CN103594252A - Manufacturing method for graphene fiber super capacitor carrying polyaniline nanometer particles - Google Patents
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- CN103594252A CN103594252A CN201310570359.8A CN201310570359A CN103594252A CN 103594252 A CN103594252 A CN 103594252A CN 201310570359 A CN201310570359 A CN 201310570359A CN 103594252 A CN103594252 A CN 103594252A
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Abstract
The invention discloses a manufacturing method for a graphene fiber super capacitor carrying polyaniline nanometer particles. The method comprises the following steps: (1) dissolving oxidized graphene materials in deionized water, and processing in an ultrasonic bath so as to obtain oxidized graphene solution, (2) concentrating the solution so as to obtain oxidized graphene dispersion liquid with high viscosity, (3) using a spinning head to extrude the solution to solidified liquid so as to obtain oxidized graphene fiber, (4) placing the oxidized graphene fiber in a reducing environment to reduce so as to obtain graphene fiber, (5) soaking the graphene fiber in aniline solution, adding ammonium persulfate, and standing to obtain graphene fiber carrying the polyaniline nanometer particles, (6) fixing two pieces of obtained graphene fiber carrying the polyaniline nanometer particles to a substrate, using gel electrolyte to wrap the graphene fiber, and drying the graphene fiber. The manufacturing method is simple, convenient, low in cost, capable of protecting the environment, suitable for large-scale industrialized production, high in capacitor specific capacitance, good in cyclicity, excellent in tenacity, and capable of being used in fields of energy storage and flexible materials.
Description
Technical field
The present invention relates to the preparation method of fibre supercapacitors, relate in particular to a kind of preparation method of graphene fiber ultracapacitor of load Nano particles of polyaniline.
Background technology
Ultracapacitor, is again double electric layer capacitor, electrochemical capacitor, and gold electric capacity, farad capacitor are a kind of brand-new capacitors being based upon in the interfacial electric double layer theoretical foundation that roentgen Helmholtz proposes, and by polarization electrolyte, carry out energy storage.It is a kind of electrochemical element, but in the process of its energy storage, chemical reaction does not occur, and this thermal energy storage process is reversible, also just because of can repeated charge hundreds thousand of times of this ultracapacitor.Material with carbon element, because of its high-specific surface area having, high conductivity and cheap price, makes it become the preferred material of ultracapacitor.
As the representative of Two-dimensional Carbon material, Graphene in the A. K. of 2004 Nian Bei Britain Geim (K. S. Novoselov, et al. Science, 2004,306,666-669) find at scientific research field and industrial circle, to have opened up new direction so far.Graphene is the thinnest two-dimensional material, and has high intensity, very big specific area and high conductance.Everything advantage makes it have into the ability of ultracapacitor.Meanwhile, take native graphite as raw material, we can realize batch production graphene oxide by chemical oxidation-reducing process, and then reduction obtains the assorted less Graphene of functional group content.This also lays the foundation for the industrialization of Graphene ultracapacitor.
But capacitor at present on the market exists mainly with paper shape or solid shape, and the use of liquid electrolyte has limited the range of application of capacitor greatly, make capacitor comparatively heavy and huge.And the electric double layer capacitance specific volume value that full material with carbon element itself provides is very little, is difficult to meet jumbo demand.
Summary of the invention
The object of the invention is to propose a kind of preparation method of graphene fiber ultracapacitor of load Nano particles of polyaniline, for the assembling form of ultracapacitor provides new approaches, and then obtain good chemical property.
The preparation method of the graphene fiber ultracapacitor of load Nano particles of polyaniline comprises the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in ultra sonic bath, processes, obtain graphene oxide solution;
2) by graphene oxide solution after concentrated, obtain the graphene oxide dispersion liquid of 10-20mg/ml;
3) graphene oxide dispersion liquid is expressed in solidification liquid with the spinneret of 100-200 micron bore, the standing rear taking-up of gained fiber oven dry obtain graphene oxide fiber;
4) graphene oxide fiber is placed in to reduction atmosphere, reduction, obtains graphene fiber under 80-95 degree Celsius;
5) graphene fiber having reduced is soaked in the perchloric acid/ethanolic solution that contains aniline, and adds ammonium persulfate under uniform temperature, standing a period of time obtains the graphene fiber that load has Nano particles of polyaniline;
6) two graphene fibers are fixed in substrate, keep spacing, two graphene fiber two ends are fixed with electric conducting material, the middle parcel gel electrolyte that applies, and natural air drying obtains graphene fiber ultracapacitor.
