CN115410836A - Integrally-formed hydrogel solid-state supercapacitor and preparation method thereof - Google Patents
Integrally-formed hydrogel solid-state supercapacitor and preparation method thereof Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
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- C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an integrally formed hydrogel solid-state supercapacitor and a preparation method thereof. The method comprises the following steps: uniformly mixing porous carbon, multi-walled carbon nanotubes and polytetrafluoroethylene suspension, weighing two parts of active substances with the same mass, repeatedly pressing the active substances on two glass plates to form a film, drying the film, and standing the film for later use; dissolving sodium hydroxide in deoxygenated deionized water, adding lithium chloride and acrylic acid, uniformly stirring, adding a cross-linking agent, an initiator and an accelerator into ice water bath, and uniformly stirring to obtain a reaction solution; and assembling the glass plates into a closed mold, injecting the reaction liquid into the glass mold, ultrasonically removing bubbles, and then placing the glass mold into a thermostat for polymerization reaction to obtain the integrally formed hydrogel solid-state supercapacitor. The integrally-formed hydrogel solid supercapacitor provided by the invention can be charged and discharged under ultrahigh current density, has lower contact resistance and voltage drop, and is excellent in freezing resistance and mechanical property.
Description
Technical Field
The invention belongs to the field of preparation of double-layer hydrogel solid-state supercapacitor materials, and particularly relates to an integrally-formed hydrogel solid-state supercapacitor and a preparation method thereof.
Background
Hydrogel materials have a three-dimensional network structure, the network of which is generally formed by crosslinking through chemical or physical action, and are typical representatives of soft, flexible materials. The hydrogel has the advantages of simple preparation process, multiple functions, better mechanical property and good biocompatibility, and has wide application prospects in the fields of flexible wearability, flexible robots, new energy, medical treatment and the like.
Currently, the international energy situation is nervous, and meanwhile, in order to respond to the national call for vigorously developing new energy, the development of a novel energy material becomes one of the current research hotspots. The super capacitor gradually enters the sight of people by virtue of high charge-discharge efficiency, super-power charge-discharge, long cycle life, greenness and safety.
Hydrogel solid-state supercapacitors are one of the research hotspots of the current supercapacitors. Compared with the traditional super capacitor, the structure of the super capacitor is a simpler sandwich structure: the electrode-hydrogel solid electrolyte-electrode saves the traditional diaphragm layer; meanwhile, the hydrogel-based supercapacitor has certain flexibility and can be stretched or bent. Therefore, a larger specific capacitance can be obtained by designing a special structure such as a fold, and the specific capacitance of the folded structural type supercapacitor reported in the prior literature can reach 182mF/cm 2 (Nature Communications,2019, 10, 536). However, there are still many problems with current hydrogel-based solid-state supercapacitorsBecause the capacitor is generally assembled by three layers of materials in a sticking mode, for example, the adhesive force between a gel layer and an electrode layer is limited, and the contact is poor, so that the contact resistance is large, cracking and falling between the layers can occur even after long-time use, the voltage drop of transverse current charging and discharging is overlarge, and the charging and discharging under the heavy current density and the cycle service life are limited, wherein the charging and discharging density of the hydrogel supercapacitor prepared by adopting the assembling mode reported in the prior document is 2mA/cm 2 The voltage drop is 0.1V (Chemical Engineering Journal,2021, 425, 131505); meanwhile, the hydrogel-based supercapacitor has poor performance at low temperature due to the fact that hydrogel contains a large amount of water, specific capacity is greatly reduced, and the hydrogel cannot be normally used, so that practical application of the hydrogel solid-state supercapacitor is greatly restricted, for example, in patent application, a preparation technology of the antifreeze hydrogel supercapacitor based on the antifreeze hydrogel electrolyte and the preparation method thereof adopts a step-by-step assembly process of three layers of electrodes, gel and electrode to prepare the supercapacitor, and the specific capacitance of the antifreeze hydrogel electrolyte supercapacitor at 25 ℃ is 32.7mF/cm 2 ～110.2mF/cm 2 And a specific capacitance at-20 ℃ of 36.9mF/cm 2 。
Therefore, how to prepare the super capacitor with low contact resistance, low voltage drop and frost resistance has important significance for the field of flexible energy storage.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an integrally formed hydrogel solid-state supercapacitor and a preparation method thereof, and particularly relates to an integrally formed flexible hydrogel solid-state supercapacitor and a preparation method thereof.
