CN109473286B - Stretchable fiber fabric supercapacitor and preparation method thereof - Google Patents

Stretchable fiber fabric supercapacitor and preparation method thereof Download PDF

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CN109473286B
CN109473286B CN201811129689.2A CN201811129689A CN109473286B CN 109473286 B CN109473286 B CN 109473286B CN 201811129689 A CN201811129689 A CN 201811129689A CN 109473286 B CN109473286 B CN 109473286B
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elastic cloth
nickel
coated
cloth
elastic
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CN109473286A (en
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麦文杰
邱美佳
孙鹏
黎晋良
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Jinan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/26Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/56Solid electrolytes, e.g. gels; Additives therein
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/13Energy storage using capacitors

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

The invention discloses a stretchable fiber fabric supercapacitor, which comprises alloy coating coated metal coating elastic cloth, an electrolyte and diaphragm layer, and carbon nanotube modified alloy coating coated metal coating elastic cloth; the alloy coating layer is coated with metal coating elastic cloth to be a positive electrode; the metal coating elastic cloth coated by the carbon nano tube modified alloy coating is taken as a negative electrode; the electrolyte and the diaphragm layer are positioned between the anode and the cathode; according to the invention, a two-step chemical plating method is adopted, so that a composite plating layer with excellent conductivity and stability is obtained on the high-elasticity spandex fiber cloth; the elastic fabric with excellent conductivity has very excellent flexibility and tensile property, and can bear thousands of bending, folding and tensile tests; in addition, the composite coating has excellent electrochemical energy storage characteristics and can be made into a high-performance stretchable supercapacitor.

Description

Stretchable fiber fabric supercapacitor and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage, in particular to a stretchable fiber fabric supercapacitor and a preparation method thereof.
Background
In recent years, with the rapid development and intensive research of wearable electronic equipment, however, the conventional super capacitor is produced and used in the form of a button or a wound device, and has the disadvantages of discomfort, non-portability and the like when being used as a functional unit of the wearable electronic equipment, so that the further development of the wearable electronic equipment is greatly limited by the rigid energy storage device nowadays; therefore, if the whole electronic system is wearable, the development of a flexible, light and portable super capacitor is urgently needed. In addition, wearable electronic fabric products need to have good mechanical stability, including stretchable cyclability and foldable cyclability, so as to be suitable for various activities that people need every day.
Based on this, various types of flexible and stretchable energy storage devices have been actively focused and developed. Among the numerous problematic issues, flexible stretchable substrates with excellent and stable electrical conductivity are one of the most difficult to achieve. Heretofore, methods of stretching flexible substrates excellent in various properties have been widely reported. In the prior art, numerous lead and layout design problems exist when linear devices are woven and assembled, and the wide popularization is difficult to obtain in a short time; the electrochemical performance of the device is general, and the silver conductive substrate is easy to be oxidized in the electrochemical energy storage process so as to reduce the cycling stability, so that the silver conductive substrate is not beneficial to commercial use.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and provide a stretchable fiber fabric supercapacitor which has excellent and stable conductivity and high electrochemical energy storage performance.
The invention also aims to provide a stretchable fiber fabric supercapacitor preparation method.
The main purpose of the invention is realized by the following technical scheme:
a stretchable fiber fabric supercapacitor comprises an alloy coating layer coated metal coating elastic cloth, an electrolyte and diaphragm layer, and a carbon nanotube modified alloy coating layer coated metal coating elastic cloth;
the alloy coating layer is coated with metal coating elastic cloth to be a positive electrode;
the metal coating elastic cloth coated by the carbon nano tube modified alloy coating is taken as a negative electrode;
the electrolyte and the diaphragm layer are stretchable polymer hydrogel and are positioned between the anode and the cathode.
