CN108630448B - Stable flexible fabric-shaped supercapacitor and preparation and application thereof - Google Patents
Stable flexible fabric-shaped supercapacitor and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 103
- 125000006850 spacer group Chemical group 0.000 claims abstract description 70
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 229920000742 Cotton Polymers 0.000 claims abstract description 26
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 25
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 24
- 229920000728 polyester Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003990 capacitor Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract 4
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000000428 dust Substances 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/48—Conductive polymers
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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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a stable flexible fabric-shaped supercapacitor and preparation and application thereof. The preparation method comprises the steps of directly immersing the multi-component spacer fabric into pyrrole monomer solution, depositing pyrrole monomers on the upper layer and the bottom layer of the cotton fabric and polymerizing the pyrrole monomers by selecting a chemical polymerization method without depositing and polymerizing the pyrrole monomers on the middle layer of the polyester spacer yarn, then injecting gel electrolyte into the spacer fabric deposited with the polypyrrole, and finally packaging to obtain the flexible fabric-shaped supercapacitor. The fabric-shaped supercapacitor with the stable structure can keep stable performance under the deformation conditions of bending, torsion and the like, and is expected to be applied to wearable electronic equipment.
Description
Technical Field
The invention belongs to the field of supercapacitors and preparation and application thereof, and particularly relates to a stable flexible fabric-shaped supercapacitor and preparation and application thereof.
Background
The rapid rise of wearable electronics has led to an increasing demand for flexible, lightweight energy storage devices. In the energy storage device, the super capacitor has the advantages of high power density, long cycle life, environmental friendliness and the like, and has attracted people's extensive attention and a series of research works are developed for the purpose. However, the conventional super capacitor is rigid and not flexible, and cannot be used as an energy storage device of wearable electronic equipment. In order to solve the above problems, researchers have developed flexible supercapacitors.
The fabric has the characteristics of flexibility, light weight and the like, and if the super capacitor is made into a fabric shape, the requirements of flexibility and wearability of the device can be met. Current fabric-like supercapacitors consist of two fabric-like electrodes and a separator/electrolyte assembly. The fabric-like electrode is a fabric deposited with an electrochemically active material, such as a polyester fabric deposited with polyethylene dioxythiophene (adv. mater. technol.,2016,1,1600009), a cotton fabric deposited with carbon nanotubes (Cellulose,2017,24,1121), a carbon fabric deposited with manganese dioxide (chem. eng.j.,2017,309,151), a non-woven fabric deposited with graphene/polyaniline (Nanoscale,2015,7,7318), and the like. The membrane/electrolyte assembly has filter paper/sodium sulfate solution (adv. mater, 2012,24,3246), fabric/sulfuric acid solution without deposited active material (Carbon,2014,73,87), glass fiber membrane/potassium hydroxide solution (ACS Nano,2013,7,5453), and the like. In addition, the gel electrolyte can directly bear the diaphragm/electrolyte assembly, and the common gel electrolyte is polyvinyl alcohol/phosphoric acid electrolyte and polyvinyl alcohol/sulfuric acid electrolyte. One of the major problems with existing fabric-like supercapacitors, however, is that the fabric-like electrodes and separator/electrolyte assemblies are separate entities. Under the action of external force, under the condition that the device is bent, twisted and deformed, the electrode is separated from the diaphragm/electrolyte assembly, so that the performance is cracked and unstable, and the use of the device is seriously influenced. Therefore, in order to overcome the problems of performance cracking and instability of the current fabric-like supercapacitor under bending and torsional deformation conditions, it is necessary to develop a fabric-like supercapacitor with a stable structure.
Disclosure of Invention
The invention aims to solve the technical problem of providing a stable flexible fabric-shaped supercapacitor and preparation and application thereof, solving the problems of performance cracking and instability of the conventional fabric-shaped supercapacitor under bending and torsional deformation conditions, and obtaining the fabric-shaped supercapacitor with a stable structure.
The invention relates to a stable flexible fabric-shaped supercapacitor, which is composed of a multi-component spacer fabric, polypyrrole and a gel electrolyte; the multi-component spacer fabric is a cotton fabric upper layer/a polyester spacer yarn middle layer/a cotton fabric bottom layer, polypyrrole is deposited on the upper layer and the bottom layer of the multi-component spacer fabric, and gel electrolyte is filled in the multi-component spacer fabric.
