CN114805675B - Ion transition and Grotthus transport mechanism-based freeze-resistant zwitterionic hydrogel electrolyte - Google Patents

Ion transition and Grotthus transport mechanism-based freeze-resistant zwitterionic hydrogel electrolyte Download PDF

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CN114805675B
CN114805675B CN202210484239.5A CN202210484239A CN114805675B CN 114805675 B CN114805675 B CN 114805675B CN 202210484239 A CN202210484239 A CN 202210484239A CN 114805675 B CN114805675 B CN 114805675B
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刘利彬
孙伟刚
班青
姜海辉
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Qilu University of Technology
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Abstract

The invention relates to the technical field of supercapacitors, in particular to an antifreeze zwitterionic hydrogel electrolyte based on ion transition and Grotthus transmission mechanisms and a preparation method thereof. At 1M H 2 SO 4 And Ethylene Glycol (EG), N-Methylenebisacrylamide (MBA) as a crosslinking agent, for Acrylamide (AM) and zwitterionic [2- (methacryloyloxy) ethyl ]]Dimethyl- (3-sulfopropyl) ammonium hydroxide (SBMA) was subjected to one-step radical polymerization to prepare an antifreeze proton hydrogel electrolyte. The electrolyte exhibits good mechanical properties and freeze protection. The low-temperature conductivity of the hydrogel electrolyte can reach 1.51mS cm at-50 DEG C ‑1

Description

Ion transition and Grotthus transport mechanism-based freeze-resistant zwitterionic hydrogel electrolyte
Technical Field
The invention relates to the technical field of supercapacitors, relates to a PolyAS electrolyte-based supercapacitor and a preparation method thereof, and in particular relates to a supercapacitor of an antifreeze zwitterionic hydrogel electrolyte based on ion transition and Grotthus transmission mechanisms and a preparation method thereof.
Background
Cryogenic energy storage devices are essential for extremely cold climates, such as aerospace exploration, polar exploration, and high altitude activities. As an important component of the energy storage device, the freezing resistance of the electrolyte directly affects the low temperature performance of the energy storage device. Although there are a great deal of research reports on low-melting nonaqueous electrolytes, such as liquefied gas, fluorinated solvents, and ethyl acetate, these nonaqueous electrolytes are generally costly, leaky, flammable, and toxic, limiting their use. In contrast, water-based electrolytes perform well in terms of low cost, nonflammability, non-toxicity, and the like. In particular, as a water-based solid electrolyte, a hydrogel electrolyte solves the problem that a liquid water-based electrolyte is easily leaked, and thus, the hydrogel electrolyte has attracted more and more attention in the field of large-scale energy storage. However, a large amount of free water in the hydrogel electrolyte inevitably freezes at a sub-zero temperature, resulting in a decrease in ionic conductivity and a loss of flexibility of the hydrogel.
Currently, there are three main strategies to solve the problem of freezing hydrogel electrolytes. One is by using salts as inhibitors of water freezing. In these systems, only high concentrations of salts can lower the freezing point. For example, 30wt% CaCl 2 The freezing point of the hydrogel system can be reduced to-57℃with low salt concentration (10 wt% CaCl) 2 ) Can only be reduced to-7 ℃ (x. P.Morelle, W.R.Illeperuma, K.Tian, R.Bai, Z.Suo, J.J.Vlassak, adv.Mater.2018,30, 1801541). In these antifreeze hydrogels, high concentrations of salts have a corrosive effect on the energy storage device. Another strategy is to improve the freeze protection properties of hydrogels by using ionic liquids. For example, zang et al developed an ionic liquid based supercapacitor that could operate at-40 ℃ (X.Zang, R.Zhang, Z.Zhen, W.Lai, C.Yang, F.Kang, H.Zhu, nano Energy 2017,40,224). However, ionic liquids also have a high viscosity at low temperatures and poor ionic conductivity, which is disadvantageous for a wide range of applications. A third strategy is to inhibit ice crystal formation by introducing an organic liquid into the hydrogel. Common organic liquids are dimethyl sulfoxide, ethylene Glycol (EG), glycerol, acetonitrile, and the like. Although progress has been made so far in aqueous proton electrolytes and proton hydrogel electrolytes, these proton electrolytes are either not freeze resistant or freeze resistant by high concentrations of the proton acid. For example, H at a high concentration 2 SO 4 (5M), which may have a corrosive effect on the electrode, is applied to an antifreeze lead quinone water battery. Therefore, it is very necessary to develop a proton hydrogel electrolyte having good low-temperature conductivity and mechanical flexibility by using a low concentration of a proton acid.