The hydrogel solid-state supercapacitor provided by the invention is an integrated hydrogel solid-state supercapacitor which is formed in situ through polymerization and does not need to be assembled, has lower contact impedance and voltage drop, and can realize charging and discharging under high current density; the polyelectrolyte hydrogel is used as the solid electrolyte, so that the supercapacitor has high conductivity, and the supercapacitor is endowed with the characteristic of flexibility and stretchability, and has a huge application prospect in the field of flexible energy storage.
The integrated high-capacity anti-freezing hydrogel solid-state supercapacitor provided by the invention uses a polyelectrolyte system, uses inorganic salt as a carrier, has high area specific capacity, excellent anti-freezing performance and high specific capacitance, and can still normally work at-40 ℃.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of an integrally formed hydrogel solid-state supercapacitor, which comprises the following steps:
(1) Weighing a proper amount of porous carbon, multi-walled carbon nanotubes and polytetrafluoroethylene suspension, adding a proper amount of ethanol solution, and uniformly mixing and stirring to obtain a raw material 1;
(2) Dividing the raw material 1 in the step (1) into two parts, respectively transferring the two parts to two glass plates, repeatedly pressing a roller to form a film, and then drying to obtain the glass plate coated with an active substance film;
(3) Adding sodium hydroxide into water, uniformly stirring to obtain a solution 1, adding lithium chloride and acrylic acid into the solution 1, uniformly stirring, and cooling to obtain a solution 2;
(4) Placing the solution 2 in the step (3) in an ice water bath, then adding a cross-linking agent, an initiator and an accelerator to obtain a final reaction solution, and carrying out ultrasonic treatment on the reaction solution to remove bubbles;
(5) Assembling a sealed mold by sandwiching a gasket between the two glass plates coated with the active material film in the step (2), wherein one side coated with the active material film faces inwards, injecting the reaction solution in the step (4) into the mold, and then ultrasonically treating the mold to remove bubbles;
(6) And (4) placing the mould filled with the reaction liquid in the step (5) into a thermostat for polymerization reaction, after the reaction is finished, tightly combining an active substance film coated on a glass plate with hydrogel obtained by the polymerization reaction to form a sandwich structure, and opening the mould to obtain the integrally formed hydrogel solid-state supercapacitor formed by the active substance film and the hydrogel.
Further, in the step (1), the mass of the porous carbon is 10% -80% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension, the mass of the multi-walled carbon nanotube is 10% -80% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension, the mass of the polytetrafluoroethylene suspension is 5% -10% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension, the solid content of polytetrafluoroethylene in the polytetrafluoroethylene suspension is 60%, the polytetrafluoroethylene suspension is a water dispersion of polytetrafluoroethylene particles, and the using amount of an ethanol solution is 3-10mL.
Further, in the step (2), the raw material 1 is divided into two parts according to the mass ratio of 1: 1, so that the loading capacity of the active substances of the two glass plates is 1: 1; the drying is drying in an oven, the drying time is 3-6 h, and the drying time is 60-80 ℃.
Further, the ratio of the amount of the substance added with the inorganic salt lithium chloride to the total volume of the added water and the acrylic acid is 0.5mol/L to 2.5mol/L, the ratio of the amount of the substance added with the sodium hydroxide to the total volume of the added water and the acrylic acid is 1mol/L to 4mol/L, the ratio of the amount of the substance added with the acrylic acid to the total volume of the added water and the acrylic acid is 1mol/L to 4mol/L, and the molar ratio of the sodium hydroxide to the acrylic acid is 1: 1.
