CN115410836B - Integrally formed hydrogel solid super capacitor and preparation method thereof - Google Patents

Integrally formed hydrogel solid super capacitor and preparation method thereof Download PDF

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CN115410836B
CN115410836B CN202211035189.9A CN202211035189A CN115410836B CN 115410836 B CN115410836 B CN 115410836B CN 202211035189 A CN202211035189 A CN 202211035189A CN 115410836 B CN115410836 B CN 115410836B
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integrally formed
super capacitor
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CN115410836A (en
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王涛
何哲健
袁忠和
邵楚茵
孙尉翔
童真
陈欣
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South China University of Technology SCUT
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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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    • 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
    • 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
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses an integrally formed hydrogel solid super capacitor and a preparation method thereof. The method comprises the following steps: uniformly mixing porous carbon, multi-wall carbon nano-tubes and polytetrafluoroethylene suspension, weighing two active substances with the same mass, repeatedly pressing the active substances on two glass plates to form a film, drying and standing for later use; dissolving sodium hydroxide in deoxidized deionized water, adding lithium chloride and acrylic acid, stirring uniformly, putting into an ice-water bath, adding a cross-linking agent, an initiator and an accelerator, and stirring uniformly 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 plates in an incubator for polymerization reaction to obtain the integrally formed hydrogel solid super capacitor. The integrally formed hydrogel solid super capacitor provided by the invention can be charged and discharged under the ultra-high current density, has lower contact resistance and voltage drop, and is excellent in freezing resistance and mechanical property.

Description

Integrally formed hydrogel solid super capacitor and preparation method thereof
Technical Field
The invention belongs to the field of preparation of double-layer hydrogel solid super capacitor materials, and particularly relates to an integrally formed hydrogel solid super capacitor and a preparation method thereof.
Background
Hydrogel materials have a three-dimensional network structure, the network of which is typically formed by crosslinking, either chemically or physically, and are typical of soft-matter flexible materials. The hydrogel has the advantages of simple preparation process, multifunction, good mechanical property and good biocompatibility, and has wide application prospect in the fields of flexible wearable, flexible robots, new energy sources, medical treatment and the like.
Currently, the international energy situation is tense, and meanwhile, in order to respond to the call of the state to develop new energy, the development of novel energy materials becomes one of the current research hotspots. The super capacitor gradually enters the sight of people by virtue of high charge and discharge efficiency, capability of ultra-high power charge and discharge, longer cycle life, greenness and safety.
Hydrogel solid state supercapacitors are one of the current research hotspots for supercapacitors. Compared with the traditional super capacitor, the structure is a simpler sandwich structure: the electrode-hydrogel solid electrolyte-electrode omits the traditional diaphragm layer; meanwhile, the super capacitor based on the hydrogel has certain flexibility and can be stretched or bent. Therefore, the specific capacitance can be increased by designing special structures such as folds, and the specific capacitance of the folds structural super capacitor reported in the prior literature can reach 182mF/cm 2 (Nature Communications,2019, 10, 536). However, there are still many problems in the current solid super capacitor based on hydrogel, because the capacitor is generally assembled by three layers of materials through a pasting mode, for example, the adhesive force between the gel layer and the electrode layer is limited, the contact resistance is high, cracking and falling between the layers can occur even if the capacitor is used for a long time, the voltage drop of cross flow charge and discharge is overlarge, the charge and discharge and the cycle service life under the high current density are limited, and the charge and discharge density of the hydrogel super capacitor prepared by adopting the assembling mode reported in the prior literature is 2mA/cm 2 When the voltage drops to 0.1V (Chemical Engineering Journal,2021, 425, 131505); meanwhile, the hydrogel-based supercapacitor has poor performance at low temperature due to the fact that the hydrogel contains a large amount of water, the specific capacity is extremely reduced and the supercapacitor cannot be used normally, and the practical application of the hydrogel solid supercapacitor is greatly restricted, for example, the patent application discloses an anti-freezing hydrogel supercapacitor based on the anti-freezing hydrogel electrolyte and a preparation method thereofThe preparation technology adopts three layers of electrode, gel and electrode to prepare by step-by-step assembly process, and the specific capacitance of the antifreeze hydrogel electrolyte super capacitor at 25 ℃ is 32.7mF/cm 2 ～110.2mF/cm 2 The specific capacitance at-20℃was 36.9mF/cm 2 。
Therefore, how to prepare the super capacitor with low contact resistance, low voltage drop and freezing 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 super capacitor and a preparation method thereof, in particular to an integrally formed flexible hydrogel solid super capacitor 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 by polymerization without assembly, has lower contact impedance and voltage drop, and can realize charge and discharge under high current density; the polyelectrolyte hydrogel is used as solid electrolyte, so that the super capacitor has high conductivity, and meanwhile, the flexible and stretchable characteristics of the super capacitor are also endowed, and the super capacitor has a huge application prospect in the field of flexible energy storage.