Furthermore, the alloy coating wraps the metal coating elastic cloth and comprises the alloy coating, the metal coating and the elastic cloth;
further, the alloy plating layer is an alloy material with high conductivity, stability and energy storage characteristics, and specifically is one of nickel-cobalt-phosphorus, nickel-cobalt-boron, nickel-molybdenum-phosphorus and nickel-copper-boron;
further, the metal plating layer is a metal material capable of carrying out the next catalytic and chemical plating reaction, and specifically is one of nickel, copper and cobalt;
further, the elastic cloth is a fiber cloth capable of being stretched to a certain extent, and specifically is one of spandex fibers and polyester fibers;
further, the alloy coating layer coated metal coating elastic cloth modified by the carbon nano tube is obtained by soaking the alloy coating layer coated metal coating elastic cloth in carbon nano tube slurry, drying and then circularly soaking;
furthermore, the electrolyte and the diaphragm layer are stretchable polymer hydrogel with hydrogen bonding function.
The other purpose of the invention is realized by the following technical scheme:
a stretchable fiber fabric supercapacitor preparation method is characterized by comprising the following steps:
preparing elastic cloth: modifying the elastic cloth by utilizing a macromolecule grafting process to obtain the elastic cloth;
preparing metal coating elastic cloth: soaking the elastic cloth in an activating solution, and then placing the elastic cloth in a chemical plating metal solution for reaction to obtain the elastic cloth;
preparing the alloy coating layer coated metal coating elastic cloth: the metal coating is elastically arranged in the chemical plating alloy plating solution to react to obtain the alloy plating solution;
preparing the carbon nano tube modified alloy coating layer coated metal coating layer elastic cloth: soaking the alloy coating layer coated metal coating layer elastic cloth in carbon nano tube slurry, drying and then circularly soaking to obtain the carbon nano tube elastic cloth;
preparing an electrolyte and a diaphragm layer: polymerizing to prepare a stretchable hydrogel electrolyte carrier and a diaphragm, and adsorbing a sufficient amount of electrolyte solution.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method obtains a composite plating layer with excellent conductivity and stability on the high-elasticity spandex fiber cloth by a two-step chemical plating method; the elastic fabric with excellent conductivity has excellent flexibility and tensile property, and can bear thousands of bending, folding and tensile tests. In addition, the composite coating has excellent electrochemical energy storage characteristics, and can be made into a high-performance stretchable supercapacitor as wearable energy storage equipment.
Drawings
FIG. 1 is a schematic structural diagram of an asymmetric stretchable supercapacitor based on Ni-Co-P coated nickel-plated stretch fabric in example 1;
FIG. 2 is a scanning electron microscope photograph of the spandex fiber elastic fabric in each process of example 2, wherein (a) and (b) are scanning electron microscope photographs of the spandex fiber elastic fabric; (c) and (d) is a scanning electron microscope image of the nickel-plated elastic cloth; (e) (f) is a scanning electron microscope picture of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth;
FIG. 3 is the X-ray diffraction spectra of the spandex fiber elastic cloth, the nickel-plated elastic cloth and the nickel-cobalt-phosphorus coated nickel-plated elastic cloth in the example;
FIG. 4 is a diagram showing the composition of the Ni-Co-P coated nickel-plated stretch fabric in example 2; wherein (a) is an energy spectrum of nickel-cobalt-phosphorus coated nickel-plated elastic cloth, and (b), (c) and (d) are X-ray photoelectron energy spectrums of Ni, Co and P respectively;
FIG. 5 is a schematic view showing the electrical stability of the Ni-Co-P coated nickel-plated elastic fabric and the nickel-plated elastic fabric at room temperature of 25 ℃ in example 2;
FIG. 6 is a schematic diagram showing the electrical stability at a high temperature of 80 ℃ of the Ni-Co-P coated nickel-plated elastic fabric and the nickel-plated elastic fabric in example 2;
FIG. 7 is a schematic drawing showing the tensile properties of the Ni-Co-P coated nickel-plated elastic fabric and the initial elastic fabric in example 2;