Preferably, 15000 rpms of described simmer down tos carry out centrifugal or vacuum filtration.
Preferably, the solidification liquid formula described in step 3) is: the volume ratio of ethanol and water be 1:3 to 3:1, the quality percentage composition of calcium chloride is 1% to 10%.
Preferably, described reduction atmosphere is one or more in hydrazine hydrate steam, hydrogen iodide solution, vitamin c solution, thermal reduction.
Preferably, described in step 4) the diameter of graphene fiber at 20-150 micron.
Preferably, the length of the graphene fiber described in step 5) at 2cm between 20cm.
Preferably, aniline described in step 5) in polymerization reaction system and the concentration of ammonium persulfate are respectively 0.045mol/L to 0.05mol/L, 0.03mol/L to 0.035mol/L, perchloric acid concentration is 1mol/L, concentration of alcohol is 3.5mol/L, and described polymerization reaction system remains on zero degree to carry out to subzero 10 degree.
Preferably, described in step 6), the fixed form of the graphene fiber of two load Nano particles of polyaniline is for being arranged in parallel, being fixed in substrate by double faced adhesive tape, described graphene fiber spacing is 3-5mm, and described substrate is polyethylene terephthalate transparent elastic plastic film.
Preferably, the electric conducting material described in step 6) is the conductive plastics of copper, silver, gold, platinum or high conductivity.
Preferably, described in step 6), the formula of gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.
The load that the present invention has set forth a kind of novel preparation flexibility has the graphene fiber material of Nano particles of polyaniline to be assembled into the all-solid-state supercapacitor with favorable elasticity.This fibre-like capacitor owing to thering is good flexibility so upwards have very large supplementing than traditional ultracapacitor carrying with transportation and user.The technology of the Wetting spinning that moreover, we adopt is produced high-performance fiber for extensive, serialization and then the ultracapacitor that obtains weaving becomes possibility.More worth the wait, the fake capacitance that the Nano particles of polyaniline of load provides has strengthened the performance of pure graphene fiber greatly, the ultracapacitor specific capacity of assembling is pure graphene fiber 20 times, this provides for the demand that meets high-energy and store
Strong assurance.
The beneficial effect that the present invention compared with prior art has:
1) raw material adopts graphene oxide, and raw material is easy to get, cost is low;
2) simple preparation reduced graphene fiber;
3) very easy load on graphene fiber a large amount of Nano particles of polyaniline;
4) adopt two-wire parallel method to prepare fiber capacitor, simple to operate, environmental protection;
5) length of the fiber capacitor making can be according to the fibre length of using and free adjustment;
6) the fiber capacitor making has very high specific capacity and stable charge-discharge characteristic;
7) the fiber capacitor making has good pliability.
Accompanying drawing explanation
Fig. 1 is the graphene fiber ultracapacitor schematic diagram of the load Nano particles of polyaniline prepared of the present invention, and in figure, 1 is electric conducting material, and 2 is the graphene fiber of load Nano particles of polyaniline, and 3 is gel electrolyte;
Fig. 2 is the graphene fiber radial scan Electronic Speculum figure of the load Nano particles of polyaniline prepared of the present invention, and scale is 2 microns;
Fig. 3 a is the graphene fiber ultracapacitor cyclic voltammogram of the load Nano particles of polyaniline prepared of the present invention;
Fig. 3 b is the graphene fiber ultracapacitor constant current charge-discharge figure of the load Nano particles of polyaniline prepared of the present invention, current density 0.1mA/cm
2;
Fig. 4 is that in example 1 of the present invention, to adopt length be the ultracapacitor pictorial diagram of graphene fiber assembling of the load Nano particles of polyaniline of 2cm.