Further, the cross-linking agent in the step (4) is N, N' -methylene-bis-acrylamide, and the amount of the cross-linking agent is 0.01-0.15% of that of acrylic acid.
Further, the initiator in the step (4) is potassium persulfate, and the mass amount of the initiator is 0.1-0.5% of that of the acrylic acid.
Further, the accelerator in the step (4) is N, N, N ', N' -tetramethylethylenediamine, and the amount of the accelerator is 0.1-1% of the amount of the acrylic acid.
Further, the time for ultrasonically removing bubbles of the glass mold filled with the reaction liquid in the step (5) is 2 min-10 min.
Further, the temperature of the constant temperature box in the step (6) is 10-40 ℃, and the time of polymerization reaction is 1-6 h.
The invention provides an integrally formed hydrogel solid-state supercapacitor prepared by the preparation method.
The integrally formed hydrogel solid-state supercapacitor can realize charging and discharging (40 mA/cm) under high current density 2 ) The activated carbon layer is tightly contacted with the gel layer, so that the activated carbon layer has lower contact resistance and voltage drop, has excellent anti-freezing performance, can normally work at the temperature of minus 40 ℃, has higher specific capacitance and excellent flexibility, and does not change the bending specific capacity of 0-180 degrees.
The preparation method provided by the invention abandons the traditional method of preparing a solid super capacitor with a sandwich structure by a pasting method, creatively pre-coats an active substance film on glass, and enables the hydrogel solid electrolyte to be tightly combined with the active substance film as an electrode layer through the in-situ polymerization reaction of hydrogel, so as to realize integrated molding, so that the electrode layer and the hydrogel layer are firmly combined without a gap (as shown in figure 1); meanwhile, polyelectrolyte gel and lithium chloride are used as raw materials, so that the gel has high conductivity and excellent anti-freezing performance, the electric performance of the super capacitor is improved, and the working temperature range of the super capacitor is widened.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the integrally formed high-capacity anti-freezing hydrogel solid-state supercapacitor provided by the invention abandons the traditional method of pasting, creatively uses an in-situ polymerization integrally forming process, improves the fatal defect of large contact resistance caused by poor direct contact between an electrode layer and a gel layer, and can obtain the integrated supercapacitor with higher specific capacitance (up to 210 mF/cm) without fold structural design 2 ) Can realize the large current density of 40mA/cm 2 The charge and discharge are 20 times of those reported previously, and simultaneously have lower voltage drop (2 mA/cm) 2 The next only 0.01V) was 1/10 of that previously reported.
(2) The integrally formed hydrogel solid-state supercapacitor with high capacity and frost resistance creatively uses the polyelectrolyte monomer (sodium acrylate), the sodium acrylate monomer is prepared by neutralization reaction of sodium hydroxide and acrylic acid and is used for synthesizing sodium polyacrylate hydrogel, the integrally formed hydrogel solid-state supercapacitor has excellent low temperature resistance and can still normally work in an environment of-40 ℃, the coulombic efficiency is high, and compared with the traditional frost-resistant organic gel solid-state supercapacitor, the integrally formed hydrogel solid-state supercapacitor is more green and safe, and the flammable and explosive risks are lower.
(3) Compared with the traditional supercapacitor, the integrally formed hydrogel solid-state supercapacitor with high capacity and freeze resistance has better flexibility, the specific capacitance of the capacitor is basically not changed under the condition that the bending angle is 0-180 degrees, and the integrally formed hydrogel solid-state supercapacitor has great application prospect in the field of flexible energy storage.
Drawings
Fig. 1 is a scanning electron microscope photograph of the integrally formed hydrogel solid-state supercapacitor prepared in example 1.