FIG. 8 is a schematic diagram showing the tensile properties of the Ni-Co-P coated nickel-plated elastic fabric in example 2 under different tensile conditions;
FIG. 9 is a schematic diagram showing the resistance change of the Ni-Co-P coated nickel-plated elastic fabric in example 2 under different stretching amounts;
FIG. 10 is a schematic view showing the cyclic stretching performance of the Ni-Co-P coated nickel-plated stretch fabric in example 2;
FIG. 11 is a schematic view showing the folding cycle performance of the Ni-Co-P coated nickel-plated stretch fabric of example 2;
FIG. 12 is a graph showing cyclic voltammogram and cyclic stability of the Ni-Co-P coated nickel-plated elastic fabric of example 2;
FIG. 13 is a scanning electron microscope image of the Ni-Co-P coated nickel-plated stretch fabric with the single-walled carbon nanotube modified in example 2;
fig. 14 is a schematic view of (a) cyclic voltammogram and (b) constant current charging and discharging curve of the nickel-cobalt-phosphorus coated nickel-plated elastic fabric with the modified single-walled carbon nanotube in example 2;
fig. 15 is (a) a cyclic voltammogram graph and (b) a constant current charging and discharging graph of the asymmetric stretchable supercapacitor based on the nickel-cobalt-phosphorus coated nickel-plated elastic fabric in example 2;
fig. 16 is a schematic diagram of (a) electrochemical stability, (b) bending stability and (c) tensile stability of the asymmetric stretchable supercapacitor based on the ni — po coated nickel plated spandex in example 2.
In the figure, the 1-carbon nanotube modified alloy coating is coated with metal coating elastic cloth, 2-electrolyte and diaphragm layer, and 3-alloy coating is coated with metal coating elastic cloth.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1:
a stretchable fiber fabric supercapacitor comprises an alloy coating layer coated metal coating layer elastic cloth 3, an electrolyte and diaphragm layer 2, and a carbon nanotube modified alloy coating layer coated metal coating layer elastic cloth 1 as shown in figure 1;
the alloy coating layer coated metal coating layer elastic cloth 3 is a positive electrode;
the metal coating elastic cloth 1 coated by the carbon nano tube modified alloy coating is taken as a negative electrode;
the electrolyte and the diaphragm layer 2 are stretchable polymer hydrogel and are positioned between the anode and the cathode.
Further, the metal plating elastic cloth 3 is wrapped by the alloy plating and comprises the alloy plating, the metal plating and the elastic cloth;
further, the alloy plating layer is an alloy material with high conductivity, stability and energy storage characteristics, and specifically is one of nickel-cobalt-phosphorus, nickel-cobalt-boron, nickel-molybdenum-phosphorus and nickel-copper-boron;
further, the metal plating layer is a metal material capable of carrying out the next catalytic and chemical plating reaction, and specifically is one of nickel, copper and cobalt;
further, the elastic cloth is a fiber cloth capable of being stretched to a certain extent, and specifically is one of spandex fibers and polyester fibers;
further, the alloy coating layer coated metal coating elastic cloth 1 modified by the carbon nano tube is obtained by soaking the alloy coating layer coated metal coating elastic cloth in carbon nano tube slurry, drying and then circularly soaking;
further, the electrolyte and the diaphragm layer 2 are stretchable polymer hydrogel with hydrogen bonding function.
Example 2:
the detailed process of the high-conductivity stretchable elastic cloth comprises the following steps:
(1) surface modification of elastic cloth: the method comprises the steps of using spandex fibers as a base material, respectively cleaning the surface of cloth by using acetone, deionized water and alcohol, then placing the cloth in a surface modification solution 1 to soak for 1-2 hours at normal temperature, taking out the cloth, and then transferring the cloth to a surface modification solution 2 to soak for 1-2 hours at 85 ℃. The surface modification solution 1 adopts alcohol solution containing 10 percent of vinyl trimethoxy silane by volume fraction; the surface modification solution 2 adopts a method that potassium persulfate of 60mg/100mL solution is added into an aqueous solution containing 20% volume fraction of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride. Taking out and washing with alcohol and deionized water to complete the modification.
