CN111354576B - Fabric-based flexible supercapacitor and manufacturing method thereof - Google Patents
Fabric-based flexible supercapacitor and manufacturing method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
-
- 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
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a fabric-based flexible supercapacitor and a manufacturing method thereof, wherein the fabric-based flexible supercapacitor is low in manufacturing cost, simple in manufacturing process, small in influence on air permeability of fabric, and excellent in specific capacitance characteristic and bending stability. The method comprises the steps of mixing ammonium molybdate and carboxymethyl cellulose according to a specified proportion and dissolving in water to obtain a molybdenum-containing coating liquid; uniformly coating a molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing at the temperature of 40-80 ℃ to form the fabric with a molybdenum-containing coating; irradiating the molybdenum-containing coating by using a green laser to carbonize carboxymethyl cellulose in the molybdenum-containing coating to form a molybdenum-containing composite conductive layer; and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode slices, and overlapping the two electrode slices in a manner of clamping electrolyte to obtain the super capacitor. The flexible super capacitor is suitable for wearable electronic equipment and has wide application prospect in the fields of intelligent artificial limbs, biological medicine, robots and the like.
Description
Technical Field
The invention relates to the field of supercapacitors, in particular to a method for forming a molybdenum-containing composite conductive layer on a fabric and manufacturing a fabric-based flexible supercapacitor by the same, and the fabric-based flexible supercapacitor manufactured by the method.
Background
With the rapid development of global economy and industrial technology, energy problems become a focus of attention in all countries of the world, and the development of renewable energy conversion and storage devices is particularly critical. Development of high-performance energy devices to meet future requirements for high energy density, high power density and long cycle life has been a focus of research. From 2012, along with wearable electronic products represented by google glasses and smart bracelets, flexible/wearable equipment has gained great attention and rapid development, and new challenges are brought to energy devices. A wearable device is a portable device that is worn directly on the body or integrated into the clothing or accessories of the user. Most of the traditional energy devices are difficult to effectively meet the development requirements of light weight, miniaturization, flexibility and integration of wearable equipment, and also difficult to meet the requirement of large capacity. Only wearable energy devices with high efficiency, high quality and wearing comfort are developed, consumers can like and use the wearable electronic devices, and the research of people on the wearable energy devices is more and more deep.
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of rapid charging and discharging of the capacitor and the energy storage characteristic of the battery. Compared with a storage battery and a traditional physical capacitor, the super capacitor is mainly characterized by (1) high power density, (2) long cycle life, (3) wide working temperature limit, (4) no maintenance, and (5) environmental protection.
The technologies reported at present for preparing flexible supercapacitors on fabrics mainly include weaving technology, chemical deposition technology and the like.
Patent document 1 proposes a method for preparing a supercapacitor on a fabric by using a weaving technology, in which a strip-shaped all-solid-state supercapacitor is prepared by using a flexible film as an electrode material, and a supercapacitor fabric formed by combining a plurality of strip-shaped capacitor units in a certain manner is obtained by weaving. Although the prepared device has the performance of a flexible capacitor, the process flow is complex.
Patent document 2 also discloses a method for manufacturing a flexible supercapacitor electrode based on a chemical fiber fabric, in which a nano nickel conductive layer is uniformly grown on the chemical fiber fabric by a chemical method similar to a silver mirror reaction, and the nano nickel conductive layer is used as an electrode substrate and a current collector. And then growing the electrode active material on the substrate in situ by adopting a hydrothermal method to obtain the ultrahigh-flexibility electrode. The disadvantage of this method is that organic solvents can affect the flexible fabric and thus the lifetime of the device.
Patent document 3 discloses Mo2C/MoO2Method for producing an/C composite electrode material, wherein a gel is produced using a molybdenum salt and a carbon-containing precursor, and is dried by freeze-drying andcarbonizing at the high temperature of 400-1600 ℃ to obtain a composite material, then preparing a coating liquid from the obtained composite material, and coating the coating liquid on a copper foil to form an electrode. The method adopts very high carbonization temperature, has high manufacturing cost and complicated manufacturing process of the electrode.