FIG. 2 is a constant current charging and discharging curve diagram of the integrally formed hydrogel solid-state supercapacitor prepared in example 1 at different current densities.
Fig. 3 is a cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 1 at different temperatures.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below in particular detail are those that can be implemented or understood by those skilled in the art in light of the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The invention is further described below with reference to examples of implementation. The electrical properties of the hydrogel solid supercapacitors obtained in the examples were determined using the test methods disclosed in the Roman et al ACS appl. Mater. Interfaces 2021, 13, 48030-48039 references, which are intended to illustrate the invention and not to limit the scope of the invention.
Example 1
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 1 shows a good rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.014V, the contact impedance is 3.5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 65mF/cm 2 The coulombic efficiency is 93.9 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Fig. 1 is a scanning electron microscope photograph of the integrally formed hydrogel solid-state supercapacitor prepared in example 1, and it can be seen from fig. 1 that the hydrogel layer and the electrode layer of the integrally formed hydrogel solid-state supercapacitor are in close contact without a gap therebetween, which is beneficial to greatly reduce the contact impedance of the supercapacitor and improve the specific capacitance thereof; meanwhile, the risk that the super capacitor is cracked after deformation in the working process is avoided.
FIG. 2 shows the integrated hydrogel solid-state supercapacitor prepared in example 1 at different current densities (2 mA/cm) 2 、4mA/cm 2 、8mA/cm 2 、10mA/cm 2 、12mA/cm 2 、15mA/cm 2 、20mA/cm 2 、40mA/cm 2 ) The constant current charging and discharging curve shows that the integrally formed hydrogel solid-state supercapacitor is symmetrically triangular in charging and discharging and has small voltage drop at 2mA/cm according to the figure 2 2 The voltage drop is 0.014V, the voltage drop is improved along with the increase of the current density, but the charging and discharging curve is still maintained in a symmetrical triangular shape, and the current density is 40mA/cm at an overlarge value 2 The hydrogel super solid-state capacitor prepared by the preparation method provided by the invention has excellent charge and discharge performance.
Fig. 3 is a cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 1 at different temperatures (20 ℃,10 ℃,0 ℃, -10 ℃, -20 ℃, -30 ℃, -40 ℃), and it can be seen from fig. 3 that at 20 ℃, the cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor is in a regular rectangular-like shape, the coulombic efficiency is that the charge-discharge efficiency is 99%, and the charge-discharge efficiency is reduced with the temperature reduction, but even under the extreme low temperature condition of-40 ℃, the cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor still presents a regular rectangular-like shape, and the charge-discharge efficiency is more than 90%.
Example 2
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 3mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 60 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 2 is better like a rectangle, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.013V, the contact impedance is 3.2 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 69mF/cm 2 The coulombic efficiency is 94 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 3
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 8mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into an oven at 80 ℃ for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 3 shows a good rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.011V, the contact impedance is 3.0 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 68mF/cm 2 The coulombic efficiency is 93.1 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 4
Respectively weighing 0.1677g of activated carbon, 1.3416g of multi-walled carbon nanotubes and 0.1677g of polytetrafluoroethylene suspension, adding 10mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 4 shows a good rectangular-like shape, and the specific capacitance is 80mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.01V, the contact impedance is 0.5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 70mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 5
Respectively weighing 0.3354g of activated carbon, 1.1739g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 5 shows betterQuasi-rectangular shape with specific capacitance of 100mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.012V, the contact impedance is 0.9 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 70mF/cm 2 The coulombic efficiency is 93.3 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 6
Respectively weighing 0.5031g of activated carbon, 1.0062g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 3mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, and repeatedly rolling to uniformly mix the two parts to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 6 shows a better rectangular-like shape, and the specific capacitance is 120mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.013V, the contact impedance is 1.3 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 66mF/cm 2 The coulombic efficiency is 94 percent, and the high-current density of 40mA/cm can be realized 2 Charging and discharging at 180 deg.C, repeatedly bending for 20 times, and constant current charging and discharging curveStill present a similar triangle, the specific capacitance does not change.