(2) Chemical nickel plating elastic cloth: soaking the surface-modified spandex fiber cloth in an activation solution for 15-30 minutes, taking out, cleaning with deionized water, then placing in a chemical nickel plating solution, reacting at 40 ℃ for 30 minutes, taking out, cleaning with deionized water, and drying. The activating solution adopts an ammonium chloropalladate aqueous solution containing 5 mM; the electroless nickel plating solution comprises a solution A and a solution B, wherein the solution A comprises 50g L-1Nickel sulfate pentahydrate, 25g L-112.5g L sodium citrate-1The lactic acid of (a); and liquid B comprises 5g L-1Dimethylamine borane.
(3) Preparing nickel-cobalt-phosphorus coated nickel-plated elastic cloth: and (3) placing the prepared nickel plating elasticity in a nickel-cobalt-phosphorus plating solution, reacting for 15 minutes at 90 ℃, taking out, cleaning and drying to obtain the final high-conductivity stretchable fiber fabric energy storage electrode. The nickel-cobalt-phosphorus plating solution comprises 30g L-130g L-1Cobalt chloride, 20g L-1Sodium dihydrogen hypophosphite, 100g L-1Sodium citrate and 30g L-1Boric acid.
The scanning electron microscope images of the spandex stretch fabric in each process are shown in fig. 2, wherein (a) and (b) are the scanning electron microscope images of the spandex stretch fabric; (c) and (d) is a scanning electron microscope image of the nickel-plated elastic cloth; (e) (f) is a scanning electron microscope picture of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth; FIG. 3 is an X-ray diffraction pattern of spandex fiber elastic cloth, nickel-plated elastic cloth and nickel-cobalt-phosphorus coated nickel-plated elastic cloth; FIG. 4 is a diagram showing the composition of Ni-Co-P coated nickel-plated elastic cloth; wherein (a) is an energy spectrum of nickel-cobalt-phosphorus coated nickel-plated elastic cloth, and (b), (c) and (d) are X-ray photoelectron energy spectrums of Ni, Co and P respectively;
the nickel-cobalt-phosphorus coated nickel plating elastic cloth is obtained by a two-step chemical plating method; some nickel nanospheres of dozens to hundreds of nanometers are distributed on the surface of the nickel-plated elastic cloth, and after nickel-cobalt-phosphorus coating, micron-level nickel-cobalt-phosphorus balls are firmly wrapped outside the nickel nanospheres; the nickel nanospheres have certain crystallinity, while the nickel-cobalt-phosphorus microspheres show an amorphous structure.
The nickel-cobalt-phosphorus coated nickel-plated elastic cloth is subjected to electrical performance test by a four-probe electrical tester. The stability is excellent, and the resistance can be kept stable at the normal temperature of 25 ℃ for more than 14 days, as shown in figure 5, or at the temperature of 80 ℃ for more than 90 minutes, as shown in figure 6; the sheet resistance of the alloy is 0.19 omega □-1Conductivity of 532S cm-1
And testing the mechanical properties of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth and the initial elastic cloth by using a universal mechanical testing machine. Compared with the initial elastic cloth, the ultimate tensile strength of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth is improved, and the tensile amount is correspondingly reduced, as shown in fig. 7, which is a schematic drawing of the tensile properties of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth and the initial elastic cloth. In addition, in the cyclic tensile test, the nickel cobalt phosphorus coated nickel plating elastic fabric can be recovered under the tensile amount within 80%, as shown in fig. 8, which is a schematic diagram of the resistance change condition of the nickel cobalt phosphorus coated nickel plating elastic fabric under different tensile amounts, and the insets are photographs of the original nickel cobalt phosphorus coated nickel plating elastic fabric and the tensile amount of 100% in the test process.