The integrated hydrogel solid super capacitor with high capacity and freezing resistance provided by the invention uses a polyelectrolyte system and inorganic salt as a carrier, has higher area specific capacity, and simultaneously has excellent freezing resistance, can still normally work at-40 ℃, and has higher specific capacitance.
The object of the invention is achieved by at least one of the following technical solutions.
The invention provides a preparation method of an integrally formed hydrogel solid super capacitor, which comprises the following steps:
(1) Weighing a proper amount of porous carbon, multi-wall carbon nano tubes 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 the two parts to form a film, and then drying the film to obtain the glass plate coated with the active substance film;
(3) Adding sodium hydroxide into water, stirring uniformly to obtain a solution 1, adding lithium chloride and acrylic acid into the solution 1, stirring uniformly, 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, carrying out ultrasonic treatment on the reaction solution, and removing bubbles;
(5) Assembling a sealing mould by sandwiching a gasket between the two glass plates coated with the active material film in the step (2), wherein one surface coated with the active material 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 die filled with the reaction liquid in the step (5) into an incubator for polymerization reaction, after the reaction is finished, tightly combining the active substance film coated on the glass plate with hydrogel obtained by the polymerization reaction to form a sandwich structure, and opening the die to obtain the integrally formed hydrogel solid super capacitor 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-wall carbon nano tube and the polytetrafluoroethylene suspension, the mass of the multi-wall carbon nano tube is 10% -80% of the total mass of the porous carbon, the multi-wall carbon nano tube and the polytetrafluoroethylene suspension, the mass of the polytetrafluoroethylene suspension is 5% -10% of the total mass of the porous carbon, the multi-wall carbon nano tube and the polytetrafluoroethylene suspension, the solid content of polytetrafluoroethylene in the polytetrafluoroethylene suspension is 60%, the polytetrafluoroethylene suspension is an aqueous dispersion of polytetrafluoroethylene particles, and the use amount of the ethanol solution is 3-10mL.
Further, in the step (2), the raw material 1 is divided into two parts in a mass ratio of 1:1 so that the active material loading of the two glass plates is 1:1; the drying is carried out in an oven, the drying time is 3-6 h, and the drying temperature 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 bisacrylamide, and the amount of the cross-linking agent substance is 0.01-0.15% of the amount of the acrylic acid substance.
Further, the initiator in the step (4) is potassium persulfate, and the amount of the initiator substance is 0.1% -0.5% of the amount of the acrylic acid substance.
Further, the accelerator in the step (4) is N, N, N ', N' -tetramethyl ethylenediamine, and the amount of the accelerator substance is 0.1% -1% of the amount of the acrylic acid substance.
Further, the time for ultrasonic bubble removal of the glass mold filled with the reaction liquid in the step (5) is 2-10 min.
Further, the temperature of the incubator in the step (6) is 10-40 ℃, and the polymerization time is 1-6 h.
The invention provides an integrally formed hydrogel solid-state supercapacitor prepared by the preparation method.