Fig. 5 is that in example 2 of the present invention, to adopt length be the ultracapacitor pictorial diagram of graphene fiber assembling of the load Nano particles of polyaniline of 20cm.
Embodiment
The object of the invention is to propose a kind of graphene fiber ultracapacitor of load Nano particles of polyaniline
Preparation method, for the assembling form of ultracapacitor provides new approaches, be the electric double layer electricity that material with carbon element is lower
Hold higher fake capacitance is provided.
The preparation method of the graphene fiber ultracapacitor of load Nano particles of polyaniline comprises the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in the ultra sonic bath of 1～50Hz, processes 0.1～1 hour, obtain graphene oxide solution;
2) by the graphene oxide solution obtaining through centrifugal, obtain the graphene oxide dispersion liquid that concentration is higher;
3) graphene oxide dispersion liquid is expressed in the solidification liquid preparing with the spinneret of 200 μ m bores.Gained fiber took out and obtains graphene oxide fiber 60 degrees Celsius of oven dry after standing 30 minutes;
4) graphene oxide fiber is placed in to reducing agent environment, reduces 4 hours under 80 degrees Celsius, obtain graphene fiber;
5) graphene fiber having reduced is soaked in aniline solution, and under uniform temperature, add appropriate ammonium persulfate, standing a period of time obtains load the graphene fiber of Nano particles of polyaniline (as shown in Figure 2, nano particle has been carried on graphene fiber surface);
6) have the graphene fiber of Nano particles of polyaniline to be fixed in substrate by certain way two loads, keep a determining deviation, two ends are fixed with copper sheet, and mid portion applies gel electrolyte that parcel is joined.Products obtained therefrom obtains the graphene fiber ultracapacitor of Nano particles of polyaniline through natural air drying.(as shown in Figure 1)
Described centrifugal condition be 15000 rpms carry out 30 minutes centrifugal.Described solidification liquid formula is: the volume ratio of ethanol and water be 3:1 to 1:3, the mass fraction of calcium chloride is 1% to 10%.Described reducing environment is hydrogen iodide solution.The diameter of described graphene fiber at 20 μ m between 100 μ m.The concentration of described aniline and ammonium persulfate is respectively 0.045mol/L to 0.05mol/L, 0.03mol/L to 0.035mol/L, and perchloric acid concentration is 1mol/L, and concentration of alcohol is 3.5mol/L.The temperature of described polymerization reaction is that zero degree arrives subzero 10 degree.The described substrate for the preparation of ultracapacitor is poly terephthalic acid second
Diester transparent elastic plastic film.Described two fibre lengths for the preparation of capacitor be 2cm to 20cm, fixed form is for being arranged in parallel, adhering on double faced adhesive tape.Described fiber spacing is 3-5mm.The formula of described gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.
The graphene fiber that this method obtains is oriented owing to extruding thereby has stratiform ordered structure, and electronics can pass through smoothly in direction of orientation, so its conductance is very high.Diameter is by regulating the outlet size of spinneret and adjusted, and amplitude of variation is controlled, at 20 μ m between 100 μ m.Nano particles of polyaniline is loaded on the radial surface of graphene fiber in a large number by the method for weak solution polymerization, good fake capacitance is provided.The capacitor obtaining by parallel double collimation method assembling, through take the effect that phosphoric acid is electrolyte, the polyvinyl alcohol solid gel electrolyte that is skeleton, demonstrates the characteristic of comparatively good capacitor.
Fig. 3 a is the cyclic voltammogram of the graphene fiber ultracapacitor of load Nano particles of polyaniline.As seen from the figure, under high sweep speed, without obvious redox peak, occur, and have obvious redox peak to occur low sweep speed is next, this has shown in successful grafting of polyaniline graphene fiber.Fig. 3 b is the constant current charge-discharge figure of the graphene fiber ultracapacitor of load Nano particles of polyaniline, and as seen from the figure, curve is divided into two sections, at 1.0V to being that electric double layer plays a major role between 0.45V, at 0.45V to being that fake capacitance plays a major role between 0V.By curve, can be calculated, be 0.1mA/cm in current density
2under, the graphene fiber of load Nano particles of polyaniline shows 66.6mF/cm
2super high specific capacitance, this is current peak at fiber capacitor area.