The nickel-cobalt-phosphorus coated nickel-plated elastic cloth is used as a conductive intermediate, so that an LED bulb can be lightened, and the light emission of the bulb is not influenced by 40% stretching; the nickel-cobalt-phosphorus coated nickel-plated elastic cloth can keep stable conductivity within 80% of stretching amount, and after 1000 stretching cycles and 5000 folding cycles, the electrical property is almost kept 100%; therefore, the nickel-cobalt-phosphorus coated nickel-plated elastic cloth can be used as a wearable conductive fabric in the future and has a great application prospect; FIG. 9 is a schematic diagram of the resistance change of the Ni-Co-P coated nickel-plated elastic fabric under different stretching amounts, and the inset is a photograph of the original and 100% stretched state during the testing process; FIG. 10 shows the cyclic tensile properties of Ni-Co-P coated nickel plated stretch fabric, and the inset is a photograph of the original and 100% stretched fabric during the test; fig. 11 shows the folding cycle performance of the ni — co-phosphorus coated nickel-plated elastic fabric, and the inset is the photographs of the original, folded and folded states during the testing process.
The electrochemical energy storage performance of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth is activated by a three-electrode testing system, wherein the nickel-cobalt-phosphorus coated nickel-plated elastic cloth is used as a working electrode, a carbon rod is used as a counter electrode, and saturated calomel is used as a reference electrode. The electrochemical energy storage performance obtained by testing is much higher than that of nickel-cobalt-phosphorus coated nickel-plated elastic cloth at 5mV s-1At a sweeping speed of 877.6mF cm in capacitance-2And 713F g-1. After the cyclic voltammetry test of 6000, the capacitance of the nickel-cobalt-phosphorus coated nickel-plated elastic fabric can still keep 101% of the original electric quantity, as shown in fig. 12, a cyclic voltammetry curve diagram and a cyclic stability diagram of the nickel-cobalt-phosphorus coated nickel-plated elastic fabric.
The nickel-cobalt-phosphorus-coated nickel-plated elastic cloth-based negative electrode material is obtained by soaking commercial single-walled carbon nanotube aqueous slurry. The specific method comprises the following steps: immersing the nickel-cobalt-phosphorus coated nickel-plated elastic cloth in the commercial single-walled carbon nanotube aqueous slurry for 10 seconds, taking out the nickel-cobalt-phosphorus coated nickel-plated elastic cloth, drying the nickel-cobalt-phosphorus coated nickel-plated elastic cloth at 60 ℃ for 30 minutes, then immersing the nickel-cobalt-phosphorus coated nickel-plated elastic cloth in the commercial single-walled carbon nanotube aqueous slurry for 10 seconds again, drying, and repeating the steps for 10 times. The single-walled carbon nanotubes can be uniformly dispersed on the surface of the nickel-cobalt-phosphorus coated nickel-plated elastic cloth; as shown in fig. 13, it is a scanning electron microscope image of the nickel-cobalt-phosphorus coated nickel-plated elastic fabric with the single-walled carbon nanotube modified, and has good electrochemical energy storage performance in a potential window interval of 0 to-0.6V, as shown in fig. 14, it is a schematic view of a cyclic voltammetry curve and a schematic view of a constant current charging and discharging curve of the nickel-cobalt-phosphorus coated nickel-plated elastic fabric with the single-walled carbon nanotube modified.
The electrolyte and the diaphragm of the stretchable asymmetric supercapacitor adopt high-elasticity stretchable hydrogel, in particular polyacrylamide soaked in a potassium hydroxide aqueous solution, and the preparation method comprises the following steps: 3.8g of vinyltrimethoxysilane was added to 30mL of deionized water, and stirring was continued for 12 hours, followed by dilution to 0.067 wt%. Subsequently, 12g of acrylamide monomer and 0.06g of ammonium persulfate were added to the diluted aqueous vinyltrimethoxysilane solution and stirred for 30 minutes. The dispersion was then left to react at 40 ℃ for 30 minutes. The hydrogel obtained was then soaked in a 1M potassium hydroxide solution for 20 minutes to obtain the final stretchable electrolyte and separator layer.