The integrally formed hydrogel solid super capacitor provided by the invention can realize charge and discharge (40 mA/cm) under high current density 2 ) The active carbon layer is tightly contacted with the gel layer, has lower contact resistance and voltage drop, has excellent freezing resistance, can normally work at the temperature of minus 40 ℃, has higher specific capacitance, has excellent flexibility, and has no change of the bending specific capacity of 0-180 degrees.
According to the preparation method provided by the invention, the traditional solid super capacitor with a sandwich structure prepared by a pasting method is abandoned, an active material film is creatively pre-coated on glass, and the hydrogel solid electrolyte is tightly combined with the active material film serving as an electrode layer through in-situ polymerization reaction of the hydrogel, so that integrated forming is realized, the electrode layer and the hydrogel layer are firmly combined, and no gap exists between the electrode layer and the hydrogel layer (as shown in figure 1); meanwhile, the polyelectrolyte gel and lithium chloride are used as raw materials, so that the gel has higher conductivity and excellent freezing resistance, and the electric performance of the supercapacitor is improved and the working temperature range of the supercapacitor is widened.
Compared with the prior art, the invention has the following advantages:
(1) The preparation method of the integrally formed hydrogel solid super capacitor with high capacity and freezing resistance provided by the invention eliminates the traditional pasting method, creatively uses an in-situ polymerization integrated 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 super capacitor with higher specific capacitance (up to 210mF/cm without carrying out fold structural design 2 ) Can realize high current density of 40mA/cm 2 The charge and discharge under the condition are 20 times of those reported before, and have lower voltage drop (2 mA/cm 2 The lower 0.01V) is 1/10 of that reported previously.
(2) The integrally formed hydrogel solid super capacitor creatively uses polyelectrolyte monomers (sodium acrylate), uses neutralization reaction of sodium hydroxide and acrylic acid to prepare sodium acrylate monomers for synthesizing sodium polyacrylate hydrogel, has excellent low-temperature resistance, can still normally work in an environment of minus 40 ℃, has higher coulomb efficiency, and is more green and safer and has lower flammable and explosive risks compared with the traditional anti-freezing organic gel solid super capacitor.
(3) Compared with the traditional supercapacitor, the integrally formed hydrogel solid supercapacitor with high capacity and freezing resistance provided by the invention has better flexibility, and the specific capacitance of the capacitor is not basically changed under the condition that the bending angle is 0-180 degrees, so that the integrally formed hydrogel solid supercapacitor has a huge application prospect in the field of flexible energy storage.
Drawings
FIG. 1 is a scanning electron micrograph of an integrally formed hydrogel solid state supercapacitor made according to example 1.
Fig. 2 is a constant current charge-discharge graph of the integrally formed hydrogel solid state supercapacitor prepared in example 1 at different current densities.
FIG. 3 is a cyclic voltammogram of an integrally formed hydrogel solid state supercapacitor made in example 1 at different temperatures.
Detailed Description
The following examples are provided to further illustrate the practice of the invention, but are not intended to limit the practice and protection of the invention. It should be noted that the following processes, if any, are specifically detailed, can be implemented or understood by those skilled in the art in light of the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
The invention is further described below in connection with examples. For the hydrogel solid state supercapacitors obtained in the examples, the electrical properties of the capacitors were measured using the test methods disclosed in the Roman et al ACS appl. Mater. Interfaces 2021, 13, 48030-48039 literature, these examples being for illustration of the invention and not for limiting the scope of the invention.
Example 1
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 1 shows a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.014V, the contact resistance was 3.5. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 65mF/cm 2 The coulomb efficiency is 93.9%, and the high current density of 40mA/cm can be realized 2 And 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 an 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, and there is no gap therebetween, which is beneficial to greatly reducing the contact resistance and improving the specific capacitance of the supercapacitor; meanwhile, the risk of cracking of the supercapacitor after deformation is avoided in the working process.