202111537424.8A method for synthesizing CMC-P (MAEDS-co-AA) polymer zwitterionic hydrogel is disclosed. The preparation process comprises the following steps: with carboxymethyl cellulose, acrylic acid, [2- (methacryloyloxy) ethyl ]]Dimethyl- (3-sulfopropyl) ammonium hydroxide is taken as a raw material, and the hydrogel electrolyte is synthesized through dissolution and thermal polymerization. After one hour of immersion in a zinc trifluoromethane sulfonate solution, the hydrogel electrolyte had a thickness of 25.3mS cm -1 Is excellent in ion conductivity. The hydrogel electrolyte to be obtainedThe quasi-solid zinc ion mixed capacitor is assembled for electrochemical performance test, and the current density is 0.25-20A g during the test -1 The voltage range is 0.2-1.8V. However, the process is complex, and the preparation method is formed by copolymerizing a plurality of monomers and needs to be soaked; the H+ released by the acrylic acid is insufficient to support the conductivity of the hydrogel, and additional conductive substances are required to be added; the cost is relatively high, and both zinc trifluoromethane sulfonate and conductive polymer are expensive.
202111403416.4A swelling-resistant zwitterionic hydrogel sensing material with controllable rehydration and high strain sensitivity, and a preparation method and application thereof are disclosed. The hydrogel is a conductive polymer hydrogel composed of acrylic acid, octadecyl methacrylate and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide. In this hydrogel, SBMA ([ 2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide) and a conductive polymer impart conductivity to the hydrogel, and SMA (octadecyl methacrylate) as a hydrophobic monomer in hydrophilic-hydrophobic balance with hydrophilic zwitterionic SBMA imparts swelling resistance to the hydrogel. Without the freeze resistance, the water in the hydrogel can freeze at low temperature, losing mechanical properties and conductivity. However, the hydrogel sensing material has no freezing resistance, and water in the hydrogel can freeze at low temperature, so that mechanical properties and conductivity are lost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an antifreeze zwitterionic hydrogel electrolyte based on ion transition and Grotthus transmission mechanism, and a preparation method and application thereof. The electrolyte exhibits good mechanical properties and freeze protection properties and can be used even at very low temperatures of-70 ℃.
The invention is realized by the following technical scheme:
a method for preparing a PolyAS hydrogel electrolyte, comprising the steps of:
1) Configuration of H containing 2 And (3) an O/EG binary solvent system, so that the O/EG binary solvent system is uniformly mixed.
2) To H 2 Sulfur addition to O/EG binary solvent systemsThe concentration of the sulfuric acid and MBA is regulated to be 0.8-1.5 mol/L, and the concentration of the MBA is regulated to be 0.15-0.25 g/L, so that the sulfuric acid and the MBA are uniformly mixed.
3) AM: the SBMA molar ratios were 1: monomers of 0 to 0.1, added to H already prepared 2 The O/EG binary solvent system is stirred in an ice bath for 0.5 to 1.5 hours.
4) Initiator APS was added to the above solution with stirring in an ice bath. The addition amount of APS is 1-2 wt% relative to the total mass of the monomers, and the precursor solution is obtained.
5) The resulting precursor solution was sonicated for 10 minutes to remove bubbles.
6) The precursor solution is injected into a mould, sealed and polymerized for 10 to 14 hours at a temperature of between 40 and 50 ℃.
