CN104264267A - Porous polyaniline-doped nano fiber material with three-dimensional structure as well as preparation method and application of porous polyaniline-doped nano fiber material - Google Patents
Porous polyaniline-doped nano fiber material with three-dimensional structure as well as preparation method and application of porous polyaniline-doped nano fiber material Download PDFInfo
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Abstract
The invention discloses a porous polyaniline-doped nano fiber material with a three-dimensional structure, and a preparation method and application of the porous polyaniline-doped nano fiber material. The preparation method of the fiber material comprises the following steps: (1) dissolving an aniline monomer into an inorganic protonic acid to obtain a solution A; (2) adding a surfactant into the solution A, and uniformly dispersing to obtain a solution B; (3) adding an oxidizing agent into the solution B, and performing polymerization reaction to obtain a latex solution C, wherein the weight ratio of a raw material namely the aniline monomer to the oxidizing agent is 1:(0.5-2); and (4) collecting a product in the latex solution C, washing, and drying to obtain the porous polyaniline-doped nano fiber material with the three-dimensional structure. The polyaniline-doped nano fiber material prepared by using the method disclosed by the invention is regular in morphology and uniform in hole, and has a relatively large specific surface area and high specific capacitance; and when the polyaniline-doped nano fiber material is applied to a super-capacitor, the super-capacitor has a relatively high specific capacitance value and good recycling life.
Description
Technical field
The present invention relates to a kind of nano-fiber material, be specifically related to doped polyaniline nano-fiber material of a kind of porous three-dimensional structure and its preparation method and application.
Background technology
Ultracapacitor, be otherwise known as electrochemical capacitor, is a kind of model electrochemical energy storage device.Have that power density is high, charge maintenance capability be strong, have extended cycle life, the feature such as the good and environmental friendliness of security performance.These advantages make ultracapacitor have broad application prospects in the field such as electronic flight, national defence.
Ultracapacitor can be divided into double layer capacitor and Faradic pseudo-capacitor according to the mechanism of stored charge.Its electrode material mainly contains conducting polymer, material with carbon element and metal oxide.Wherein, relative material with carbon element and metal oxide containing precious metals, conducting polymer have raw material be easy to get, cheap outside, also there is larger specific capacity and energy density.Common conducting polymer has polyaniline (PANI), polythiophene (PTH), polypyrrole (PPy) etc.Wherein, PANI is because of its raw material is easy to get that cheapness, synthesis are simple, the feature such as stability and good reversibility has become electrode material for super capacitor research focus.
Current synthesis PANI method has: chemical polymerization, electrochemical polymerization method, interfacial polymerization, microemulsion polymerization method, emulsion polymerization etc., wherein, the reaction speed of emulsion polymerization fast and be easy to control, the PANI uniform particles that generates and aqueous medium pollute the advantage such as little and receive much concern.Publication number is the patent of invention of CN102050947A, disclose a kind of preparation method of polyaniline nano fiber, with ammonium persulfate be specifically oxidant, with the electronegative anion neopelex template that is emulsion polymerisation, with the system of water and water-soluble micella for reaction medium, cause aniline monomer at oil and aqueous phase interface place by oxidant and be polymerized and form product.The polyaniline nano fiber diameter that the method obtains is about 100nm, size is comparatively even, can be applicable to the fields such as antistatic material, electromagnetic shielding material, sensor, secondary cell, stealth material, anti-corrosion material and nano functional device, but do not relate to report material being made into application of electrode related data when ultracapacitor.In the patent of invention of publication number CN102532891A and CN102558857A, all refer to a kind of grapheme/polyaniline nanometer fibrous composite material and preparation method thereof, and this composite is applied to the preparation method of ultracapacitor and this ultracapacitor as electrode material.The preparation method of wherein said ultracapacitor comprises obtained grapheme/polyaniline nanometer fibrous composite material and an additive is dispersed to the step obtaining graphene/ conductive polymer colloidal sol in a solvent, and the additive described in this step can be Nafion, Kynoar, tetrafluoroethylene, CNT or its mixture.It can thus be appreciated that, this additive just adds after having prepared grapheme/polyaniline nanometer fibrous composite material, and in patent, point out the caking property acting as increase graphene oxide/polyaniline nano fiber composite and the shape retentivity of this additive, make, with the collector body in subsequent step, there is stronger adhesion, and avoid swelling by electrolyte and come off.In addition, although the materials application of above-mentioned patent report has good capacitance in ultracapacitor, this is owing to adding the Graphene with better electric conductivity in the composite.