Therefore, there is still a need for a method of manufacturing a supercapacitor that is inexpensive to manufacture, simple in manufacturing process, and has little effect on the air permeability of the fabric.
Documents of the prior art
Patent document
Patent document 1: chinese patent publication CN110172771A
Patent document 2: chinese patent publication CN109859961A
Patent document 3: chinese patent publication CN109148869A
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a method for manufacturing a supercapacitor which is low in manufacturing cost, simple in manufacturing process, less in influence on air permeability of a fabric, and excellent in specific capacitance characteristics and bending stability, and further to provide a supercapacitor manufactured by the above-mentioned manufacturing method.
The present inventors have conducted intensive studies and, as a result, have found that an electrode sheet, and thus a fabric-based flexible supercapacitor, can be simply obtained by laser-irradiating a coating layer comprising ammonium molybdate and carboxymethylcellulose on a fabric by means of laser irradiation.
Specifically, the technical solution of the present invention is as follows.
The manufacturing method of the fabric-based flexible supercapacitor comprises the following steps:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to a specified proportion and dissolving in water to prepare a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at the temperature of 40-80 ℃ to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser to carbonize carboxymethyl cellulose in the molybdenum-containing coating to form a molybdenum-containing composite conductive layer;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode slices, and superposing the two electrode slices in a manner of clamping electrolyte, thereby obtaining the fabric-based flexible supercapacitor.
In the method for manufacturing a fabric-based flexible supercapacitor, the mass ratio of the ammonium molybdate to the carboxymethyl cellulose is preferably 1:3 to 1: 8.
In the method for manufacturing a fabric-based flexible supercapacitor, the mass mixing ratio of the ammonium molybdate to the carboxymethyl cellulose is more preferably 1:4 to 1: 6.
In the method for manufacturing the fabric-based flexible supercapacitor, the laser wavelength of the green laser is preferably 532nm, the irradiation power is preferably 0.25-0.35 w, and the scanning speed is preferably 2-10 mm/s.
In the method for manufacturing a fabric-based flexible supercapacitor, in the step (2), after the coating liquid containing molybdenum is applied, the coating liquid is preferably dried at 60 ℃ for 2 to 6 hours to be dried and cured.
In the above method for manufacturing a fabric-based flexible supercapacitor, it is preferable that the electrolyte contains phosphoric acid and polyvinyl alcohol.
In the above method for manufacturing a fabric-based flexible supercapacitor, it is preferable that the electrolyte is obtained by adding phosphoric acid and polyvinyl alcohol to water at a mass ratio of 1:1, and stirring at 85 ℃ until a transparent solution is formed.
In the method for manufacturing a fabric-based flexible supercapacitor, the fabric is preferably made of at least one of cotton, hemp, nylon, polyester, polypropylene and nylon.
The invention also provides a manufacturing method of the fabric-based flexible supercapacitor, which comprises the following steps:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to the mass ratio of 1:5, and dissolving in deionized water to obtain a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at 60 ℃ for 4 hours to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser under the conditions that the laser wavelength is 532nm, the irradiation power is 0.25-0.35 w and the scanning speed is 2-10 mm/s, so that carboxymethyl cellulose in the molybdenum-containing coating is carbonized to form a molybdenum-containing composite conductive layer;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode plates, and superposing the two electrode plates in a manner of clamping electrolyte containing phosphoric acid and polyvinyl alcohol to obtain the fabric-based flexible supercapacitor.
The invention also provides a fabric-based flexible supercapacitor obtained by the manufacturing method of any one of the fabric-based flexible supercapacitors, which comprises two electrode plates with a molybdenum-containing composite conductive layer and electrolyte sandwiched between the two electrode plates.
Technical effects
Compared with the prior art, the method for preparing the molybdenum oxide/carbon composite electrode material by using the green laser and manufacturing the fabric-based flexible supercapacitor by using the molybdenum oxide/carbon composite electrode material has the advantages that:
(1) the molybdenum oxide/carbon composite electrode material does not need high-temperature calcination during manufacturing, has low manufacturing cost, and can be obtained by simple laser irradiation.