The polypyrrole is deposited on the upper layer and the bottom layer of the multi-component spacing fabric, and the loading capacity of the polypyrrole is 2.5-6mg cm-2。
The thickness of the upper layer and the bottom layer of the multi-component spacer fabric is 0.5-1.5 mm, and the thickness of the middle layer of the polyester spacer yarn is 1.0-2.5 mm.
The gel electrolyte comprises the raw material components of polyvinyl alcohol, phosphoric acid and water in a mass ratio of 0.5-1:0.5-1:6, and preferably the mass ratio is 1:1: 6.
The gel electrolyte is specifically described as follows: adding 60g of water into 5-10g of polyvinyl alcohol powder, and stirring and dissolving at 90 ℃ for 180 min. After cooling, 5-10g of phosphoric acid is added dropwise and rapidly stirred uniformly, and the stirring time is 30 min.
The invention relates to a preparation method of a stable flexible fabric-shaped supercapacitor, which comprises the following steps:
(1) respectively bonding the upper surface and the lower surface of the cotton fabric and the polyester spacer yarn intermediate layer to obtain a multi-component spacer fabric;
(2) polypyrrole is deposited on the upper layer and the bottom layer of the cotton fabric, but not deposited on the middle layer of the polyester spacing yarn;
(3) and injecting the gel electrolyte into the multi-component spacer fabric deposited with the electrochemical active material by adopting a vacuum auxiliary injection method, and finally packaging to obtain the flexible fabric-shaped supercapacitor.
And (2) respectively bonding the upper surface and the lower surface of the cotton fabric and the middle layer of the polyester spacing yarn by a hot melting bonding machine in the step (1).
The step (2) of depositing polypyrrole on the upper layer and the bottom layer of the cotton fabric by adopting a chemical polymerization method comprises the following specific steps: the multi-component spacer fabric is sequentially placed into acetone and deionized water for cleaning, impurities such as dust, grease and the like on the surface of the spacer fabric are removed, then the multi-component spacer fabric is placed into a drying oven for drying, the dried multi-component spacer fabric is directly immersed into a mixed solution of pyrrole and sodium dodecyl sulfate, the immersion time is 10-20min, then an ammonium persulfate solution is dropwise added into the mixed solution to initiate polymerization, the polymerization temperature is 0 ℃, the polymerization time is 0.5-3 h, and finally, washing and drying are carried out.
In the mixed solution of the pyrrole and the sodium dodecyl sulfate, the concentration of the pyrrole is 0.1-0.3 mol L-1。
The molar ratio of the pyrrole to the sodium dodecyl sulfate is 1: 0.1-0.5, and the molar ratio of the pyrrole to the ammonium persulfate is 1: 1.
The step (3) adopts a vacuum auxiliary injection method, which comprises the following steps: sucking gel electrolyte with needle tube, filling the gel electrolyte into the middle layer of the multi-component spacer fabric, standing for 5-10min, placing into a vacuum oven, maintaining for 10-20min under vacuum and room temperature, taking out, and repeating the above steps for 2-3 times.
The invention relates to application of a stable flexible fabric-shaped supercapacitor, in particular to application of the stable flexible fabric-shaped supercapacitor in wearable electronic equipment.
The stable flexible fabric-shaped super capacitor provided by the invention changes the respective separated positive and negative electrodes and electrolyte/diaphragm components of the traditional super capacitor into a whole with stable structure. And by constructing the multi-component spacer fabric and adopting a selective chemical polymerization method, the electrochemical active material is only deposited on the upper surface and the lower surface of the spacer fabric, and simultaneously, the gel electrolyte is introduced into the spacer fabric through a vacuum auxiliary injection method, so that the fabric-shaped supercapacitor with a stable structure is finally realized, the performance of the fabric-shaped supercapacitor is kept stable under the deformation conditions of bending, twisting and the like, and the fabric-shaped supercapacitor is expected to be applied to wearable electronic equipment.
Advantageous effects
The invention overcomes the problems of performance cracking and instability of the prior fabric-shaped super capacitor under the conditions of bending and torsional deformation, and obtains the fabric-shaped super capacitor with a stable structure;
the fabric-shaped supercapacitor with the stable structure keeps stable performance under deformation conditions of bending, torsion and the like, and is expected to be applied to wearable electronic equipment;
the electrochemical test result of the invention shows that the current density is 0.1Ag-1Then, the specific capacitance of the prepared high-stability flexible fabric-shaped supercapacitor is 140--1After 1000 times of circulation, the capacitance can still keep about 85-88%, and in a bending test (bending angle is 90 degrees), the capacitance retention rate is 93-96% after 200 times of bending.