In emulsion polymerization, although surfactant does not directly participate in chemical reaction, it is surfactant and proton reagent, and it will directly affect trigger rate, rate of chain growth and particle size of the gel and distribution.Therefore, the selection of surfactant, to the pattern controlling polyaniline, improves the ratio capacitance of polyaniline, chemical stability, invertibity and cycle performance, expands it and have great importance in the application in ultracapacitor field.
Summary of the invention
The technical problem to be solved in the present invention is to provide doped polyaniline nano-fiber material of a kind of porous three-dimensional structure and its preparation method and application.The doped polyaniline nano-fiber material pattern rule obtained by the method for the invention, hole evenly, there is larger specific area and ratio capacitance is high, when being applied to ultracapacitor, ultracapacitor is made to have higher ratio capacitance value and good service life cycle.
The preparation method of the doped polyaniline nano-fiber material of porous three-dimensional structure of the present invention, comprises the following steps:
1) get aniline monomer to be dissolved in inorganic proton acid, obtain solution A;
2) in solution A, add surfactant, be uniformly dispersed, obtain solution B; Described surfactant is Nafion, neopelex or lauryl sodium sulfate, and described surfactant is 1:10 ~ 100 with the ratio of the volume of benzene feedstock amine monomers;
3) in solution B, add oxidant, carry out polymerisation, obtain latax C; Described benzene feedstock amine monomers is 1:0.5 ~ 2 with the ratio of the amount of substance of oxidant;
4) product in latax C is collected, washing, dry, obtain the doped polyaniline nano-fiber material of porous three-dimensional structure.
In order to make the pattern of the doped polyaniline nano-fiber material obtained more regular, hole evenly, join again in solution A after preferably surfactant ethanol being dissolved.Normally surfactant being made into concentration is that the ethanolic solution of 0.01 ~ 1.0wt% joins in solution A again, adopts existing conventional method to stir as ultrasonic wave dispersion, high-strength mechanical or the ethanolic solution of method to the surfactant joined in solution A such as magnetic agitation is uniformly dispersed.
The step 1 of technique scheme) in, the concentration of described aniline monomer in solution A is same as the prior art, is generally 1 ~ 3mol/L.In this step, the concentration of described inorganic proton acid is generally 0.5 ~ 1.5mol/L, described inorganic proton acid can be one or more the combination be selected from hydrochloric acid, nitric acid and sulfuric acid, when inorganic proton acid be chosen as above-mentioned two or more combination time, the proportioning between them can be any proportioning.In this step, preferably pure for commercially available analysis or chemical pure aniline are carried out decompression distillation and use as raw material using the aniline collecting purity higher, higher productive rate can be obtained like this.
The step 2 of technique scheme) in, adopt existing conventional method such as the methods such as ultrasonic wave dispersion, high-strength mechanical stirring or magnetic agitation to be uniformly dispersed to the surfactant joined in solution A.Usually with the speed of 50 ~ 100r/min, magnetic agitation 20 ~ 30min makes the ethanolic solution of surfactant or surfactant be uniformly dispersed in solution A.In this step, preferably adopt Nafion as surfactant, the doped polyaniline nano-fiber material of cycle life excellence can be prepared like this.
The Nafion used in technical scheme of the present invention is du pont company's product, and it is a kind of copolymer by tetrafluoroethylene and perfluor-2-(sulfonic acid ethyoxyl) propyl vinyl ether, has following structure:
The step 3 of technique scheme) in, described oxidant is identical with oxidant used in existing conventional emulsion polymerization method, it can be specifically one or more the combination be selected from manganese dioxide, ammonium persulfate, hydrogen peroxide and iron chloride, when oxidant be chosen as above-mentioned two or more combination time, the proportioning between them can be any proportioning.In this step, the temperature and time of polymerisation is identical with existing conventional emulsion polymerization method, and in the application, polymerisation is carried out usually under ice bath or normal temperature condition, the time usual 3 ~ 24h of polymerisation.
The step 4 of technique scheme) in, normally collect the product in latax C by the mode of suction filtration, and then use ethanol, acetone and deionized water washed product (wherein the order of ethanol and acetone can be exchanged) successively, until filtrate colourless and NaOH inspection does not measure containing Mn
2+ion.Dry condition is same as the prior art, normally under 40 ~ 100 DEG C of conditions, carries out vacuumize.
