 is a typical stress-strain curve for a BC-CNT wet fiber;
FIG. 6 is a typical stress-strain curve for BC-CNT/PANI fibers.
Figure 7 is a graph comparing the Ragone of the miniature supercapacitors of the invention with that of the optical fiber based miniature supercapacitors.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
The reagents used in the present invention:
bacterial cellulose (BC, solid content 0.79 wt%, diameter 50-100 nm, length 10-20 um) is provided by Guilin Daizhiji, Inc., China.
Aniline (ANI), Sodium Alginate (SA), Ammonium Persulfate (APS), and calcium chloride (CaCl) from Chinese medicinal chemical reagents, Inc2) Isopropyl alcohol (IPA), ethanol (C)2H5OH) and phosphoric acid (H)3PO4) Phosphoric acid (H)3PO495-98 wt%, Nanjing chemical reagent Co., Ltd.) to 1.0 mol/L.
Carbon nanotubes (CNTs, purity > 97%, diameter 10-20 nm, length 30-100 μm) obtained from Shenzhen nanometer technology Port, Inc., China.
Polyvinyl alcohol (PVA) has a molecular weight of 124000-186000 g/mol (99% hydrolyzed) and is available from Sigma Aldrich chemical, USA.
Polydimethylsiloxane (PDMS, Sylgard 184 silicone elastomer) was obtained from dow corning, and contained a base material (PDMS) and a curing agent (Sylgard 184 silicone elastomer).
Epoxy conductive silver paste, supplied by Nanjing Xiliet Adhesives Co.
The solvents and reagents used were of analytical grade.
Apparatus for detection:
Figure GDA0002784544340000051
examples
Reaction microchannel: a core cavity is arranged in the tube cavity, and the tube cavity outside the core cavity is a sheath cavity; the inlet ends of the core cavity and the sheath cavity are respectively connected with the core tube and the sheath tube.
Self-making:
step 1: coaxially inserting a plastic steel needle (core cavity) with the inner diameter of 0.61mm into another plastic steel needle (lumen) with the inner diameter of 0.84 mm; a third plastic steel needle (sheath tube) with the diameter of 0.61mm is inserted into the needle with the diameter of 0.84mm from the side surface, so that the third needle is communicated with a gap (sheath cavity) between the first two needles;
step 2: after the linker was fixed using alpha-cyanoacrylate as the transient adhesive, a Y-shaped microchannel was established. The raw materials enter from two inlets and then exit from the same outlet to form a core-shell structure.
Example (b):
a preparation method of bacterial cellulose-carbon nano tube/polyaniline composite microfiber comprises the following steps:
step 1: preparation of dispersions of SA and BC-CNT
A1, and mixing the components in a mass ratio of 1:1,1: 1.25,1: 1.5,1: 2, CNTs was added to 31.65g (0.79%) of the BC dispersion;
diluting the mixed solution to 50.0ml, and mechanically stirring for 30 min;
ultrasonically dispersing for 30min under the power of 400W by using an ultrasonic crusher to realize BC-CNT nano hybrid water dispersion;
a2, and the mass ratio SA: BC: CNTs 6: 1:1,6: 1: 1.25,6: 1: 1.5,6: 1:2, slowly adding SA into the BC-CNT nano hybrid aqueous dispersion, and stirring for 24 hours to form a uniform dispersion; the corresponding labels are BC-CNT-1, BC-CNT-2, BC-CNT-3 and BC-CNT-4.
Step 2: preparation of BC-CNT/PANI fibers
S1, as shown in figure 1, using the self-made mixing micro-flow pipe to continuously produce fibers based on the micro-fluid spinning technology, taking the dispersion of SA and BC-CNT as a core layer and calcium chloride (3.0 wt%) as a sheath layer, and chelating to form BC-CNT gel fibers; the flow rates of the core layer and the sheath layer are respectively 5-7ml/h and 15-20 ml/h;
then coagulating in a coagulating bath of calcium chloride (10.0 wt%), washing with deionized water repeatedly after 30-40min, drying the synthesized wet fiber (with the diameter of 500-; then heating to 800-850 ℃ at the heating rate of 2.5 ℃/min, maintaining the temperature at 800-850 ℃, and then naturally cooling at room temperature to obtain the BC-CNT fiber.