The invention is implemented by the method of the invention in the specification 1M H 2 SO 4 And Ethylene Glycol (EG), N-Methylenebisacrylamide (MBA) as a crosslinking agent, for Acrylamide (AM) and zwitterionic [2- (methacryloyloxy) ethyl ]]Dimethyl- (3-sulfopropyl) ammonium hydroxide (SBMA) was subjected to one-step radical polymerization to prepare an antifreeze proton hydrogel electrolyte (fig. 1). The electrolyte exhibits good mechanical properties and freeze protection properties due to the variety of ionic and hydrogen bonds present in the system. The low-temperature conductivity of the hydrogel electrolyte can reach 1.51mS cm at-50 DEG C -1 . The jumping migration of protons on the ionic groups of SBMA and the mechanism of grotthus proton transport are responsible for the high conductivity of protons, which predominate in the glassy state of the polymer chains in low temperature environments. The super capacitor assembled by the electrolyte has 62.0F g at-50 DEG C -1 The retention of capacitance after 10000 cycles is 81.5%, even at very low temperatures of-70 ℃.
Preferably, in step 1), the H 2 The volume concentration of the O/EG binary solvent system is 0-100%. More preferably, the H 2 The volume concentrations of the O/EG binary solvent systems were 0%, 30%, 45%, 60% and 100%. More preferably, the H 2 The volume concentration of the O/EG binary solvent system is 30-60%.
Preferably, in step 2), the concentration of sulfuric acid is 1mol/L and the concentration of MBA is 0.2g/L.
Preferably, in step 3), the total mass of AM and SBMA is equal to EG/H 2 The volume ratio of the O mixture is 2:4-2:7. More preferably, in step 3), monomers with a total mass of 2g are added to the H already formulated in a molar ratio of 1:0, 3:1, 1:1, 1:3, 0:1 (AM: SBMA), respectively 2 O/EG binary solvent System (5 ml) and stirred in an ice bath for 1 hour. The ratio of the total mass of AM and SBMA to the volume of the EG/H2O mixture is 2:5-2:6.
Preferably, in step 4), the APS is added in an amount of 1% by weight relative to the total mass of the monomers.
Preferably, in step 6), the mixture is sealed and polymerized at 45℃for 12 hours.
The invention also provides a PolyAS hydrogel electrolyte (polyAS-EG) synthesized by the method.
polyAS has two broad peaks 3205cm -1 And 3445cm -1 3445cm of polyAS-EG -1 The peak was blue shifted to 3424cm -1 Indicating that in EG-H 2 The hydrogen bonding interactions between the water molecules in the O system are impaired.
An external electric field with a frequency of millihertz to megahertz and a Broadband Dielectric Spectrum (BDS) in a low temperature range of-30 to-70 ℃, the structure/segmented relaxation time of the electrolyte is 4.61x10 from-30 ℃ along with the reduction of the temperature -7 s is increased to 3.66x10 at-70 DEG C -5 s (fig. 8 a).
The conductivity of the PolyAS hydrogel electrolyte at the temperature of minus 50 ℃ is 0.32-1.51 mS cm < -1 >, and the activation energy is 0.276-0.566 eV.
polyAS-EG 45 The adhesive strength of the electrolyte to the carbon cloth can reach 180N m-1, and the electrolyte still has 81% water retention capacity after being exposed to air for seven days.
When the EG content is 45%, the gel can better achieve both strain and stress, the strain is 1390.1%, and the stress is 21.3kPa. At an EG content of 30%, the strain was 1042.2% and the stress was 24.4kPa. Preferably, the EG content is 30 to 60 percent, the strain is 1042.2 to 1840 percent, and the stress is 17.8 to 24.4kPa. (FIG. 6 a).
The ideal antifreeze hydrogel electrolyte needs to satisfy various functions in the equilibrium system, such as low freezing point, environmental friendliness, excellent low-temperature ion conductivity and mechanical flexibility. Protons are an ideal conductive ion compared to heavy and large radius metal ions because of their small size, wide availability and negligible cost.