The present invention also comprises the doped polyaniline nano-fiber material of the porous three-dimensional structure prepared by said method.The doped polyaniline nano-fiber material prepared by said method has porous three-dimensional structure, its pattern is regular, hole is even, have larger specific area, after testing, the diameter of gained doped polyaniline nano-fiber material is between 30 ~ 40nm, and the aperture between adjacent doped polyaniline nanofiber is between 10 ~ 40nm.
The present invention also comprises the application of doped polyaniline nano-fiber material in ultracapacitor of the porous three-dimensional structure that said method obtains.When above-mentioned gained doped polyaniline nano-fiber electrode material is used as the electrode of ultracapacitor, the obtained quality of ultracapacitor when current density is 0.1A/g and potential range is 0 ~ 0.7V can reach more than 359.7F/g than electric capacity, after cycle charge-discharge 1000 times, quality is more than 150.4F/g than electric capacity, and conservation rate is more than 41.8%.
Compared with prior art, feature of the present invention is:
1, the present invention selects suitable surfactant Nafion simultaneously as emulsifying agent and adulterant, be conducive to the control of Polyaniline structure, to prepare pattern rule, hole is even, specific area is comparatively large and the doped polyaniline nano-fiber material of ratio capacitance much higher hole three-dimensional structure;
2, because obtained doped polyaniline nano-fiber material has larger specific area, its central hole structure is conducive to the transmission of proton, during used as electrode material for super capacitor, gained ultracapacitor has higher ratio capacitance value (385.3F/g) in aqueous sulfuric acid, there is good service life cycle simultaneously, after 1000 cycle charge-discharges, specific capacity is 272.4F/g, specific capacity conservation rate is 70.7%, and the special capacity fade especially to 1000 PANI-Nafion materials after 200 circulations is slower; Efficiently solve that polyaniline material is little as the specific capacity existed during electrode of super capacitor, energy density is low and the problem of electrode cycle poor-performing;
3, preparation method of the present invention is simple to operation, reaction condition is gentle, can one-step synthesis a large amount of pattern rule, ratio capacitance much higher hole three-dimensional structure doped polyaniline nanofiber, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the doped polyaniline nano-fiber material of preparation in the embodiment of the present invention 1;
Fig. 2 is the SEM figure of non-doped polyaniline nano-fiber material;
Fig. 3 is the BET figure of the doped polyaniline nano-fiber material of preparation in the embodiment of the present invention 1, and wherein (A) is the N of doped polyaniline nano-fiber material
2adsorption and desorption isotherms, the BJH graph of pore diameter distribution that (a) is doped polyaniline nano-fiber material;
Fig. 4 is the BET figure of non-doped polyaniline nano-fiber material, and wherein (B) is the N of non-doped polyaniline nano-fiber material
2adsorption and desorption isotherms, (b) is the BJH graph of pore diameter distribution of non-doped polyaniline nano-fiber material;
Fig. 5 is the doped polyaniline nano-fiber material of preparation in the embodiment of the present invention 1 and the XRD figure of non-doped polyaniline nano-fiber material, and wherein curve 1 represents doped polyaniline nano-fiber material, and curve 2 represents non-doped polyaniline nano-fiber material;
Fig. 6 is the doped polyaniline doped polyaniline nano-fiber material of preparation and the cyclic voltammogram of non-doped polyaniline nano-fiber material in the embodiment of the present invention 1, wherein curve 1 represents doped polyaniline nano-fiber material, and curve 2 represents non-doped polyaniline nano-fiber material;
Fig. 7 is the doped polyaniline nano-fiber material of preparation and the constant current charge-discharge figure of non-doped polyaniline nano-fiber material in the embodiment of the present invention 1, wherein curve 1 represents doped polyaniline nano-fiber material, and curve 2 represents non-doped polyaniline nano-fiber material;
Fig. 8 is the doped polyaniline nano-fiber material of preparation and the AC impedance figure of non-doped polyaniline nano-fiber material in the embodiment of the present invention 1, and wherein curve 1 represents doped polyaniline nano-fiber material, and curve 2 represents non-doped polyaniline nano-fiber material;
The doped polyaniline nano-fiber material of preparation and the cycle life figure of non-doped polyaniline nano-fiber material in Fig. 9 embodiment of the present invention 1, wherein curve 1 represents doped polyaniline nano-fiber material, and curve 2 represents non-doped polyaniline nano-fiber material.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but these embodiments are not limiting the scope of the invention.