S2, the BC-CNT fiber was immersed in the aniline dispersion at 0 ℃ for 1 hour, and ammonium persulfate solution (1.53g, N)ANI：NAPS1: 1.25) reacting at 0 ℃ for 10h, forming a polyaniline layer on the surface of the BC-CNT fiber based on an in-situ polymerization method, wherein the concentration of ammonium persulfate on the interface of the superfine fiber and the solution is rapidly increased along with the reaction, and the formation of a polyaniline shell layer is catalyzed;
and then washed by alcohol solution for 3 times and water for 5 times to prepare the BC-CNT/PANI fiber. Based on the different mass ratios, the materials are named BC-CNT/PANI-1, BC-CNT/PANI-2, BC-CNT/PANI-3 and BC-CNT/PANI-4 respectively.
Wherein, aniline monomer with 0.5-0.8g is dissolved in phosphoric acid (1mol/l) and stirred to form uniform dispersoid.
As shown in fig. 2, a micro supercapacitor comprises the following steps:
dipping the fibers into H prior to making the supercapacitor3PO4In PVA electrolyte for 1 day.
B1, fixing two BC-CNT/PANI fibers with the length of about 6.5cm on a PDMS substrate in parallel;
b2, fixing copper wires at the tail parts of the BC-CNT/PANI fibers respectively through epoxy conductive silver paste at 60 ℃ to obtain good electronic conduction;
and B3, covering a gel electrolyte on the BC-CNT/PANI fiber, coating a PDMS precursor, and solidifying at 75-80 ℃ to obtain the super capacitor.
The gel electrolyte comprises: phosphoric acid/polyvinyl alcohol gel electrolyte; the preparation method comprises the following steps: dissolving phosphoric acid and polyvinyl alcohol in a mass ratio of 1:1 in water, and stirring at 90-95 ℃ until the mixture is clear.
The PDMS precursor was a PDMS substrate and Sylgard 184 silicone elastomer with a thickness of 10: 1, and mixing the components in a mass ratio.
And (3) detection results:
as shown in fig. 3, is the raman spectrum of all samples; i of CNT/BCD/IGLower than the CNT ofD/IGThis is because of sp in the carbon electrode2The amount of C ═ C site moieties decreased, indicating a decrease in surface disturbance caused by BC addition.
The positions of the D wave band and the G band of the CNT and the CNT/BC have no obvious change, which shows that the carbon nano tube in the experiment keeps a good graphitized surface and is not obviously damaged after being coated with the carbon nano tube.
However, in the spectrum of BC-CNT, the intensity of these two Raman peaks is increased. The position of the two peaks is consistent with previous observations, indicating that the change in the intensity of the D and G bands is not a result of direct coupling, but rather a result of non-covalent interactions between carbon nanotubes.
Therefore, the BC can effectively prevent aggregation of the carbon nanotubes in the fiber.
As shown in figure 4 of the drawings,is FTIR plot for all samples; in the BC-CNT spectrum, the tensile vibration strength is obviously enhanced. Compared with pure BC fiber, the BC/CNT composite fiber is 1383cm in length due to the doping of the carbon nano-tube-1Peaks appear to the left and right. At 1115cm-1A new absorption band can be detected, which is designated as the characteristic peak of hydrogen bonding. It clearly shows that a new contact is formed between the carbon nanotubes as a result of the molecular interaction between the-OH of the carbon nanotubes and the carbon nanotubes.
The position of these peaks did not change in the FTIR spectra of the BC-CNT/PANI complex, indicating that the chemical interaction between PANI and CNT can be negligible or diminished. Notably, in the case of polyaniline in situ polymerization, chemical interaction between PANI and CNT was mainly observed.
As shown in fig. 5, is a typical stress-strain curve for hydrogel fibers; the tensile strength of BC/SA hydrogel fibers is much greater than that of SA, and especially the breaking elongation of pure SA hydrogel fibers is lower. This is due to the addition of a well-dispersed rigid BC to resist stress concentration and the increase in mechanical strength resulting from energy transfer across the interface and crack propagation arrest.
As shown in FIG. 6, tensile stress-strain curves of BC-CNT/PANI composite fibers with different CNT contents are shown. The maximum tensile breaking stress of the BC-CNT/PANI-3 composite fiber is far greater than that of the BC-CNT/SA-3 hydrogel fiber. But the corresponding strain at break is significantly reduced.