The nickel-cobalt-phosphorus coated nickel-plated elastic cloth, the stretchable hydrogel electrolyte, the diaphragm and the nickel-cobalt-phosphorus coated nickel-plated elastic cloth modified by the single-walled carbon nanotube are stacked in sequence to form the stretchable asymmetric supercapacitor, and the structure is shown in the figure. The cyclic voltammetry test and the constant current charge and discharge test show that the assembled stretchable asymmetric supercapacitor has good energy storage performance, and the cyclic voltammetry curve and the constant current charge and discharge curve are shown in fig. 15 of the asymmetric stretchable supercapacitor based on the nickel-cobalt-phosphorus coated nickel-plated elastic fabric. In addition, after 6000 cyclic volt-ampere tests, the capacitance of the stretchable asymmetric supercapacitor is kept at the original 98%, and after 1000 bending cycles and stretching cycles, the capacitance of the stretchable asymmetric supercapacitor can be kept at the original 94%; fig. 16 is a schematic diagram of (a) electrochemical stability, (b) bending stability, and (c) tensile stability of an asymmetric stretchable supercapacitor based on ni-co-p coated nickel plated spandex, respectively.
Example 3:
the detailed process of the high-conductivity stretchable elastic cloth comprises the following steps:
(1) surface modification of elastic cloth: the method comprises the steps of using polyester fibers as a base material, respectively cleaning the surface of cloth by using acetone, deionized water and alcohol, then placing the cloth in a surface modification solution 1 to soak for 1-2 hours at normal temperature, taking out the cloth, transferring the cloth to a surface modification solution 2, and soaking the cloth for 1-2 hours at 85 ℃. The surface modification solution 1 adopts an alcohol solution containing 20 percent of vinyl trimethoxy silane by volume fraction; the surface modification solution 2 adopts a method that potassium persulfate of 60mg/100mL solution is added into an aqueous solution containing 20% volume fraction of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride. Taking out and washing with alcohol and deionized water to complete the modification.
(2) Chemical nickel plating elastic cloth: soaking the surface-modified polyester fiber cloth into an activating solution for 15-30 minutes, taking out, cleaning with deionized water, then placing into a chemical nickel plating solution, reacting for 30 minutes at 40 ℃, taking out, cleaning with deionized water, and drying. The activating solution adopts an ammonium chloropalladate aqueous solution containing 5 mM; the electroless nickel plating solution comprises a solution A and a solution B, wherein the solution A comprises 50g L-1Nickel sulfate pentahydrate, 25g L-112.5g L sodium citrate-1The lactic acid of (a); and liquid B comprises 5g L-1Dimethylamine borane.
(3) Preparing nickel-cobalt-boron coated nickel-plated elastic cloth: and (3) arranging the prepared nickel plating elasticity in a nickel-cobalt-boron plating solution, reacting for 15 minutes at 35 ℃, taking out, cleaning and drying to obtain the final high-conductivity stretchable fiber fabric energy storage electrode. The nickel-cobalt-boron plating solution comprises 45g L-1Nickel chloride of, 5g L-1Cobalt chloride, 1g L-1Dimethylamine borane and 160mL L-1The aqueous ammonia of (1).
By means of four probesThe pin electrical tester tests the electrical property of the nickel-cobalt-boron coated nickel-plated elastic cloth. The stability is excellent, and the resistance can be kept stable for more than 10 days at normal temperature, and can also be kept stable for more than 80 minutes at 80 ℃. The square resistance of the alloy is 0.25 omega □-1Conductivity of 425S cm-1. In the electrochemical test of the nickel-cobalt-boron coated nickel-plated elastic cloth, the temperature is 5mV s-1At a scanning speed of 782mF cm in capacitance-2And 683F g-1
Example 4:
the detailed process of the high-conductivity stretchable elastic cloth comprises the following steps:
(1) surface modification of elastic cloth: the method comprises the steps of using polyester fibers as a base material, respectively cleaning the surface of cloth by using acetone, deionized water and alcohol, then placing the cloth in a surface modification solution 1 to soak for 1-2 hours at normal temperature, taking out the cloth, transferring the cloth to a surface modification solution 2, and soaking the cloth for 1-2 hours at 85 ℃. The surface modification solution 1 adopts an alcohol solution containing 20 percent of vinyl trimethoxy silane by volume fraction; the surface modification solution 2 adopts a method that potassium persulfate of 60mg/100mL solution is added into an aqueous solution containing 20% volume fraction of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride. Taking out and washing with alcohol and deionized water to complete the modification.