Embodiment 1
1) be dissolved in by 4.0mL aniline in the hydrochloric acid solution of 100mL 1.0mol/L, under the speed of 60r/min, magnetic agitation 30min, obtains solution A;
2) continue under the mixing speed of 60r/min, to step 1) slowly add the ethanolic solution (V of the 0.05wt%Nafion of 4.0mL in the solution A that obtains
aN: V
nafion=100:1), rate of addition is 2.0mL/min, magnetic agitation 20min, obtains solution B;
3) under the mixing speed of 60r/min, to step 2) add MnO in the solution B that obtains
2(n
aN: n
mnO2=1:1), at room temperature, magnetic agitation 12h, obtains latax C;
4) by latax C suction filtration, collect product (i.e. filter cake), use ethanol, acetone and redistilled water washed product successively, until filtrate is colourless, and NaOH inspection does not measure containing Mn
2+ion;
5) by the product vacuumize 24h at 60 DEG C after washing, blackish green powder is obtained, i.e. the polyaniline nano fiber material (representing with PANI-Nafion or PANI/Nafion below) of Nafion doping.
As a comparison, adopt existing typical polymerization legal system for unadulterated PANI, concrete preparation method is as follows:
1) be dissolved in the hydrochloric acid solution of 100mL 1.0mol/L by new for 4.0mL distilled aniline, under the speed of 60r/min, magnetic agitation 30min, obtains solution A;
2) continue under the mixing speed of 60r/min, to step 1) slowly add the redistilled water of 4.0mL in the solution A that obtains, rate of addition is 2.0mL/min, magnetic agitation 20min, obtains solution B;
3) under the mixing speed of 60r/min, to step 2) add MnO in the solution B that obtains
2(n
aN: n
mnO2=1:1), at room temperature, magnetic agitation 12h, obtains latax C;
4) by latax C suction filtration, collect product (i.e. filter cake), use ethanol, acetone and redistilled water washed product successively, until filtrate is colourless, and NaOH inspection does not measure containing Mn
2+ion;
5) by the product vacuumize 24h at 60 DEG C after washing, blackish green powder is obtained, i.e. PANI.
The PANI-Nafion obtained to the embodiment 1 and PANI of the above-mentioned Nafion of doping carries out morphology characterization and performance measurement:
1, characterize the PANI-Nafion pattern of gained, its scanning electron microscope (SEM) photograph as shown in Figure 1.As seen from Figure 1, PANI-Nafion has obvious nanometer fibrous pattern, and is intertwined to form porous three-dimensional network structure between fiber, and fibre diameter is all between 30 ~ 40nm.
The scanning electron microscope (SEM) photograph of the PANI of the Nafion that do not adulterate of above-mentioned preparation as shown in Figure 2, comparison diagram 1 and Fig. 2 known, PANI-Nafion fiber thickness is more even, more loose between fiber, and the distribution of hole is also very even.
2, test the specific area of the PANI of the obtained PANI-Nafion of the embodiment 1 and above-mentioned Nafion of doping and pore-size distribution further, result respectively as shown in Figure 3 and Figure 4.
The specific area adopting BET equation to calculate PANI-Nafion is 45.29m
2/ g, and to calculate its aperture by BJH method be 2 ~ 50nm; And the specific area of unadulterated PANI is 25.24m
2/ g, aperture 5 ~ 30nm.Visible, the doping of Nafion is more conducive to having the PANI three-dimensional manometer processbearing astrocyte that high-ratio surface sum enriches mesopore.
3, characterize the crystal formation of the PANI of the obtained PANI-Nafion of the embodiment 1 and above-mentioned Nafion of doping, as shown in Figure 5, wherein curve 1 represents PANI-Nafion to result, and curve 2 represents the PANI of the Nafion that do not adulterate.
XRD spectra display in Fig. 5, crystal formation and the unadulterated PANI of the PANI-Nafion of doping are basically identical, are part amorphous PANI.
4, the PANI of PANI-Nafion obtained for the embodiment 1 and above-mentioned Nafion of doping is respectively used to make ultracapacitor, and the electric capacity of the ultracapacitor of gained and electrochemical impedance characteristic are measured.