Below by embodiment, the present invention is specifically described; the present embodiment is only for the present invention is described further; can not be interpreted as limiting the scope of the invention, those skilled in the art makes some nonessential changes and adjusts according to the content of foregoing invention and all belongs to protection scope of the present invention.
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in the ultra sonic bath of 20Hz, processes 1 hour, obtain graphene oxide solution;
2) the graphene oxide solution obtaining is centrifugal through 15000 rpms, 1 hour, obtain the graphene oxide dispersion liquid of 20mg/mL;
3) graphene oxide dispersion liquid is expressed in the solidification liquid preparing with the spinneret of 200 μ m bores.Solidification liquid formula is: the volume ratio of ethanol and water is 3:1, and the mass fraction of calcium chloride is 5%.Gained fiber took out and obtains graphene oxide fiber 60 degrees Celsius of oven dry after standing 30 minutes;
4) several graphene oxide fibers are soaked and are placed in the closed container that contains 100 mL 20% HI solution.It reduces 4 hours under 80 degrees Celsius, obtains graphene fiber;
5) several graphene fibers are soaked in the perchloric acid 15mL solution of the 1mol/L that contains 0.116g aniline, add 5mL ethanol, be statically placed in subzero ten degree, the perchloric acid 5mL solution that adds again the 1mol/L of 0.190g ammonium persulfate, react 24 hours, obtain the graphene fiber of load Nano particles of polyaniline.
6) two long graphene fibers of 2 cm are fixed on polyethylene terephthalate transparent elastic plastic film by the mode being arranged in parallel, keep 3 ~ 5 mm spacing, one end is fixed with copper sheet, and the other end is fixed with double faced adhesive tape.Mid portion applies gel electrolyte that parcel is joined.The formula of described gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.Products obtained therefrom obtains through natural air drying the graphene fiber ultracapacitor of hydrogen iodide reduction that length is the load Nano particles of polyaniline of 2cm, as Fig. 4.
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in the ultra sonic bath of 100Hz, processes 0.1 hour, obtain graphene oxide solution;
2) the graphene oxide solution obtaining is centrifugal through 15000 rpms, 30 minutes, obtain the graphene oxide dispersion liquid of 15mg/mL;
3) graphene oxide dispersion liquid is expressed in the solidification liquid preparing with the spinneret of 200 μ m bores.Solidification liquid formula is: the volume ratio of ethanol and water is 3:1, and the mass fraction of calcium chloride is 5%.Gained fiber took out and obtains graphene oxide fiber 60 degrees Celsius of oven dry after standing 30 minutes;
4) several graphene oxide fibers are placed in to the closed container that 5mL hydrazine hydrate is contained in bottom.It,, in 95 degrees Celsius of lower reductase 12s hour, obtains graphene fiber;
5) several graphene fibers are soaked in the perchloric acid 15mL solution of the 1mol/L that contains 0.116g aniline, add 5mL ethanol, be statically placed in zero degree, the perchloric acid 5mL solution that adds again the 1mol/L of 0.190g ammonium persulfate, react 20 hours, obtain the graphene fiber of load Nano particles of polyaniline.
6) two long graphene fibers of 20 cm are fixed on polyethylene terephthalate transparent elastic plastic film by the mode being arranged in parallel, keep 3 ~ 5 mm spacing, one end is fixed with gold plaque, and the other end is fixed with double faced adhesive tape.Mid portion applies gel electrolyte that parcel is joined.The formula of described gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.Products obtained therefrom obtains through natural air drying the graphene fiber ultracapacitor of hydrazine hydrate reduction that length is the load Nano particles of polyaniline of 20cm, as Fig. 5.