FIG. 2 is a graph showing the results of the example 1 of the integrally formed hydrogel solid state supercapacitors 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 charge-discharge curve graph can be seen from FIG. 2, the integrally formed hydrogel solid super capacitor has a symmetrical triangular shape in charge-discharge, and has small voltage drop of 2mA/cm 2 The voltage drop is 0.014V, and the voltage drop is improved along with the increase of the current density, but the charge-discharge curve is still kept in a symmetrical triangle shape, and the current density is 40mA/cm at the ultra-large current density 2 The charge and discharge can still be normally carried out, which shows that the hydrogel super solid-state capacitor obtained based on the preparation method provided by the inventionExcellent in charge and discharge performance.
Fig. 3 is a cyclic voltammogram of the integrally formed hydrogel solid super capacitor prepared in example 1 at different temperatures (20 ℃, 10 ℃, 0 ℃, -10 ℃, -20 ℃, -30 ℃, -40 ℃), and as can be seen from fig. 3, the cyclic voltammogram of the integrally formed hydrogel solid super capacitor at 20 ℃ is regular rectangular-like, the coulomb efficiency is that the charge-discharge efficiency is 99%, and the charge-discharge efficiency is reduced along with the reduction of the temperature, but even under the extremely low temperature condition of-40 ℃, the cyclic voltammogram of the integrally formed hydrogel solid super capacitor still presents regular rectangular-like, the charge-discharge efficiency is more than 90%, and the hydrogel solid super capacitor obtained based on the preparation method provided by the invention has excellent freezing resistance and can normally work under the extremely low temperature environment.
Example 2
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 3mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 60 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
Example 2 preparationThe cyclic voltammogram of the integrally formed hydrogel solid super capacitor presents a better rectangular-like shape, and the specific capacitance is 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.013V, the contact resistance was 3.2. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 69mF/cm 2 The coulomb efficiency is 94%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 3
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 8mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into an oven at 80 ℃ for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 3 exhibited a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.011V, the contact impedance is 3.0 omega, the coulomb efficiency is 99%, and the specific capacitance is 68mF/cm 2 The coulomb efficiency is 93.1%, and can realize high current densityDegree of 40mA/cm 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 4
0.1677g of active carbon, 1.3416g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 10mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two parts are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 4 exhibited a better rectangular-like shape with a specific capacitance of 80mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.01V, the contact impedance is 0.5 omega, the coulomb efficiency is 99%, and the specific capacitance is 70mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 5
Respectively weighing 0.3354g of active carbon, 1.1739g 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, and uniformly mixing to form a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 5 shows a better rectangular-like shape with a specific capacitance of 100mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.012V, the contact resistance was 0.9Ω, the coulomb efficiency was 99%, and the specific capacitance was 70mF/cm at-40 ℃ 2 The coulomb efficiency is 93.3%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 6
0.5031g of active carbon, 1.0062g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 3mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 6 shows a better rectangular-like shape with a specific capacitance of 120mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.013V, the contact resistance was 1.3. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 66mF/cm 2 The coulomb efficiency is 94%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 7
0.6708g of active carbon, 0.8385g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 7 shows a better rectangular-like shape with a specific capacitance of 145mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.0135V, the contact resistance was 1.7Ω, the coulomb efficiency was 99%, and the specific capacitance was 67mF/cm 2 The coulomb efficiency is 93.5%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 8
0.8385g of active carbon, 0.6708g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 8mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 8 shows a better rectangular-like shape with a specific capacitance of 155mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.014V, the contact resistance was 2.1. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 66mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 9
1.0062g of active carbon, 0.5031g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 9 exhibited a better rectangular-like shape with a specific capacitance of 175mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.014V, the contact resistance was 2.6Ω, the coulomb efficiency was 99%, and the temperature was-40 ℃The time specific capacitance was 68mF/cm 2 The coulomb efficiency is 93.7%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 10
1.1739g of active carbon, 0.3354g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two parts are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 10 exhibited a good rectangular-like shape with a specific capacitance of 195mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.014V, the contact resistance was 2.9Ω, the coulomb efficiency was 99%, and the specific capacitance was 65mF/cm 2 The coulomb efficiency is 93%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 11
1.6770g of active carbon, 1.5093g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 11 exhibited a better rectangular-like shape with a specific capacitance of 205mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.012V, the contact resistance was 3.0Ω, the coulomb efficiency was 99%, and the specific capacitance was 65.8mF/cm at-40 ℃ 2 The coulomb efficiency is 94.3%, and the high current density of 40mA/cm can be realized 2 The constant current charge and discharge curve still presents a triangle shape, but is slightly offset, and the specific capacitance is not changed basically.