Example 7
Respectively weighing 0.6708g of active carbon, 0.8385g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, and repeatedly rolling to uniformly mix the two parts to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 7 shows a better rectangular-like shape, and the specific capacitance is 145mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.0135V, the contact impedance is 1.7 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 67mF/cm 2 The coulombic efficiency is 93.5 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 8
Respectively weighing 0.8385g of activated carbon, 0.6708g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 8mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 8 is better like a rectangle, and the specific capacitance is 155mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.014V, the contact impedance is 2.1 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 66mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 9
Respectively weighing 1.0062g of active carbon, 0.5031g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, and repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 9 shows a better rectangular-like shape, and the specific capacitance is 175mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.014V, the contact impedance is 2.6 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 68mF/cm 2 The coulombic efficiency is 93.7 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 10
Respectively weighing 1.1739g of active carbon, 0.3354g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, and repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 10 is better like a rectangle, and the specific capacitance is 195mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.014V, the contact impedance is 2.9 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 65mF/cm 2 The coulombic efficiency is 93 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 11
Respectively weighing 1.6770g of active carbon, 1.5093g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
EXAMPLE 11 preparation ofThe cyclic voltammogram of the prepared integrally-formed hydrogel solid-state supercapacitor is better like a rectangle, and the specific capacitance is 205mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.012V, the contact impedance is 3.0 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 65.8mF/cm 2 The coulombic efficiency is 94.3 percent, and the high-current density of 40mA/cm can be realized 2 And (3) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a triangular shape, but slightly deviates, and the specific capacitance basically does not change.
Example 12
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 10mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 3h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 12 is better like a rectangle, and the specific capacitance is 180mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.011V, the contact impedance is 3.5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 65mF/cm 2 Coulombic efficiency of 93.5 percent, and can realize the large current density of 40mA/cm 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 13
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 4h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 13 showed a better rectangular-like shape, and the specific capacitance was 190mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.0146V, the contact impedance is 3.3 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 60mF/cm 2 The coulombic efficiency is 93.9 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 14
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-wall carbon nano-tube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 5h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 14 shows a better rectangular-like shape, and the specific capacitance is 200mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.0146V, the contact impedance is 3.5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 63.5mF/cm 2 The coulombic efficiency is 93 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 15
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-wall carbon nano-tube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.2119g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 15 shows a better rectangular-like shape, and the specific capacitance is 135mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.03V, the contact impedance is 6 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 62mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 16
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.4239g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 16 is better like a rectangle, and the specific capacitance is 165mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.024V, the contact impedance is 5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 55mF/cm 2 The coulombic efficiency is 93.2 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 17
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.6357g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 17 shows a better rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.02V, the contact impedance is 4.5 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 63mF/cm 2 The coulombic efficiency is 93.2 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 18
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 1.0595g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 18 shows a better rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.015V, contactImpedance of 3.5 omega, coulombic efficiency of 99 percent, and specific capacitance of 67mF/cm at minus 40 DEG C 2 The coulombic efficiency is 92.8 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 19
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 0.4g of sodium hydroxide, dissolving the sodium hydroxide in 9.31mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 0.69mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 1.54mg of N, N ' -methylenebisacrylamide, 6.75mg of potassium persulfate and 9 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 19 showed a better rectangular-like shape, and the specific capacitance was 180mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.023V, the contact impedance is 4.6 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 60mF/cm 2 The coulombic efficiency is 93.5 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 20
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 0.8g of sodium hydroxide, dissolving the sodium hydroxide in 8.63mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 1.37mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 3.08mg of N, N ' -methylenebisacrylamide, 13.5mg of potassium persulfate and 19 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 20 shows a better rectangular-like shape, and the specific capacitance is 190mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.02V, the contact impedance is 4 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 60mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 21
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.2g of sodium hydroxide, dissolving the sodium hydroxide in 7.94mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.06mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 4.62mg of N, N ' -methylene bisacrylamide, 20.3mg of potassium persulfate and 29 μ L of N, N, N ', N ' -tetramethyl ethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 21 shows a better rectangular-like shape, and the specific capacitance is 200mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.018V, the contact impedance is 3.8 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 61mF/cm 2 The coulombic efficiency is 92.9 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance is not changed.