(2) By adding the carboxymethyl cellulose, the electrode material can be directly adhered to the surface of the fabric, a film is formed by drying, the capacitor electrode is directly formed by laser direct writing, and the operation steps are simple.
(3) The manufacturing method of the invention does not involve the use of organic solvent, has little influence on the air permeability of the fabric, and has long service life compared with the capacitor using organic solvent in the prior art.
(4) The manufacturing method can pattern the electrode plate, has strong controllability, and the obtained super capacitor has excellent specific capacitance and bending stability.
Other advantages of the method of manufacturing the fabric-based flexible supercapacitor of the present invention are further disclosed in the following description.
Drawings
FIG. 1 is a scanning electron micrograph of a molybdenum oxide/carbon composite prepared in the process of the present invention.
Fig. 2 is a graph of cyclic voltammetry tests for a supercapacitor made according to the present invention.
Fig. 3 is a graph of cyclic voltammetry tests of supercapacitors made according to the present invention after 500 bends.
Detailed Description
The technical features of the present invention are described below in connection with preferred embodiments, which are intended to illustrate the present invention and not to limit the present invention.
It should be understood that various obvious modifications, changes and equivalents may be made by those skilled in the art on the basis of the embodiments and examples shown below, and that technical features in different embodiments described below may be arbitrarily combined without contradiction, and that these are within the scope of the present invention.
[ method for manufacturing Fabric-based Flexible supercapacitor ]
The method for manufacturing a fabric-based flexible supercapacitor of the present invention (hereinafter, sometimes also simply referred to as "the manufacturing method of the present invention") comprises the steps of:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to a specified proportion and dissolving in water to prepare a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at the temperature of 40-80 ℃ to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser to carbonize carboxymethyl cellulose in the molybdenum-containing coating to form a molybdenum-containing composite conductive layer;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode plates, and superposing the two electrode plates in a manner of clamping electrolyte, thereby obtaining the fabric-based flexible supercapacitor.
In the manufacturing method, ammonium molybdate is a precursor compound of molybdenum oxide in the conductive layer of the fabric-based flexible supercapacitor, and the molybdenum oxide is used as an electrode material, so that the fabric-based flexible supercapacitor has the advantages of high specific capacitance, high conductivity, good stability and the like. The carboxymethyl cellulose is a precursor of carbon in the conductive layer of the fabric-based flexible supercapacitor, can form gel to carry ammonium molybdate, and is carbonized through laser irradiation and forms a three-dimensional pore structure, so that the specific surface area of the conductive layer is increased, and the specific capacitance is increased.
The mass mixing ratio of ammonium molybdate and carboxymethyl cellulose is preferably 1:3 to 1:8, more preferably 1:4 to 1:6, and may be, for example, 1:4, 1:5, 1:6, or may be any ratio within a range of 1:4 to 1: 6.
The amount of water used for dissolving the ammonium molybdate and the carboxymethyl cellulose is not particularly limited, and an appropriate amount of water may be added as needed, and the obtained molybdenum-containing coating solution is preferably formed into a gel. For example, the amount of water added may be 10 to 50 times, more preferably 20 to 40 times, and for example, 20, 30 or 40 times the total mass of ammonium molybdate and carboxymethyl cellulose. In addition, the water used is preferably deionized water, so that impurities brought by the water can be reduced, and particularly, the influence of metal ions such as sodium, calcium, magnesium and the like can be avoided.
In the step (2), the molybdenum-containing coating liquid is uniformly applied to the fabric, and as a coating method, for example, it can be carried out by a conventional coating method such as brush coating, bar coating, flow coating, spin coating, blade coating, and the like, and preferably, it is applied by spin coating or blade coating.