Example 12
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 10mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 3 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 12 shows a better rectangular-like shape with a specific capacitance of 180mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.011V, the contact impedance is 3.5 omega, the coulomb efficiency is 99%, and the specific capacitance at-40 ℃ is 65mF/cm 2 The coulomb efficiency is 93.5%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 13
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 4 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 13 exhibited a better rectangular-like shape with a specific capacitance of 190mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.0146V, the contact resistance was 3.3. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 60mF/cm 2 The coulomb efficiency is 93.9%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 14
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 5 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 14 exhibited a better rectangular-like shape with a specific capacitance of 200mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.0146V, the contact resistance was 3.5. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 63.5mF/cm 2 The coulomb efficiency is 93%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 15
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.2119g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the solution is stirred and mixed uniformly, the solution is cooled to room temperature to obtain solution 2, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the final reaction solution is obtained after the solution is stirred and mixed uniformly; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 15 exhibited a better rectangular-like shape with a specific capacitance of 135mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.03V, the contact impedance is 6Ω, the coulomb efficiency is 99%, and the specific capacitance is 62mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 16
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.4239g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 16 shows a better rectangular-like shape with a specific capacitance of 165mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.024V, the contact impedance is 5 omega, the coulomb efficiency is 99%, and the specific capacitance at-40 ℃ is 55mF/cm 2 The coulomb efficiency is 93.2%, and the high current density of 40mA/cm can be realized 2 The lower charge and discharge, 180 DEG repeatedly bent for 20 times, the constant current charge and discharge curve still presents a similar triangleThe specific capacitance does not change.
Example 17
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.6357g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 17 exhibited a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.02V, the contact resistance was 4.5. OMEGA., the coulomb efficiency was 99%, and the specific capacitance was 63mF/cm 2 The coulomb efficiency is 93.2%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 18
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 1.0595g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 18 shows a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.015V, the contact resistance was 3.5. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 67mF/cm 2 The coulomb efficiency is 92.8%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 19
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; weighing 0.4g of sodium hydroxide, dissolving in 9.31mL of deoxidized 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 in an ice-water bath, sequentially adding 1.54mg of N, N ' -methylenebisacrylamide, 6.75mg of potassium persulfate and 9 mu L N of N, N ', N ' -tetramethyl ethylenediamine, stirring and mixing uniformly, and obtaining a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 19 exhibited a better rectangular-like shape with a specific capacitance of 180mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ was 0.023V, the contact resistance was 4.6Ω, the coulomb efficiency was 99%, and the specific capacitance was 60mF/cm 2 The coulomb efficiency is 93.5%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 20
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; weighing 0.8g of sodium hydroxide, dissolving in 8.63mL of deoxidized deionized water to obtain a solution 1, adding 0.8476g of lithium chloride and 1.37mL of acrylic acid into the solution 1, stirring and mixing uniformly, cooling to room temperature to obtain a solution 2, placing the solution 2 in an ice-water bath, sequentially adding 3.08mg of N, N ' -methylenebisacrylamide, 13.5mg of potassium persulfate and 19 mu L N of N, N ', N ' -tetramethyl ethylenediamine, stirring and mixing uniformly, and obtaining a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 20 exhibited a better rectangular-like shape with a specific capacitance of 190mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.02V, the contact impedance is 4Ω, the coulomb efficiency is 99%, and the specific capacitance is 60mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 21
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.2g of sodium hydroxide is weighed and dissolved in 7.94mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.06mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 4.62mg of N, N ' -methylenebisacrylamide, 20.3mg of potassium persulfate and 29 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
Integrally formed water prepared in example 21The cyclic voltammogram of the gel solid super capacitor shows a better rectangular-like shape, and the specific capacitance is 200mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.018V, the contact resistance was 3.8Ω, the coulomb efficiency was 99%, and the specific capacitance was 61mF/cm 2 The coulomb efficiency is 92.9%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 22
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 0.62mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 22 exhibited a better rectangular-like shape with a specific capacitance of 200mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.01V, the contact resistance was 3.3. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 61mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 The constant current charge and discharge curve still presents triangle shape, but slightly shifts and the specific capacitance slightly changes after 180 degrees of repeated bending for 20 times.