SBMA is a zwitterionic inner salt with internally contained anions and cations which are wholly neutral, and is beneficial to dissociation of metal salts. AM carries a large number of hydrogen bond donors and hydrogen bond acceptors, and can build a good hydrogen bond system. To prepare a hydrogel electrolyte that is highly conductive while having mechanical flexibility, zwitterionic SBMA that is beneficial for ion transport and Acrylamide (AM) that has high hydrogen bond abundance are used as the core skeleton of the hydrogel. On the other hand, due to the extremely small atomic radius of the hydrogen ions and the unique ion transport line (the molar conductivity of the hydrogen ions is 350.1S cm 2 mol -1 Much larger than other ions. Thus, sulfuric acid with a large number of protons is used as the conductive medium. Finally, inexpensive and nontoxic Ethylene Glycol (EG) was selected as the antifreeze. 1mol of sulfuric acid can ionize 2mol of H + And sulfuric acid is not easy to volatilize, so that the electrolyte has great advantages as an acidic electrolyte. EG is a small molecular dihydric alcohol with a large amount of-OH, can be used as a hydrogen bond donor and a hydrogen bond acceptor, can destroy a hydrogen bond network among moisture so as to prevent water from freezing, and has the advantages of low cost, no toxicity and no harm.
The invention also provides the use of the PolyAS hydrogel electrolyte (polyAS-EG). The use is as a component of a deformation sensor and/or a temperature sensor. The method can be used as a wearable device to detect the action amplitude and the deformation amplitude; can be used as a component of a temperature detector to detect the change of temperature. Or the use is for super capacitors.
The technical scheme of the invention has at least the following excellent effects:
the antifreeze hydrogel electrolyte has higher conductivity and can provide 65.76mS cm at room temperature -1 . The hydrogel has better mechanical flexibility, and can be easily stretched for more than ten times (strain-1390.1%) at room temperature.
The antifreezing hydrogel electrolyte has good mechanical fatigue resistance, and the 35 th stress-strain cycle curve and the first cycle curve are basically overlapped.
The antifreezing hydrogel electrolyte has good low-temperature tolerance, has high ionic conductivity of 1.51mS cm < -1 >, and can be easily stretched by more than ten times even if the temperature is reduced to-50 ℃.
The antifreezing hydrogel electrolyte provided by the invention is simple in preparation process, all raw materials are blended by a one-pot method, and then the mixture is placed at 45 ℃ for 12 hours.
Drawings
FIG. 1 is a schematic diagram of the preparation and internal structure of an antifreeze zwitterionic hydrogel electrolyte.
FIG. 2 is HSO 4 - -H + 、SBMA-H + And SBMA-SBMA interaction energy.
FIG. 3 shows the effect of the molar ratio of AM to SBMA on the ionic conductivity (a) and mechanical strength (b) at room temperature.
Fig. 4 shows the interaction energy of different components in the electrolyte.
FIG. 5 shows Raman spectra of (a) water molecules and (b) DSC curves of different EG content polyAS-EG electrolytes.
Fig. 6 (a) stress-strain curves for different electrolytes. (b) Storage modulus (G') of different electrolytes at different temperatures. (c) Tan delta at different temperatures for different electrolytes. (d) polyAS-EG 45 The frequency dependence of the storage modulus (G ') and the loss modulus (G') at low temperatures of-50 ℃. (e) tensile photographs of different electrolytes at different temperatures.
Fig. 7 (a) temperature dependence of ionic conductivity of different electrolytes. (b) Hydronium ion (H) 3 O + ) FTIR spectra of flanking water molecules flexural vibrations. polyAS-EG 45 (c) -N of SBMA in electrolyte + (CH 3 ) 2 And (d) -SO 3 - Raman spectra of vibrations, with and without H 2 SO 4 Is an electrolyte of (a). (e) polyAM and polyAS-EG at different temperatures 45 H in electrolyte 3 O + Is a MSD of (C). (f) At the position of-SO in SBMA 3 - The proposed hydrated protons at the sites jump.