(2) Chemical nickel plating elastic cloth: soaking the surface-modified polyester fiber cloth into an activating solution for 15-30 minutes, taking out, cleaning with deionized water, then placing into a chemical nickel plating solution, reacting for 30 minutes at 40 ℃, taking out, cleaning with deionized water, and drying. The activating solution adopts an ammonium chloropalladate aqueous solution containing 5 mM; the electroless nickel plating solution comprises a solution A and a solution B, wherein the solution A comprises 50g L-1Nickel sulfate pentahydrate, 25g L-112.5g L sodium citrate-1The lactic acid of (a); and liquid B comprises 5g L-1Dimethylamine borane.
(3) Preparing nickel-molybdenum-phosphorus coated nickel-plated elastic cloth: the prepared nickel plating elasticity is arranged in the nickel-molybdenum-phosphorus plating solution, reacts for 15 minutes at the temperature of 98 ℃, is taken out, washed and dried to obtain the final high-conductivity stretchable fiber fabric energy storageAnd an electrode. The nickel-molybdenum-phosphorus plating solution comprises 35g L-10.06g L of nickel sulfate-1Sodium molybdate, 10g L-1Sodium hypophosphite, 85g L-1Sodium citrate, 50g L-1Ammonium chloride and 60mL L-1Ammonia water.
The nickel-molybdenum-phosphorus coated nickel-plated elastic cloth is subjected to electrical property test by a four-probe electrical tester. The stability is excellent, and the resistance can be kept stable for more than 10 days at normal temperature, and can also be kept stable for more than 100 minutes at 80 ℃. The square resistance of the alloy is 0.5 omega □-1Conductivity of 253S cm-1. In the electrochemical test of the nickel-molybdenum-phosphorus coated nickel-plated elastic cloth, the temperature is 5mV s-1At a sweep rate of 1282mF cm in capacitance-2And 983F g-1
Example 5:
the detailed process of the high-conductivity stretchable elastic cloth comprises the following steps:
(1) surface modification of elastic cloth: the method comprises the steps of using polyester fibers as a base material, respectively cleaning the surface of cloth by using acetone, deionized water and alcohol, then placing the cloth in a surface modification solution 1 to soak for 1-2 hours at normal temperature, taking out the cloth, transferring the cloth to a surface modification solution 2, and soaking the cloth for 1-2 hours at 85 ℃. The surface modification solution 1 adopts an alcohol solution containing 20 percent of vinyl trimethoxy silane by volume fraction; the surface modification solution 2 adopts a method that potassium persulfate of 60mg/100mL solution is added into an aqueous solution containing 20% volume fraction of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride. Taking out and washing with alcohol and deionized water to complete the modification.
(2) Chemical nickel plating elastic cloth: soaking the surface-modified polyester fiber cloth into an activating solution for 15-30 minutes, taking out, cleaning with deionized water, then placing into a chemical nickel plating solution, reacting for 30 minutes at 40 ℃, taking out, cleaning with deionized water, and drying. The activating solution adopts an ammonium chloropalladate aqueous solution containing 5 mM; the electroless nickel plating solution comprises a solution A and a solution B, wherein the solution A comprises 50g L-1Nickel sulfate pentahydrate, 25g L-112.5g L sodium citrate-1The lactic acid of (a); and liquid B comprises 5g L-1Dimethylamine borane.
(3) Preparing nickel-copper-boron coated nickel-plated elastic cloth: and (3) arranging the prepared nickel plating elasticity in a nickel-copper-boron plating solution, reacting for 15 minutes at 35 ℃, taking out, cleaning and drying to obtain the final high-conductivity stretchable fiber fabric energy storage electrode. The nickel-copper-boron plating solution comprises 25.8g L-12.85g L-1Copper sulfate, 1g L-1Dimethylamine borane and 160mL L-1The aqueous ammonia of (1).