And drying and curing the fabric coated with the molybdenum coating liquid at the temperature of 40-80 ℃. Specifically, the drying temperature is preferably 60 ℃ to 80 ℃, and may be, for example, 60 ℃, 70 ℃, 80 ℃. The drying time is not particularly limited, but is preferably 2 to 6 hours, and may be, for example, 2, 3, 4, 5 or 6 hours. In a preferred embodiment, the heating conditions are 60 ℃ for 4 hours. And heating to dry and solidify to form the molybdenum-containing coating on the fabric.
In the step (3), a green laser is used for irradiating laser to the molybdenum-containing coating on the fabric, and laser direct writing is carried out. By irradiation with green laser light, carboxymethyl cellulose in the molybdenum-containing coating layer can be carbonized. In the invention, the laser wavelength of the green laser is preferably 532nm, the irradiation power is preferably 0.25-0.35 w, and the scanning speed is 1-10 mm/s. In a preferred embodiment, the irradiation conditions of the green laser are a laser wavelength of 532nm, a power of 0.25W, and a scanning speed of 2.5 mm/s. By irradiating with green laser light having a laser wavelength of 532nm, it is possible to carbonize carboxymethyl cellulose without damaging the fabric as a base. In addition, by irradiating the molybdenum-containing coating with a green laser beam, the ammonium molybdate contained in the molybdenum-containing coating can be decomposed at the same time to form molybdenum oxide, whereby the molybdenum-containing coating can be formed as a molybdenum-containing composite conductive layer. In the step, the carboxymethyl cellulose in the molybdenum-containing coating is carbonized under the condition of keeping the gel, and the three-dimensional structure of the gel is kept after the carbonization, so that a spongy pore structure is formed, the specific surface area is larger, and the specific capacitance characteristic of the molybdenum-containing composite conductive layer is favorably improved.
In the step (4), the fabric with the molybdenum-containing composite conductive layer can be cut into a specified size and a specified shape according to requirements, and better controllability is achieved. The electrolyte used may be one commonly used in the art, and preferably contains phosphoric acid and polyvinyl alcohol. In a preferred embodiment, the electrolyte is formulated by: phosphoric acid and polyvinyl alcohol were added to deionized water at a mass ratio of 1:1 and stirred at 85 ℃ until a clear solution formed.
In the method for manufacturing the fabric-based flexible supercapacitor, the fabric used in the method can be any known fabric with flexibility, and for example, the fabric can be made of at least one of cotton, hemp, nylon, terylene, polypropylene and nylon. In some preferred embodiments, the fabric is cotton.
According to the manufacturing method of the fabric-based flexible supercapacitor, the molybdenum oxide/carbon composite material (namely, the molybdenum-containing composite conductive layer) is obtained by irradiating green laser, high-temperature calcination is not needed, and the manufacturing cost is low. In addition, by adding carboxymethyl cellulose, the electrode material can be directly adhered to the surface of the fabric, a film is formed by drying, the capacitor electrode is directly formed by laser direct writing, and the operation steps are simple. In addition, the manufacturing method of the invention does not need to use organic solvent, thus having little influence on the air permeability of the fabric and having long service life compared with the prior capacitor using organic solvent. In addition, according to the manufacturing method of the present invention, a patterned electrode sheet can be formed, and the resulting supercapacitor has excellent specific capacitance, and also has excellent bending stability with insignificant performance degradation after repeated bending straightening deformation.
As a preferred embodiment of the present invention, the method for manufacturing the fabric-based flexible supercapacitor of the present invention comprises the steps of:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to the mass ratio of 1:5, and dissolving in deionized water to obtain a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at 60 ℃ for 4 hours to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser under the conditions that the laser wavelength is 532nm, the irradiation power is 0.25-0.35 w and the scanning speed is 2-10 mm/s, so that carboxymethyl cellulose in the molybdenum-containing coating is carbonized to form a molybdenum-containing composite conductive layer;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode plates, and superposing the two electrode plates in a manner of clamping electrolyte containing phosphoric acid and polyvinyl alcohol to obtain the fabric-based flexible supercapacitor.