Example 22
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 0.62mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 22 shows a better rectangular-like shape, and the specific capacitance is 200mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.01V, the contact impedance is 3.3 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 61mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 And (3) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a triangle shape, but slightly deviates, and the specific capacitance slightly changes.
Example 23
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-wall carbon nano-tube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 9.24mg of N, N ' -methylene bisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethyl ethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between the two prepared glass plates loaded with the active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting the reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 23 showed a better rectangular-like shape, and the specific capacitance was 190mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.01V, the contact impedance is 3.2 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 63mF/cm 2 The coulombic efficiency is 94 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 24
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 10.8mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 24 showed betterQuasi-rectangular shape with specific capacitance of 190mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.022V, the contact impedance is 4.1 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 66mF/cm 2 The coulombic efficiency is 93.1 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance is slightly changed.
Example 25
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-wall carbon nano-tube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 54mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 40 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 25 showed a better rectangular-like shape, and the specific capacitance was 200mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.023V, the contact impedance is 4.3 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 61mF/cm 2 The coulombic efficiency is 92 percent, and the high-current density of 40mA/cm can be realized 2 Charging and discharging at 180 deg.C, repeatedly bending for 20 times, and constant current charging and discharging curveStill presents a similar triangle, and the specific capacitance does not change.
Example 26
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 6 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 40 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 1 hour.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 26 showed a better rectangular-like shape, and the specific capacitance was 195mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.01V, the contact impedance is 3.0 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 61mF/cm 2 The coulombic efficiency is 93.6 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangle, and the specific capacitance slightly changes.
Example 27
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 60 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 6 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 27 showed a better rectangular-like shape, and the specific capacitance was 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.012V, the contact impedance is 3.15 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 61.6mF/cm 2 The coulombic efficiency is 93.3 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 28
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 2min; and finally, putting the mould filled with the reaction liquid into a thermostat at 25 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 28 showed a better rectangular-like shape, and the specific capacitance was 180mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.032V, the contact impedance is 5.6 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 55mF/cm 2 The coulombic efficiency is 92.3 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 29
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a closed die by clamping a gasket between two prepared glass plates loaded with active substance films, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction liquid into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 10min; and finally, putting the mould filled with the reaction liquid into a 10 ℃ thermostat for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid-state supercapacitor prepared in example 29 shows a better rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.01V, the contact impedance is 3.45 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 68mF/cm 2 The coulombic efficiency is 94.1 percent, and the high-current density of 40mA/cm can be realized 2 And (4) performing charge and discharge, repeatedly bending for 20 times at 180 degrees, wherein the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 30
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling, and uniformly mixing to form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and stirring and mixing uniformly to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a 30 ℃ thermostat for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 1 hour.
Practice ofThe cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 30 shows a better rectangular-like shape, and the specific capacitance is 180mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.032V, the contact impedance is 4.8 omega, the coulombic efficiency is 99 percent, and the specific capacitance at minus 40 ℃ is 61mF/cm 2 The coulombic efficiency is 92.5 percent, and the high-current density of 40mA/cm can be realized 2 The constant current charging and discharging curve shows a slightly shifted triangular shape and the specific capacitance is slightly reduced after charging and discharging are carried out, and the constant current charging and discharging curve is repeatedly bent for 20 times at 180 degrees.