The nickel-copper-boron coated nickel-plated elastic cloth is subjected to electrical property test by a four-probe electrical tester. The stability is excellent, and the resistance can be kept stable for more than 10 days at normal temperature, and can also be kept stable for more than 80 minutes at 80 ℃. The square resistance of the alloy is 0.1 omega □-1Conductivity of 646S cm-1. In the electrochemical test of the nickel-copper-boron coated nickel-plated elastic cloth, the temperature is 5mV s-1At a sweeping speed of 865mF cm in capacitance-2And 790F g-1
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A stretchable fiber fabric supercapacitor is characterized by comprising an alloy coating layer coated metal coating elastic cloth, an electrolyte and diaphragm layer, and a carbon nanotube modified alloy coating layer coated metal coating elastic cloth;
the alloy coating layer is coated with metal coating elastic cloth to be a positive electrode;
the metal coating elastic cloth coated by the carbon nano tube modified alloy coating is taken as a negative electrode;
the electrolyte and the diaphragm layer are stretchable high-molecular hydrogel and are positioned between the positive electrode and the negative electrode;
the elastic cloth with the elastic layer is modified by utilizing a macromolecule grafting process, the modified elastic cloth is soaked in an activating solution, and then the elastic cloth is placed in a chemical gold-plating solution to react to obtain the elastic cloth with the metal coating.
2. The stretchable fiber fabric supercapacitor according to claim 1, wherein the alloy coating is wrapped by metal-coated elastic cloth and comprises the alloy coating, the metal coating and the elastic cloth.
3. The stretchable fiber fabric supercapacitor according to claim 2, wherein the alloy coating is an alloy material with high conductivity, stability and energy storage characteristics, and is one of nickel cobalt phosphorus, nickel cobalt boron, nickel molybdenum phosphorus and nickel copper boron.
4. The stretchable fabric supercapacitor according to claim 2, wherein the metal coating is a metal material capable of undergoing further catalytic and electroless plating reactions, in particular one of nickel, copper and cobalt.
5. The stretchable fiber fabric supercapacitor according to claim 2, wherein the elastic fabric is a fiber fabric capable of being stretched to a certain extent, and is particularly one of spandex fibers and polyester fibers.
6. The stretchable fiber fabric supercapacitor according to claim 1, wherein the carbon nanotube modified alloy coated metal coated elastic fabric is obtained by soaking the alloy coated metal coated elastic fabric in carbon nanotube slurry, and drying and then circularly soaking.
7. The stretchable fiber fabric supercapacitor according to claim 1, wherein the electrolyte and separator layer is a stretchable polymer hydrogel with hydrogen bonding effect, specifically one of polyvinyl alcohol hydrogel, polyacrylamide hydrogel and polyacrylic acid hydrogel.
8. A stretchable fiber fabric supercapacitor preparation method is characterized by comprising the following steps:
preparing elastic cloth: modifying the elastic cloth by utilizing a macromolecule grafting process to obtain the elastic cloth;
preparing metal coating elastic cloth: soaking the elastic cloth in an activating solution, and then placing the elastic cloth in a chemical plating metal solution for reaction to obtain the elastic cloth;
preparing the alloy coating layer coated metal coating elastic cloth: the metal coating is elastically arranged in the chemical plating alloy plating solution to react to obtain the alloy plating solution;
preparing the carbon nano tube modified alloy coating layer coated metal coating layer elastic cloth: soaking the alloy coating layer coated metal coating layer elastic cloth in carbon nano tube slurry, drying and then circularly soaking to obtain the carbon nano tube elastic cloth;
preparing an electrolyte and a diaphragm layer: polymerizing to prepare a stretchable hydrogel electrolyte carrier and a diaphragm, and adsorbing a sufficient amount of electrolyte solution.
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