The fabric-based flexible supercapacitor is obtained by the manufacturing method of the fabric-based flexible supercapacitor, and comprises two electrode plates with molybdenum-containing composite conductive layers and electrolyte clamped between the two electrode plates. Specifically, the two electrode sheets are stacked with the electrolyte interposed therebetween so that the respective molybdenum-containing composite conductive layers are opposed to each other, and the molybdenum-containing composite conductive layers are made of a molybdenum oxide/carbon composite material.
The fabric-based flexible supercapacitor has the advantages of simple manufacturing method, low manufacturing cost, long service life, and excellent specific capacitance characteristic and bending stability.
Examples
The method and advantages of the present invention are further illustrated by the following examples, but it should be understood that the following examples are only illustrative of the practice of the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
0.3g of ammonium molybdate and 1.5g of carboxymethyl cellulose were weighed in a beaker, 60g of deionized water was added, and stirring was carried out using a magnetic stirrer until uniform dissolution was achieved, to obtain a molybdenum-containing coating liquid in a gel state.
Subsequently, a clean 10cm × 10cm piece of cotton cloth was prepared as a fabric, the molybdenum-containing coating solution obtained above was uniformly applied on one surface of the cotton cloth by a doctor blade coating method, and then the cloth was put into an oven and dried at 60 ℃ for 4 hours to dry and cure the molybdenum-containing coating solution, thereby obtaining a fabric with a molybdenum-containing coating layer.
Next, the obtained fabric with the molybdenum-containing coating was subjected to laser direct writing using a green laser having a laser wavelength of 532nm, and the laser irradiation conditions were set as follows: the laser power was 0.25W and the scanning speed was 2.5 mm/s. By the laser irradiation, the carboxymethyl cellulose in the molybdenum-containing coating layer is carbonized, and ammonium molybdate is decomposed and changed into molybdenum oxide, thereby forming a molybdenum-containing composite conductive layer. When the molybdenum-containing composite conductive layer was observed with a scanning electron microscope (FESEM, Hitachi S4800), as shown in fig. 1, the molybdenum-containing composite conductive layer had a sponge-like three-dimensional structure in which a large number of pores of 1 μm or less were present and a specific surface area was high.
Then, two 1X 1cm pieces are cut out of the obtained fabric with the molybdenum-containing composite conductive layer2A fabric sheet of the size of (a) as an electrode sheet.
2.0g of polyvinyl alcohol and 2.0g of phosphoric acid were mixed in 20ml of deionized water, and magnetic stirring was performed at 750rpm at 85 ℃ until a transparent solution was obtained, thereby obtaining an electrolytic solution.
And then coating electrolyte on the surface of one side of one electrode plate with the molybdenum-containing composite conductive layer, overlapping the other electrode plate in a mode that the molybdenum-containing composite conductive layers are opposite, and carrying out sandwich type assembly, thereby preparing the fabric-based flexible supercapacitor provided by the invention.
To evaluate the electrical properties of the fabric-based flexible supercapacitor of the invention, the following tests were performed.
The resulting capacitor was subjected to cyclic voltammetry at a scan rate of 10mV/s, and the CV (current density-voltage) curve of the capacitor was determined, the results of which are shown in FIG. 2. According to this test, the specific capacitance of the capacitor at a scan rate of 10mV/s reaches 1.05mF/cm2. Therefore, the super capacitor of the invention has higher specific capacitance.
In addition, the resulting supercapacitor was tested for bending stability by first performing cyclic voltammetry measurements (initial CV curve) at a scan rate of 200mV/s, with the initial specific capacitance of the capacitor being 1.0mF/cm2Then, after the capacitor was bent 500 times, cyclic voltammetry was performed at a scan rate of 200mV/s (CV curve after 500 times of bending), and the specific capacitance of the capacitor after 500 times of bending was 0.94mF/cm2The capacity retention was 94%, and the test CV curve is shown in fig. 3. The supercapacitor of the present invention has excellent bending stability.