Drawings
FIG. 1 is a schematic representation of a multicomponent spacer fabric and a multicomponent spacer fabric with polypyrrole deposited.
FIG. 2 is a scanning electron micrograph of the multicomponent spacer fabric of example 1.
FIG. 3 scanning electron micrographs of the multicomponent spacer fabric of example 1 with polypyrrole deposited.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Preparing a multi-component spacer fabric: the thickness of the selected cotton fabric is 0.5mm, and the thickness of the middle layer of the polyester spacing yarn is 1.5 mm. And respectively bonding the upper surface and the lower surface of the cotton fabric and the intermediate layer of the polyester spacing yarn by a hot-melt bonding machine to obtain the multi-component spacing fabric.
(2) Preparation of a polypyrrole-deposited multicomponent spacer fabric: the polypyrrole is deposited on the upper layer and the bottom layer of the cotton fabric by adopting a selective chemical polymerization method, and is not deposited on the middle layer of the polyester spacing yarn. Firstly, the multi-component spacer fabric is sequentially put into acetone and deionized water for cleaning, impurities such as dust, grease and the like on the surface of the spacer fabric are removed, and then the spacer fabric is put into an oven for drying. Directly soaking the dried multi-component spacer fabric into a mixed solution of pyrrole and sodium dodecyl sulfate, wherein the soaking time is 20min, and the pyrrole concentration is 0.1mol L-1. Subsequently, an ammonium persulfate solution was added dropwise to the above solution to initiate polymerization. Wherein the molar ratio of the pyrrole to the sodium dodecyl sulfate is 1:0.2, the molar ratio of the pyrrole to the ammonium persulfate is 1:1, the polymerization temperature is 0 ℃, and the polymerization time is 1.5 h. Finally, the fabric obtained after polymerization is washed by deionized water and then is put into an oven for drying, and the polypyrrole loading capacity of the obtained spacer fabric is 2.61mg cm-2。
(3) Preparing a high-stability flexible fabric-shaped supercapacitor: injecting gel electrolyte into the multi-component spacer fabric deposited with polypyrrole by adopting a vacuum auxiliary injection method, and finally packaging to obtain the flexible fabric-shaped supercapacitor, wherein the gel electrolyte comprises the following raw material components: polyvinyl alcohol, phosphoric acid and water in a mass ratio of 1:1: 6. The electrochemical test result shows that the current density is 0.1Ag-1Then, the specific capacitance of the prepared high-stability flexible fabric-shaped supercapacitor is 141.62F g-1After 1000 times of circulation, the capacitance can still keep about 85%. In the bending test (bending angle 90 °), the capacity retention rate was 95% through 200 times of bending.
Example 2
(1) Preparing a multi-component spacer fabric: the thickness of the selected cotton fabric is 1mm, and the thickness of the middle layer of the polyester spacing yarn is 2 mm. And respectively bonding the upper surface and the lower surface of the cotton fabric and the intermediate layer of the polyester spacing yarn by a hot-melt bonding machine to obtain the multi-component spacing fabric.