Example 23
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 9.24mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 23 shows a better rectangular-like shape with a specific capacitance of 190mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.01V, the contact resistance was 3.2. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 63mF/cm 2 The coulomb efficiency is 94%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 24
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 10.8mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 24 shows a better rectangular-like shape with a specific capacitance of 190mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40 ℃ is 0.022V, the contact impedance is 4.1 omega, the coulomb efficiency is 99%, and the specific capacitance at-40 ℃ is 66mF/cm 2 The coulomb efficiency is 93.1%, and the high current density of 40mA/cm can be realized 2 The constant current charge and discharge curve still presents a similar triangle shape after repeated bending for 20 times at 180 degrees, and the specific capacitance is slightly changed.
Example 25
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 54mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die filled with the reaction liquid into a 40 ℃ incubator for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 25 exhibited a better rectangular-like shape with a specific capacitance of 200mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.023V, the contact resistance was 4.3Ω, the coulomb efficiency was 99%, and the specific capacitance was 61mF/cm 2 The coulomb efficiency is 92%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 26
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 6 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die filled with the reaction liquid into a 40 ℃ incubator for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid super capacitor after 1 h.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 26 shows a better rectangular-like shape with a specific capacitance of 195mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.01V, the contact resistance was 3.0Ω, the coulomb efficiency was 99%, and the specific capacitance was 61mF/cm 2 The coulomb efficiency is 93.6%, and the high current density of 40mA/cm can be realized 2 The constant current charge and discharge curve still presents a similar triangle shape with slightly changed specific capacitance after repeated bending for 20 times at 180 degrees.
Example 27
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 60 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die 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 super capacitor after 6 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 27 exhibited a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.012V, the contact resistance was 3.15. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 61.6mF/cm at-40 ℃ 2 The coulomb efficiency is 93.3%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 28
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 2min; and finally, placing the die 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 super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 28 shows a better rectangular-like shape with a specific capacitance of 180mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.032V, the contact resistance was 5.6Ω, the coulomb efficiency was 99%, and the temperature was-40 ℃Specific capacitance of 55mF/cm 2 The coulomb efficiency is 92.3%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 29
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 10min; and finally, placing the die filled with the reaction liquid into a 10 ℃ incubator for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid super capacitor after 3 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 29 exhibited a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.01V, the contact resistance was 3.45. OMEGA, the coulomb efficiency was 99%, and the specific capacitance was 68mF/cm 2 The coulomb efficiency is 94.1%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle, and the specific capacitance does not change.
Example 30
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die filled with the reaction liquid into a 30 ℃ incubator for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid super capacitor after 1 h.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 30 exhibited a better rectangular-like shape with a specific capacitance of 180mF/cm 2 Current density 2mA/cm 2 The voltage drop was 0.032V, the contact resistance was 4.8Ω, the coulomb efficiency was 99%, and the specific capacitance was 61mF/cm at-40 ℃ 2 The coulomb efficiency is 92.5%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve shows a slightly offset triangle shape, and the specific capacitance is slightly reduced.