Finally, it should be understood that the above description of the embodiments is illustrative in all respects, and not restrictive, and that various modifications may be made without departing from the spirit of the invention. The scope of the present invention is indicated by the claims, rather than the embodiments described above. The scope of the present invention includes all modifications within the meaning and range equivalent to the claims.
Industrial applicability of the invention
According to the manufacturing method of the fabric-based flexible supercapacitor, the molybdenum oxide/carbon composite material is obtained by the laser irradiation method and is used as the electrode material, the manufacturing method is simple, high-temperature calcination is not needed, the manufacturing cost is low, and the method can be used for mass production of the electrode material of the capacitor with excellent specific capacitance and bending stability and the fabric-based flexible supercapacitor. The flexible super capacitor is suitable for wearable electronic equipment and has wide application prospect in the fields of intelligent artificial limbs, biological medicine, robots and the like.
Claims (9)
1. A manufacturing method of a fabric-based flexible supercapacitor is characterized by comprising the following steps:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to a specified proportion and dissolving in water to prepare a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at the temperature of 40-80 ℃ to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser to carbonize carboxymethyl cellulose in the molybdenum-containing coating to form a molybdenum-containing composite conductive layer, wherein the laser wavelength of the green laser is 532nm, the irradiation power is 0.25-0.35 w, and the scanning speed is 2-10 mm/s;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode plates, and superposing the two electrode plates in a manner of clamping electrolyte, thereby obtaining the fabric-based flexible supercapacitor.
2. The method for manufacturing the fabric-based flexible supercapacitor according to claim 1, wherein the mass mixing ratio of the ammonium molybdate to the carboxymethyl cellulose is 1:3 to 1: 8.
3. The method for manufacturing the fabric-based flexible supercapacitor according to claim 1, wherein the mass ratio of the ammonium molybdate to the carboxymethyl cellulose is 1:4 to 1: 6.
4. The method for manufacturing a fabric-based flexible supercapacitor according to claim 1, wherein in the step (2), after the coating solution containing molybdenum is applied, the substrate is dried at 60 ℃ for 2 to 6 hours to be dried and cured.
5. The method of manufacturing a fabric-based flexible supercapacitor of claim 1, wherein the electrolyte comprises phosphoric acid and polyvinyl alcohol.
6. The method of manufacturing a fabric-based flexible supercapacitor according to claim 5, wherein the electrolyte is obtained by adding phosphoric acid and polyvinyl alcohol to deionized water at a mass ratio of 1:1, and stirring at 85 ℃ until a transparent solution is formed.
7. The method for manufacturing the fabric-based flexible supercapacitor according to any one of claims 1 to 6, wherein the fabric is made of at least one of cotton, hemp, nylon, terylene, polypropylene and nylon.
8. A manufacturing method of a fabric-based flexible supercapacitor is characterized by comprising the following steps:
(1) mixing ammonium molybdate and carboxymethyl cellulose according to the mass ratio of 1:5, and dissolving in deionized water to obtain a molybdenum-containing coating liquid;
(2) uniformly coating the molybdenum-containing coating liquid on one side surface of a flexible fabric, and then drying and curing the flexible fabric at 60 ℃ for 4 hours to form the fabric with the molybdenum-containing coating;
(3) performing laser irradiation on the molybdenum-containing coating on the fabric by using a green laser under the conditions that the laser wavelength is 532nm, the irradiation power is 0.25-0.35 w and the scanning speed is 2-10 mm/s, so that carboxymethyl cellulose in the molybdenum-containing coating is carbonized to form a molybdenum-containing composite conductive layer;
(4) and cutting the fabric with the molybdenum-containing composite conductive layer into a specified size to prepare electrode plates, and superposing the two electrode plates in a manner of clamping electrolyte containing phosphoric acid and polyvinyl alcohol to obtain the fabric-based flexible supercapacitor.
9. A fabric-based flexible supercapacitor obtained by the method for manufacturing the fabric-based flexible supercapacitor according to any one of claims 1 to 8, comprising two electrode plates with a molybdenum-containing composite conductive layer and an electrolyte sandwiched between the two electrode plates.
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