(2) Preparation of a polypyrrole-deposited multicomponent spacer fabric: the polypyrrole is deposited on the upper layer and the bottom layer of the cotton fabric by adopting a selective chemical polymerization method, and is not deposited on the middle layer of the polyester spacing yarn. Firstly, the multi-component spacer fabric is sequentially put into acetone and deionized water for cleaning, impurities such as dust, grease and the like on the surface of the spacer fabric are removed, and then the spacer fabric is put into an oven for drying. Directly soaking the dried multi-component spacer fabric into a mixed solution of pyrrole and sodium dodecyl sulfate, wherein the soaking time is 20min, and the pyrrole concentration is 0.1mol L-1. Subsequently, an ammonium persulfate solution was added dropwise to the above solution to initiate polymerization. Wherein the molar ratio of the pyrrole to the sodium dodecyl sulfate is 1:0.2, the molar ratio of the pyrrole to the ammonium persulfate is 1:1, the polymerization temperature is 0 ℃, and the polymerization time is 1.5 h. Finally, the fabric obtained after polymerization is washed by deionized water and then is put into an oven for drying, and the polypyrrole loading capacity of the obtained spacer fabric is 3.04mg cm-2。
(3) Preparing a high-stability flexible fabric-shaped supercapacitor: injecting gel electrolyte into multi-component spacer deposited with polypyrrole by vacuum assisted injectionAnd finally packaging in the fabric to obtain the flexible fabric-shaped supercapacitor, wherein the gel electrolyte comprises the following raw material components: polyvinyl alcohol, phosphoric acid and water in a mass ratio of 1:1: 6. The electrochemical test result shows that the current density is 0.1Ag-1Then, the specific capacitance of the prepared high-stability flexible fabric-shaped supercapacitor is 163.26F g-1After 1000 times of circulation, the capacitance can still keep about 85%. In the bending test (bending angle 90 °), the capacity retention rate was 95% after 100 bending.
Example 3
(1) Preparing a multi-component spacer fabric: the thickness of the selected cotton fabric is 1mm, and the thickness of the middle layer of the polyester spacing yarn is 2 mm. And respectively bonding the upper surface and the lower surface of the cotton fabric and the intermediate layer of the polyester spacing yarn by a hot-melt bonding machine to obtain the multi-component spacing fabric.
(2) Preparation of a polypyrrole-deposited multicomponent spacer fabric: the polypyrrole is deposited on the upper layer and the bottom layer of the cotton fabric by adopting a selective chemical polymerization method, and is not deposited on the middle layer of the polyester spacing yarn. Firstly, the multi-component spacer fabric is sequentially put into acetone and deionized water for cleaning, impurities such as dust, grease and the like on the surface of the spacer fabric are removed, and then the spacer fabric is put into an oven for drying. Directly soaking the dried multi-component spacer fabric into a mixed solution of pyrrole and sodium dodecyl sulfate, wherein the soaking time is 20min, and the pyrrole concentration is 0.2mol L-1. Subsequently, an ammonium persulfate solution was added dropwise to the above solution to initiate polymerization. Wherein the molar ratio of the pyrrole to the sodium dodecyl sulfate is 1:0.2, the molar ratio of the pyrrole to the ammonium persulfate is 1:1, the polymerization temperature is 0 ℃, and the polymerization time is 1.5 h. Finally, the fabric obtained after polymerization is washed by deionized water and then is put into an oven for drying, and the polypyrrole loading capacity of the obtained spacer fabric is 5.7mg cm-2。
(3) Preparing a high-stability flexible fabric-shaped supercapacitor: injecting gel electrolyte into the multi-component spacer fabric deposited with polypyrrole by adopting a vacuum auxiliary injection method, and finally packaging to obtain the flexible fabric-shaped supercapacitor, wherein the gel electrolyte comprises the following raw material components: polyvinyl alcohol, phosphoric acid and water in a mass ratio of 1:1: 6. Electrochemical testingThe results showed that the current density was 0.1Ag-1Then, the specific capacitance of the prepared high-stability flexible fabric-shaped supercapacitor is 241.76F g-1After 1000 times of circulation, the capacitance can still keep about 85%. In the twist test (twist angle 90 °), the capacity retention was 95% after 100 twists.
Example 4
(1) Preparing a multi-component spacer fabric: the thickness of the selected cotton fabric is 1mm, and the thickness of the middle layer of the polyester spacing yarn is 2 mm. And respectively bonding the upper surface and the lower surface of the cotton fabric and the intermediate layer of the polyester spacing yarn by a hot-melt bonding machine to obtain the multi-component spacing fabric.