Example 31
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-wall carbon nano-tube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, uniformly mixing and stirring, uniformly dividing into two parts, respectively transferring to two glass plates, repeatedly rolling to uniformly mix and form a film; then putting the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6h, and standing for later use; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; assembling a gasket between the two prepared glass plates loaded with the active substance films to form a closed die, wherein one surface loaded with the active substance films faces inwards, then injecting a reaction solution into the die, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; and finally, putting the mould filled with the reaction liquid into a thermostat at 40 ℃ for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid-state supercapacitor after 6 hours.
The cyclic voltammetry curve of the integrally formed hydrogel solid-state supercapacitor prepared in example 31 shows a better rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.014V, the contact impedance is 3.15 omega, the coulombic efficiency is 99 percent, and the specific capacitance at-40 ℃ is 65.9mF/cm 2 Coulombic efficiency of 93.2%, canTo realize a high current density of 40mA/cm 2 And (4) performing charging and discharging, repeatedly bending for 20 times at 180 degrees, wherein the constant current charging and discharging curve still presents a similar triangular shape, and the specific capacitance does not change.
Comparative example 1 (preparation of solid-state supercapacitor by stepwise preparation of electrode layer and hydrogel layer, respectively, and subsequent Assembly by paste method)
Respectively weighing 1.3421g of active carbon, 0.1674g of multi-walled carbon nanotube and 0.1677g of polytetrafluoroethylene suspension, adding 5mL of absolute ethyl alcohol, mixing and stirring uniformly, repeatedly rolling, and uniformly mixing to form an active substance film; then putting the active substance membrane into a 70 ℃ oven for drying for 6h, taking out and cutting into a plurality of circular electrode plates with the diameter of 10 mm; weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 7.25mL of deoxygenated deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 2.75mL of acrylic acid into the solution 1, uniformly stirring and mixing, cooling to room temperature to obtain a solution 2, placing the solution 2 into an ice water bath, sequentially adding 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 μ L of N, N, N ', N ' -tetramethylethylenediamine, and uniformly stirring and mixing to obtain a final reaction solution; then injecting the reaction solution into a glass mold, sealing, and then carrying out ultrasonic treatment to remove bubbles for 5min; finally, putting the die filled with the reaction solution into a thermostat at 25 ℃ for free radical polymerization reaction, obtaining the final hydrogel solid electrolyte after 3 hours, and cutting the prepared hydrogel solid electrolyte into 10mm circular hydrogel solid electrolyte sheets with the thickness of 1 mm; taking out the two circular electrode plates, attaching the two circular electrode plates with the hydrogel solid electrolyte sheet with the thickness of 10mm and the circular thickness of 1mm to one piece of 10mm, and tabletting the hydrogel solid electrolyte sheet with the thickness of 1mm in the middle of the two circular electrode plates by using a 1kg weight for 5min to obtain the solid supercapacitor.
The cyclic voltammogram of the solid-state supercapacitor prepared in comparative example 1 appears like a rectangle, and the specific capacitance is only 120mF/cm 2 Current density 2mA/cm 2 The voltage drop is 0.4V, the contact impedance is 20 omega, the coulombic efficiency is 89 percent, and the specific capacitance at minus 40 ℃ is only 16mF/cm 2 The coulombic efficiency is only 75 percent, and the large current density of 40mA/cm can not be realized 2 Charging and discharging, and repeatedly bending for 180 degrees by 20 degreesSecondly, the constant current charging and discharging curve has obvious deviation, and the specific capacitance is obviously reduced.
Compared with the solid-state super capacitor prepared by the integrated forming method provided by the invention, the solid-state super capacitor prepared by respectively preparing the electrode layer and the hydrogel layer in a step-by-step manner and then assembling by the pasting method has the advantages that the specific capacity and the coulomb efficiency are greatly reduced, the voltage drop and the contact impedance are obviously increased, and the low-temperature resistance and the bending resistance are obviously reduced. Therefore, the integrated forming technology provided by the invention provides an effective method for preparing the high-performance solid-state supercapacitor.