4.1) PANI-Nafion prepared by the present embodiment 1 is as the electrode material of the 3D nanostructured for the preparation of ultracapacitor, preparation method is: the PANI-Nafion nanofiber according to as active material: the acetylene black as conductive agent: the mass ratio as the PTFE of binding agent is that 80:10:10 mixes, and obtains the mixed slurry of electrode material.
4.2) by the electrode material of the mixed slurry of the electrode material described in above-mentioned preparing for the preparation of the electrode slice in ultracapacitor, its preparation method is: mixed slurry is pressed into the thin electrodes sheet that about 0.1mm is thick, and finally it being cut into area with mould is 1.0cm
2circular electric pole piece, dry.The electrode slice choosing two pieces of quality close does positive and negative electrode respectively, and centre one deck porous septum paper is separated, with 1.0mol/L H
2sO
4solution does electrolyte, adopts 2032 type battery cases, pad and steel disc to be assembled into the button cell of sandwich style, is assembled into ultracapacitor A.
4.3) repeat above-mentioned 4.1) and 4.2) step, just the PANI of PANI-Nafion material wherein with the above-mentioned Nafion that do not adulterate is replaced, composition obtain ultracapacitor B.
4.4) two electrode systems are utilized to test electric capacity and the electrochemical impedance characteristic of sandwich symmetric form ultracapacitor A and ultracapacitor B obtained above, its result is as shown in Fig. 6 ~ 9, in figure, curve 1 represents PANI-Nafion, and curve 2 represents the PANI of the Nafion that do not adulterate.
Result shows, and be 0.1A/g in current density, when potential range is 0 ~ 0.7V, the specific capacitance of single electrode of the PANI-Nafion of doping is 385.3F/g, and the specific capacitance of single electrode of PANI is only 235.8F/g; The ratio that capacity declines in front 200 cycle charge-discharges is very fast, and the specific capacity both when 200 times is respectively 295.2F/g and 130.1F/g, and the specific capacity conservation rate of PANI-Nafion and PANI two electrode is respectively 76.6% and 55.2%.After 200 ~ 1000 cycle charge-discharges, the specific capacity of two electrodes tends towards stability, and after 1000 circulations, specific capacity is respectively 272.4F/g and 93.1F/g, and the specific capacity conservation rate of PANI-Nafion and PANI is respectively 70.7% and 39.5%.The specific capacity of the PANI-Nafion of doping and cycle life are all higher than unadulterated PANI.EIS result shows, the PANI-Nafion of doping and the ohmage (R of unadulterated PANI
s) being all about 0.7 Ω, ohmage is all very little; And charge transfer resistance (R
ct) being respectively 1.87 Ω and 2.7 Ω, the charge transfer resistance of the PANI of doping Nafion obviously reduces; At low frequency end, the diffusion impedance slope of curve of the PANI-Nafion after doping is obviously greater than the diffusion impedance curve of PANI electrode, shows that the PANI-Nafion after adulterating has higher electric capacity equally.
Embodiment 2
1) be dissolved in by 4.0mL aniline in the hydrochloric acid solution of 100mL 1.0mol/L, under the speed of 60r/min, magnetic agitation 30min, obtains solution A;
2) continue under the mixing speed of 60r/min, to step 1) add the lauryl sodium sulfate ethanolic solution (V that 4.0mL concentration is 0.1wt% in the solution A that obtains
aN: V
surf=1:1), rate of addition is 0.25 ~ 2.5mL/min, magnetic agitation 30min, obtains solution B;
3) under the mixing speed of 100r/min, to step 2) slowly add MnO in the solution B that obtains
2(n
aN: n
mnO2=1:2), at 15 DEG C, magnetic agitation 8h, obtain latax C;
4) by latax C suction filtration, collect product (i.e. filter cake), use ethanol, acetone and redistilled water washed product successively, until filtrate is colourless, and NaOH inspection does not measure containing Mn
2+ion;
5) by the product vacuumize 24h at 50 DEG C after washing, blackish green powder is obtained, i.e. the doped polyaniline nano-fiber material of porous three-dimensional structure of the present invention.
The doped polyaniline nano-fiber material of the above-mentioned porous three-dimensional structure prepared is used for the electrode material of the 3D nanostructured of ultracapacitor, and prepares, be assembled into ultracapacitor.The Integration Assembly And Checkout of capacitor is with embodiment 1, and test result: specific capacitance of single electrode is 359.7F/g, after 1000 circulations, specific capacity conservation rate is 41.8%.