Example 31
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being uniformly mixed and stirred, the mixture is divided into two parts and respectively transferred to two glass plates, and the two glass plates are repeatedly rolled to be uniformly mixed and formed into a film; then placing the glass plate attached with the active substance film into a 70 ℃ oven for drying for 6 hours, and placing for standby; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; a gasket is clamped between the two glass plates with the active substance film to assemble a closed mould, one surface with the active substance film is inwards arranged, then the reaction liquid is injected into the mould to seal, and then ultrasonic treatment is carried out to remove bubbles for 5min; and finally, placing the die filled with the reaction liquid into a 40 ℃ incubator for free radical polymerization reaction, and obtaining the final integrally formed hydrogel solid super capacitor after 6 hours.
The cyclic voltammogram of the integrally formed hydrogel solid state supercapacitor prepared in example 31 exhibited a better rectangular-like shape with a specific capacitance of 210mF/cm 2 Current density 2mA/cm 2 The voltage drop at-40℃was 0.014V, the contact resistance was 3.15. OMEGA, the coulomb efficiency was 99%, and the specific capacitance at-40℃was 65.9mF/cm 2 The coulomb efficiency is 93.2%, and the high current density of 40mA/cm can be realized 2 And the constant current charge and discharge curve still presents a similar triangle shape, and the specific capacitance is not changed.
Comparative example 1 (preparation of electrode layer and hydrogel layer separately by step and then assembling solid super capacitor by paste method)
1.3421g of active carbon, 0.1674g of multi-wall carbon nano tube and 0.1677g of polytetrafluoroethylene suspension are respectively weighed, 5mL of absolute ethyl alcohol is added, and after being mixed and stirred uniformly, the mixture is rolled repeatedly, so that the mixture is uniformly mixed to form a film, and an active substance film is obtained; then placing the active material film into a 70 ℃ oven for drying for 6 hours, taking out, and cutting into a plurality of round electrode plates with the diameter of 10 mm; 1.6g of sodium hydroxide is weighed and dissolved in 7.25mL of deoxidized deionized water to obtain solution 1, 0.8476g of lithium chloride and 2.75mL of acrylic acid are added into the solution 1, the mixture is stirred and mixed uniformly, the solution 2 is obtained after cooling to room temperature, the solution 2 is placed in an ice-water bath, 6.16mg of N, N ' -methylenebisacrylamide, 27mg of potassium persulfate and 38 mu L N of N, N ', N ' -tetramethyl ethylenediamine are sequentially added, and the mixture is stirred and mixed uniformly to obtain a final reaction solution; then injecting the reaction liquid into a glass die, sealing, and then performing ultrasonic treatment to remove bubbles for 5min; finally, placing the die filled with the reaction liquid into a constant temperature box at 25 ℃ for free radical polymerization reaction, obtaining a final hydrogel solid electrolyte after 3 hours, and cutting the prepared hydrogel solid electrolyte into a hydrogel solid electrolyte sheet with a circular thickness of 1mm and 10 mm; taking out two circular electrode plates, attaching the two circular electrode plates to a hydrogel solid electrolyte sheet with the circular thickness of 10mm and the 1mm, and tabletting the hydrogel solid electrolyte sheet with the circular thickness of 10mm between the two circular electrode plates for 5min by using a 1kg weight to obtain the solid super capacitor.
The cyclic voltammogram of the solid super capacitor prepared in comparative example 1 shows a rectangular-like shape with a specific capacitance of only 120mF/cm 2 Current density 2mA/cm 2 The lower voltage is 0.4V, the contact impedance is 20Ω, the coulomb efficiency is 89%, and the specific capacitance is only 16mF/cm at-40 DEG C 2 The coulomb efficiency was only 75%, and a large current density of 40mA/cm could not be achieved 2 And the constant current charge and discharge curve has obvious deviation and obviously reduced specific capacitance after repeated bending for 20 times at 180 degrees.
As can be seen from the comparison example, the electrode layer and the hydrogel layer are prepared respectively in steps, and then compared with the solid super capacitor prepared by the integrated forming method provided by the invention, the solid super capacitor prepared by the assembly method through a pasting method has the advantages that the specific capacity and the coulomb efficiency are greatly reduced, the voltage drop and the contact resistance are obviously increased, and the low temperature resistance and the bending resistance are obviously reduced. Therefore, the integrated molding technology provided by the invention provides an effective method for preparing the high-performance solid super capacitor.