Claims (10)
1. The preparation method of the integrally formed hydrogel solid-state supercapacitor is characterized by comprising the following steps:
(1) Weighing porous carbon, multi-walled carbon nanotubes and polytetrafluoroethylene suspension, adding an ethanol solution, and uniformly mixing and stirring to obtain a raw material 1;
(2) Dividing the raw material 1 in the step (1) into two parts, respectively transferring the two parts to two glass plates, repeatedly pressing a roller to form a film, and then drying to obtain the glass plate coated with an active substance film;
(3) Adding sodium hydroxide into water, uniformly stirring to obtain a solution 1, adding lithium chloride and acrylic acid into the solution 1, uniformly stirring, and cooling to obtain a solution 2;
(4) Placing the solution 2 in the step (3) in an ice water bath, then adding a cross-linking agent, an initiator and an accelerator to obtain a final reaction solution, and carrying out ultrasonic treatment on the reaction solution to remove bubbles;
(5) Assembling a sealing mould by sandwiching a gasket between the two glass plates coated with the active substance film in the step (2), wherein one surface coated with the active substance film faces inwards, injecting the reaction liquid in the step (4) into the mould, and then carrying out ultrasonic treatment on the mould to remove bubbles;
(6) And (3) placing the mould filled with the reaction liquid in the step (5) into a thermostat for polymerization reaction, after the reaction is finished, tightly combining an active substance film coated on a glass plate with hydrogel obtained by the polymerization reaction to form a sandwich structure, and opening the mould to obtain the integrally formed hydrogel solid-state supercapacitor formed by the active substance film and the hydrogel.
2. The method for preparing the integrally formed hydrogel solid-state supercapacitor according to claim 1, wherein the mass of the porous carbon is 10% -80% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension, the mass of the multi-walled carbon nanotube is 10% -80% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension, and the mass of the polytetrafluoroethylene suspension is 5% -10% of the total mass of the porous carbon, the multi-walled carbon nanotube and the polytetrafluoroethylene suspension.
3. The method for preparing the integrally formed hydrogel solid-state supercapacitor according to claim 1, wherein in the step (2), the drying time is 3-6 h, and the drying temperature is 60-80 ℃.
4. The method of claim 1, wherein the ratio of the amount of lithium chloride added to the total volume of water and acrylic acid added is 0.5mol/L to 2.5mol/L, the ratio of the amount of sodium hydroxide added to the total volume of water and acrylic acid added is 1mol/L to 4mol/L, and the ratio of the amount of acrylic acid added to the total volume of water and acrylic acid added is 1mol/L to 4mol/L.
5. The method for preparing an integrally formed hydrogel solid-state supercapacitor according to claim 1, wherein the crosslinking agent in the step (4) is N, N' -methylenebisacrylamide, and the amount of the crosslinking agent is 0.01% to 0.15% of the amount of the acrylic acid.
6. The method for preparing an integrally formed hydrogel solid supercapacitor according to claim 1, wherein in the step (4), the initiator is potassium persulfate, and the amount of the initiator is 0.1-0.5% of the amount of the acrylic acid.
7. The method for preparing an integrally formed hydrogel solid-state supercapacitor according to claim 1, wherein the accelerator in step (4) is N, N' -tetramethylethylenediamine, and the amount of the accelerator is 0.1% to 1% of the amount of the acrylic acid.
8. The method for preparing the integrally formed hydrogel solid-state supercapacitor according to claim 1, wherein in the step (5), the time for ultrasonically removing bubbles from the glass mold filled with the reaction liquid is 2min to 10min.
9. The method for preparing the integrally formed hydrogel solid supercapacitor according to claim 1, wherein the temperature of the incubator in the step (6) is 10 ℃ to 40 ℃, and the polymerization reaction time is 1h to 6h.
10. The integrally formed hydrogel solid-state supercapacitor prepared by the preparation method of any one of claims 1 to 9.
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