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in the ultra sonic bath of 50Hz, processes 0.5 hour, obtain graphene oxide solution;
2) the graphene oxide solution obtaining is centrifugal through 15000 rpms, 15 minutes, obtain the graphene oxide dispersion liquid of 10mg/mL;
3) graphene oxide dispersion liquid is expressed in the solidification liquid preparing with the spinneret of 200 μ m bores.Solidification liquid formula is: the volume ratio of ethanol and water is 1:1, and the mass fraction of calcium chloride is 1%.Gained fiber took out and obtains graphene oxide fiber 60 degrees Celsius of oven dry after standing 30 minutes;
4) several graphene oxide fibers are soaked and are placed in the closed container that contains 100 mL 20% vitamin c solutions.It reduces 8 hours under 90 degrees Celsius, obtains graphene fiber;
5) several graphene fibers are soaked in the perchloric acid 15mL solution of the 1mol/L that contains 0.106g aniline, add 5mL ethanol, be statically placed in subzero ten degree, the perchloric acid 5mL solution that adds again the 1mol/L of 0.172g ammonium persulfate, react 28 hours, obtain the graphene fiber of load Nano particles of polyaniline.
6) two long graphene fibers of 10 cm are fixed on polyethylene terephthalate transparent elastic plastic film by the mode being arranged in parallel, keep 3 ~ 5 mm spacing, one end is fixed with platinized platinum, and the other end is fixed with double faced adhesive tape.Mid portion applies gel electrolyte that parcel is joined.The formula of described gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.Products obtained therefrom obtains through natural air drying the graphene fiber ultracapacitor of vitamin C reduction that length is the load Nano particles of polyaniline of 10cm.
embodiment 4
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in the ultra sonic bath of 75Hz, processes 0.2 hour, obtain graphene oxide solution;
2) the graphene oxide solution obtaining is centrifugal through 15000 rpms, 30 minutes, obtain the graphene oxide dispersion liquid of 15mg/mL;
3) graphene oxide dispersion liquid is expressed in the solidification liquid preparing with the spinneret of 200 μ m bores.Solidification liquid formula is: the volume ratio of ethanol and water is 1:3, and the mass fraction of calcium chloride is 10%.Gained fiber took out and obtains graphene oxide fiber 60 degrees Celsius of oven dry after standing 30 minutes;
4) several graphene oxide fibers are placed under 800 degrees Celsius and are reduced 4 hours, obtain graphene fiber;
5) several graphene fibers are soaked in the perchloric acid 15mL solution of the 1mol/L that contains 0.118g aniline, add 5mL ethanol, be statically placed in five degrees below zero, the perchloric acid 5mL solution that adds again the 1mol/L of 0.202g ammonium persulfate, react 24 hours, obtain the graphene fiber of load Nano particles of polyaniline.
6) two long graphene fibers of 5 cm are fixed on polyethylene terephthalate transparent elastic plastic film by the mode being arranged in parallel, keep 3 ~ 5 mm spacing, one end is fixed with silver strip, and the other end is fixed with double faced adhesive tape.Mid portion applies gel electrolyte that parcel is joined.The formula of described gel electrolyte is: by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.Products obtained therefrom obtains through natural air drying the graphene fiber ultracapacitor of thermal reduction that length is the load Nano particles of polyaniline of 5cm.
Claims (10)
1. a preparation method for the graphene fiber ultracapacitor of load Nano particles of polyaniline, is characterized in that, comprises the following steps:
1) the graphene oxide raw material of 1 weight portion is dissolved in to the deionized water of 1000 weight portions, in ultra sonic bath, processes, obtain graphene oxide solution;
2) by graphene oxide solution after concentrated, obtain the graphene oxide dispersion liquid of 10-20mg/ml;
3) graphene oxide dispersion liquid is expressed in solidification liquid with the spinneret of 100-200 micron bore, the standing rear taking-up of gained fiber oven dry obtain graphene oxide fiber;
4) graphene oxide fiber is placed in to reduction atmosphere, reduction, obtains graphene fiber under 80-95 degree Celsius;
5) graphene fiber is soaked in the perchloric acid/ethanolic solution that contains aniline, and adds ammonium persulfate, standingly obtain the graphene fiber that load has Nano particles of polyaniline;
6) two graphene fibers are fixed in substrate, keep spacing, two graphene fiber two ends are fixed with electric conducting material, and the middle parcel gel electrolyte that applies air-dryly obtains the graphene fiber ultracapacitor that load has Nano particles of polyaniline.