Embodiment 3
1) 4.0mL newly being steamed aniline (namely collecting the aniline obtained in the mode of decompression distillation) is dissolved in the hydrochloric acid solution of 100mL 1.5mol/L, and under the speed of 50r/min, magnetic agitation 25min, obtains solution A;
2) continue under the mixing speed of 80r/min, to step 1) add the lauryl sodium sulfate ethanolic solution (V that 4.0mL concentration is 0.1wt% in the solution A that obtains
aN: V
surf=1:1), rate of addition is 0.25 ~ 2.5mL/min, magnetic agitation 30min, obtains solution B;
3) under the mixing speed of 100r/min, to step 2) slowly add ammonium persulfate (n in the solution B that obtains
aN: n
ammonium persulfate=1:0.5), at 30 DEG C, magnetic agitation 24h, obtain latax C;
4) by latax C suction filtration, collect product (i.e. filter cake), use ethanol, acetone and redistilled water washed product successively, until filtrate is colourless, and N
aoH inspection does not measure containing Mn
2+ion;
5) by the product vacuumize 20h at 60 DEG C after washing, blackish green powder is obtained, i.e. the doped polyaniline nano-fiber material of porous three-dimensional structure of the present invention.
The doped polyaniline nano-fiber material of the above-mentioned porous three-dimensional structure prepared is used for the electrode material of the 3D nanostructured of ultracapacitor, and prepares, be assembled into ultracapacitor.The Integration Assembly And Checkout of capacitor is with embodiment 1, and test result: specific capacitance of single electrode is 401.6F/g, after 1000 circulations, specific capacity conservation rate is 44.5%.
Claims (7)
1. a preparation method for the doped polyaniline nano-fiber material of porous three-dimensional structure, comprises the following steps:
1) get aniline monomer to be dissolved in inorganic proton acid, obtain solution A;
2) in solution A, add surfactant, be uniformly dispersed, obtain solution B; Described surfactant is Nafion, neopelex or lauryl sodium sulfate, and described surfactant is 1:10 ~ 100 with the ratio of the volume of benzene feedstock amine monomers;
3) in solution B, add oxidant, carry out polymerisation, obtain latax C; Described benzene feedstock amine monomers is 1:0.5 ~ 2 with the ratio of the amount of substance of oxidant;
4) product in latax C is collected, washing, dry, obtain the doped polyaniline nano-fiber material of porous three-dimensional structure.
2. preparation method according to claim 1, is characterized in that: step 2) in, join again in solution A after surfactant ethanol is dissolved.
3. preparation method according to claim 1 and 2, is characterized in that: step 1) in, the concentration of described aniline monomer in solution A is 1 ~ 3mol/L.
4. preparation method according to claim 1 and 2, is characterized in that: step 1) in, the concentration of described inorganic proton acid is 0.5 ~ 1.5mol/L.
5. preparation method according to claim 1 and 2, is characterized in that: step 3) in, described oxidant is one or more the combination be selected from manganese dioxide, ammonium persulfate, hydrogen peroxide and iron chloride.
6. the doped polyaniline nano-fiber material of porous three-dimensional structure for preparing of method according to any one of Claims 1 to 5.
7. the application of doped polyaniline nano-fiber material in ultracapacitor of porous three-dimensional structure according to claim 6.
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| CN105470003B (en) * | 2016-01-12 | 2017-12-22 | 东华大学 | A kind of preparation method of the stretchable electrode material of three dimensional carbon nanotubes/textile fabric |
| CN106935414A (en) * | 2017-04-24 | 2017-07-07 | 福州大学 | A kind of cross linked porous polyaniline electrode material and preparation method thereof |
| CN110931261A (en) * | 2019-12-18 | 2020-03-27 | 中原工学院 | Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance |
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| CN113161162A (en) * | 2021-04-22 | 2021-07-23 | 广西师范大学 | Doped polyaniline electrode material for super capacitor and preparation method and application thereof |
| CN115424867A (en) * | 2022-08-12 | 2022-12-02 | 湖北工业大学 | Flexible super capacitor and preparation method thereof |
| CN115424867B (en) * | 2022-08-12 | 2023-06-27 | 湖北工业大学 | Flexible super capacitor and preparation method thereof |
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