(2) Preparation of a polypyrrole-deposited multicomponent spacer fabric: the polypyrrole is deposited on the upper layer and the bottom layer of the cotton fabric by adopting a selective chemical polymerization method, and is not deposited on the middle layer of the polyester spacing yarn. Firstly, the multi-component spacer fabric is sequentially put into acetone and deionized water for cleaning, impurities such as dust, grease and the like on the surface of the spacer fabric are removed, and then the spacer fabric is put into an oven for drying. Directly soaking the dried multi-component spacer fabric into a mixed solution of pyrrole and sodium dodecyl sulfate, wherein the soaking time is 20min, and the pyrrole concentration is 0.2mol L-1. Subsequently, an ammonium persulfate solution was added dropwise to the above solution to initiate polymerization. Wherein the molar ratio of the pyrrole to the sodium dodecyl sulfate is 1:0.2, the molar ratio of the pyrrole to the ammonium persulfate is 1:1, the polymerization temperature is 0 ℃, and the polymerization time is 2 h. Finally, the fabric obtained after polymerization is washed by deionized water and then is put into an oven for drying, and the polypyrrole loading capacity of the obtained spacer fabric is 5.81mg cm-2。
(3) Preparing a high-stability flexible fabric-shaped supercapacitor: injecting gel electrolyte into the multi-component spacer fabric deposited with polypyrrole by adopting a vacuum auxiliary injection method, and finally packaging to obtain the flexible fabric-shaped supercapacitor, wherein the gel electrolyte comprises the following raw material components: polyvinyl alcohol, phosphoric acid and water in a mass ratio of 1:1: 6. The electrochemical test result shows that the current density is 0.1Ag-1Then, the specific capacitance of the prepared high-stability flexible fabric-shaped supercapacitor is 245.07F g-1After 1000 cycles, the electricity is suppliedStill can keep about 85 percent. In the twist test (twist angle 90 °), the capacity retention was 93% after 200 twists.
Claims (7)
1. A stable flexible fabric-like supercapacitor characterized by: the super capacitor is composed of a multi-component spacer fabric, polypyrrole and gel electrolyte; the multi-component spacer fabric is a cotton fabric upper layer/a polyester spacer yarn middle layer/a cotton fabric bottom layer, polypyrrole is deposited on the upper layer and the bottom layer of the multi-component spacer fabric, and gel electrolyte is filled in the multi-component spacer fabric; wherein the super capacitor is prepared by the following method:
(1) respectively bonding the upper surface and the lower surface of the cotton fabric and the polyester spacer yarn intermediate layer to obtain a multi-component spacer fabric;
(2) depositing polypyrrole on the upper layer and the bottom layer of the cotton fabric; wherein the step (2) of depositing polypyrrole on the upper layer and the bottom layer of the cotton fabric comprises the following specific steps: cleaning and drying a multi-component spacer fabric, directly soaking the dried multi-component spacer fabric in a mixed solution of pyrrole and sodium dodecyl sulfate for 10-20min, then dropwise adding an ammonium persulfate solution into the mixed solution at the polymerization temperature of 0 ℃ for 0.5-3 h, and finally, washing and drying;
(3) and injecting the gel electrolyte into the multi-component spacer fabric deposited with the electrochemical active material by adopting a vacuum auxiliary injection method, and finally packaging to obtain the flexible fabric-shaped supercapacitor.
2. A stable flexible fabric-like supercapacitor according to claim 1, characterised in that: the thickness of the upper layer and the bottom layer of the multi-component spacer fabric is 0.5-1.5 mm, and the thickness of the middle layer of the polyester spacer yarn is 1.0-2.5 mm.
3. A stable flexible fabric-like supercapacitor according to claim 1, characterised in that: and (2) respectively bonding the upper surface and the lower surface of the cotton fabric and the middle layer of the polyester spacing yarn by a hot melting bonding machine in the step (1).
4. A stable flexible fabric-like supercapacitor according to claim 1, characterised in that: in the mixed solution of the pyrrole and the sodium dodecyl sulfate in the step (2), the concentration of the pyrrole is 0.1-0.3 mol L-1。
5. A stable flexible fabric-like supercapacitor according to claim 1, characterised in that: in the step (2), the molar ratio of pyrrole to sodium dodecyl sulfate is 1: 0.1-0.5, and the molar ratio of pyrrole to ammonium persulfate is 1: 1.
6. A stable flexible fabric-like supercapacitor according to claim 1, characterised in that: the step (3) adopts a vacuum auxiliary injection method, which comprises the following steps: sucking gel electrolyte with needle tube, filling the gel electrolyte into the middle layer of the multi-component spacer fabric, standing for 5-10min, placing into a vacuum oven, maintaining for 10-20min under vacuum and room temperature, taking out, and repeating the above steps for 2-3 times.
7. Use of a stable flexible fabric-like supercapacitor according to any one of claims 1 to 6, characterized in that: use of a stable flexible fabric-like supercapacitor in wearable electronics.
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