The comparison shows that the mechanical properties of the hybrid microfibers are enhanced due to the enhancement of the shell PANI layer. The interactions of the PANI and BC-CNT layer interfaces, including van der Waals interactions and hydrogen bonding, contribute to the mechanical improvement of the hybrid microfiber.
As shown in FIG. 7, the power density is 0.32-3.2 mW/cm2The CNT/PANI micro-supercapacitor is 27.9-35.5 mW hcm-2The range shows higher energy density, much larger than other micro-supercapacitors.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims (10)

1. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber is characterized in that the preparation method comprises the following steps:
s1, chelating to form BC-CNT gel fibers by taking a dispersion of sodium alginate and BC-CNT as a core layer and calcium chloride as a sheath layer based on a microfluid spinning technology; then carrying out coagulating bath, washing, thermal shrinkage and cooling to obtain the BC-CNT fiber;
s2, immersing the BC-CNT fiber into an aniline dispersion, adding an ammonium persulfate solution for reaction, and forming a polyaniline layer on the surface of the BC-CNT fiber by adopting an in-situ polymerization method; and washing to obtain the BC-CNT/PANI fiber.
2. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber as claimed in claim 1, wherein said microfluid spinning technology of step S1 comprises a reaction microchannel;
a core cavity is arranged in a tube cavity of the reaction microchannel, and the tube cavity outside the core cavity is a sheath cavity;
the inlet ends of the core cavity and the sheath cavity are respectively connected with the core tube and the sheath tube.
3. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber according to claim 1, wherein said preparation of sodium alginate/BC-CNT dispersion in step S1 comprises the following steps:
a1, mixing bacterial cellulose and CNTs in an aqueous solution according to a certain mass ratio, stirring, and performing ultrasonic dispersion to obtain a BC-CNT dispersion liquid;
a2, adding sodium alginate into the BC-CNT dispersion liquid according to a certain mass ratio, and stirring to form a dispersion.
4. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber according to claim 3, wherein in the step A1, the mass ratio of bacterial cellulose to CNTs is 1:1-1: 2; the mass ratio of sodium alginate to bacterial cellulose in step a2 was 6: 1.
5. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber as claimed in claim 1, wherein said coagulating bath in step S1 is washed with deionized water, the coagulating bath is calcium chloride solution, and the coagulating bath is heat-shrunk to be dried in a vacuum oven at 100 ℃ for 2-3h, and then heated at a heating rate of 2.5 ℃/min and maintained at 800-;
in the step S2, the BC-CNT fiber is soaked in aniline dispersion at the temperature of 0 ℃ for 1-2 h;
the reaction temperature is 0 ℃, and the reaction time is 10-12 h;
the washing solution comprises ethanol and water in sequence.
6. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber according to claim 1, wherein said aniline dispersion in step S2 is a dispersion formed by dissolving aniline monomer in phosphoric acid and stirring.
7. The bacterial cellulose-carbon nanotube/polyaniline composite microfiber according to claim 6, wherein said phosphoric acid concentration is 1mol/l, and the mass of aniline monomer is 0.5-0.8 g.
8. A miniature super capacitor is characterized by comprising the following preparation steps:
b1, placing a bacterial cellulose-carbon nanotube/polyaniline composite microfiber as set forth in any one of claims 1 to 7 on a polydimethylsiloxane substrate in parallel;
b2, fixing copper wires at the tail parts of the BC-CNT/PANI fibers through conductive silver paste;
and B3, covering a gel electrolyte on the BC-CNT/PANI fiber, and then coating a polydimethylsiloxane precursor to obtain the super capacitor.
9. The miniature ultracapacitor of claim 8, wherein the gel electrolyte is: phosphoric acid/polyvinyl alcohol gel electrolyte;
the preparation method comprises the following steps: dissolving phosphoric acid and polyvinyl alcohol in a mass ratio of 1:1 in water, and stirring at 90-95 ℃ until the mixture is clear.
10. The micro supercapacitor of claim 8, wherein the polydimethylsiloxane precursor is a polydimethylsiloxane substrate and a curing agent in a ratio of 10: 1, and mixing the components in a mass ratio.
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