2. preparation method according to claim 1, is characterized in that, 15000 rpms of described simmer down tos carry out centrifugal.
3. preparation method according to claim 1, is characterized in that, the solidification liquid formula described in step 3) is: the volume ratio of ethanol and water be 1:3 to 3:1, the quality percentage composition of calcium chloride is 1% to 10%.
4. preparation method according to claim 1, is characterized in that, described reduction atmosphere is one or more in hydrazine hydrate steam, hydrogen iodide solution, vitamin c solution, thermal reduction.
5. preparation method according to claim 1, is characterized in that, the diameter of graphene fiber is at 20-150 micron described in step 4).
6. preparation method according to claim 1, is characterized in that, the length of the graphene fiber described in step 5) at 2cm between 20cm.
7. preparation method according to claim 1, it is characterized in that, aniline described in step 5) in polymerization reaction system and the concentration of ammonium persulfate are respectively 0.045mol/L to 0.05mol/L, 0.03mol/L to 0.035mol/L, perchloric acid concentration is 1mol/L, concentration of alcohol is 3.5mol/L, and described polymerization reaction system remains on zero degree to carry out to subzero 10 degree.
8. preparation method according to claim 1, it is characterized in that, described in step 6), the fixed form of the graphene fiber of two load Nano particles of polyaniline is for being arranged in parallel, being fixed in substrate by double faced adhesive tape, described graphene fiber spacing is 3-5mm, and described substrate is polyethylene terephthalate transparent elastic plastic film.
9. preparation method according to claim 1, is characterized in that, the electric conducting material described in step 6) is the conductive plastics of copper, silver, gold, platinum or high conductivity.
10. preparation method according to claim 1, is characterized in that, the formula of gel electrolyte is described in step 6): by quality, calculate polyvinyl alcohol: water: phosphoric acid=1:10:1.
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Cited By (6)
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| CN104119529A (en) * | 2014-08-02 | 2014-10-29 | 桂林理工大学 | Preparation method of polyaniline/graphene composite material with nano tubular structure |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN104036971B (en) * | 2014-05-29 | 2017-01-18 | 浙江大学 | Preparation method for graphene/carbon nano-tube composite fibre-based super capacitor |
| CN110060878A (en) * | 2019-04-28 | 2019-07-26 | 福州大学 | A kind of polyaniline/graphene oxide nano-fiber composite material and the preparation method and application thereof |
| CN111004390A (en) * | 2018-10-08 | 2020-04-14 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| CN114899016A (en) * | 2022-05-09 | 2022-08-12 | 晋江瑞碧科技有限公司 | Preparation method of graphene oxide-based flexible supercapacitor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036971B (en) * | 2014-05-29 | 2017-01-18 | 浙江大学 | Preparation method for graphene/carbon nano-tube composite fibre-based super capacitor |
| CN104119529A (en) * | 2014-08-02 | 2014-10-29 | 桂林理工大学 | Preparation method of polyaniline/graphene composite material with nano tubular structure |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN111004390A (en) * | 2018-10-08 | 2020-04-14 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| CN111004390B (en) * | 2018-10-08 | 2022-07-08 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| CN110060878A (en) * | 2019-04-28 | 2019-07-26 | 福州大学 | A kind of polyaniline/graphene oxide nano-fiber composite material and the preparation method and application thereof |
| CN114899016A (en) * | 2022-05-09 | 2022-08-12 | 晋江瑞碧科技有限公司 | Preparation method of graphene oxide-based flexible supercapacitor |
| CN114899016B (en) * | 2022-05-09 | 2023-08-04 | 武夷学院 | Preparation method of graphene oxide-based flexible supercapacitor |
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