Claims (7)

1. The preparation method of the integrally formed hydrogel solid super capacitor is characterized by comprising the following steps of:
(1) Weighing porous carbon, multi-wall carbon nano tubes and polytetrafluoroethylene suspension, adding ethanol solution, and uniformly mixing and stirring to obtain a raw material 1; the mass of the porous carbon is 10% -80% of the total mass of the porous carbon, the multi-wall carbon nano tube and the polytetrafluoroethylene suspension, the mass of the multi-wall carbon nano tube is 10% -80% of the total mass of the porous carbon, the multi-wall carbon nano tube and the polytetrafluoroethylene suspension, and the mass of the polytetrafluoroethylene suspension is 5% -10% of the total mass of the porous carbon, the multi-wall carbon nano tube and the polytetrafluoroethylene suspension;
(2) Dividing the raw material 1 in the step (1) into two parts, respectively transferring the two parts to two glass plates, repeatedly pressing the two parts to form a film, and then drying the film to obtain the glass plate coated with the active substance film; the drying time is 3-6 hours, and the drying temperature is 60-80 ℃;
(3) Adding sodium hydroxide into water, stirring uniformly to obtain a solution 1, adding lithium chloride and acrylic acid into the solution 1, stirring uniformly, and cooling to obtain a solution 2; the ratio of the amount of the substance added with lithium chloride to the total volume of the added water and acrylic acid is 0.5 mol/L to 2.5 mol/L, the ratio of the amount of the substance added with sodium hydroxide to the total volume of the added water and acrylic acid is 1 mol/L to 4 mol/L, and the ratio of the amount of the substance added with acrylic acid to the total volume of the added water and acrylic acid is 1 mol/L to 4 mol/L;
(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, carrying out ultrasonic treatment on the reaction solution, and removing 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 die filled with the reaction liquid in the step (5) into an incubator for polymerization reaction, after the reaction is finished, tightly combining the active substance film coated on the glass plate with hydrogel obtained by the polymerization reaction to form a sandwich structure, and opening the die to obtain the integrally formed hydrogel solid super capacitor formed by the active substance film and the hydrogel.
2. The method for preparing the integrally formed hydrogel solid super capacitor according to claim 1, wherein the cross-linking agent in the step (4) is N, N' -methylenebisacrylamide, and the amount of the cross-linking agent is 0.01% -0.15% of the amount of the acrylic acid.
3. The method for preparing the integrally formed hydrogel solid super capacitor 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.
4. The method for preparing the integrally formed hydrogel solid super capacitor according to claim 1, wherein the accelerator in the step (4) is N, N, N ', N' -tetramethyl ethylenediamine, and the amount of the accelerator is 0.1% -1% of the amount of the acrylic acid.
5. The method for preparing the integrally formed hydrogel solid super capacitor according to claim 1, wherein in the step (5), the time for removing bubbles of the glass mold filled with the reaction liquid by ultrasonic is 2-10 min.
6. The method for preparing the integrally formed hydrogel solid super capacitor according to claim 1, wherein the temperature of the incubator in the step (6) is 10-40 ℃, and the polymerization reaction time is 1-6 h.
7. An integrally formed hydrogel solid state supercapacitor made by the method of any one of claims 1-6.
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CN107591252A (en) * 2017-07-21 2018-01-16 同济大学 A kind of flexibility can cut solid-state super capacitor and preparation method thereof
CN110767470A (en) * 2019-10-25 2020-02-07 华南理工大学 Super capacitor based on anti-freezing hydrogel electrolyte and preparation method thereof
CN113571343A (en) * 2021-06-17 2021-10-29 南京邮电大学 Integrated super capacitor and preparation method thereof
CN113611545A (en) * 2021-08-18 2021-11-05 齐鲁工业大学 Stretchable, compressible and anti-freezing organic hydrogel electrolyte-based supercapacitor and preparation method thereof

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