FIG. 8 (a, b) polyAS-EG 45 Broadband dielectric spectrum of the electrolyte. (a) Electrode polarization process and (b) dielectric modulus (M') and dielectric loss modulus (M ") as a function of frequency at different temperatures. (c) schematic representation of Grothuss mechanism in electrolyte.
FIG. 9 is a polyAS-EG 45 Mechanical fatigue of the electrolyte. (a) a photograph of compression rebound and a 50g weight load. (b) Stress-strain cycling test at room temperature with fixed strain (600%) and (d) different strains (100%, 400%, 800% and 1200%). (c) G' and G "at-50 ℃ under alternating strains of 1% (100 s) and 200% (100, 200 and 400 s).
FIG. 10 is a diagram of (a) polyAS-EG adhered to iron, silicon, wood, glass, plastic, copper rod, rubber and PTFE 45 Photographs of the electrolyte. (b) T-peel test of different electrolytes on carbon cloth substrates. (c) polyAS-EG at room temperature 0 And polyAS-EG 45 The weight of the electrolyte changes.
FIG. 11 is a diagram of (a) polyAS-EG 45 The resistance response of the electrolyte under different tensile strains (inset: photograph of electrolyte in released and stretched state, respectively). (b) polyAS-EG 45 The electrolyte has a resistive response at different cooling temperatures.
FIG. 12 is a graph showing the T-peel test of (a) different electrolytes on carbon cloth substrates. (b) polyAS-EG at room temperature 0 And polyAS-EG 45 The weight of the electrolyte changes. (c) The resistance response of the electrolyte under different tensile strains (inset: photograph of electrolyte in released and stretched state, respectively).
FIG. 13 is a diagram of (a) polyAS-EG using activated carbon electrodes 45 Photographs of electrolyte assembled SC. (b) voltage window of assembled SC.
Detailed Description
Raw materials and reagents: [2- (methacryloyloxy) ethyl ]]Dimethyl- (3-sulfopropyl) ammonium hydroxide (SBMA, C 11 H 21 NO 5 S), N-methylenebisacrylamide (MBA, C 7 H 10 N 2 O 2 ) Acrylamide (AM, C) 3 H 5 NO 3 ) Ammonium persulfate (APS, H) 8 N 2 O 8 S 2 ) Ethylene glycol (EG, (CH) 2 OH) 2 ) Purchased from aladin reagents limited. Polyvinylidene fluoride (PVDF, [ CH ] 2 CF 2 ] n ) N-methylpyrrolidone (NMP, C) 5 H 9 NO) was purchased from Macklin biochemical technologies limited. Sulfuric acid (H) 2 SO 4 ) Purchased from kangde chemical industry limited, lyyang, city. Carbon cloth was purchased from taiwan CeTech limited. Activated carbon was purchased from Kuraray corporation, japan. Carbon black was purchased from Alfa Aesar limited.
Model and manufacturer of experimental instrument equipment: ultrasonic cleaner, KQ3200 type B, kunshan ultrasonic instruments Inc. The reaction bath was stirred at constant temperature, type DHJF-4002, a company of trade, inc., great wall, zhengzhou. Constant temperature blast oven, DHG-9123A type, shanghai-Heng science instruments Co. Laser confocal raman spectrometer, model Lab RAM H600, HORIBA JY company, france. Microcomputer controlled universal mechanical tester, model WDW-02, jinan Hengsi Sheng Dai instruments. Heat collection type constant temperature stirrer, DF-101S type, henan Hehua Instrument Co., ltd. Broadband dielectric spectrometer, concept80 alpha-A, NOVOCONTROL, germany. Electrochemical workstation, CHI-660E type, shanghai Chen Hua instruments Co., ltd. A rotarheometer, ARES-G2 type; differential scanning calorimeter, type TA 2500; are all available from TA company in the united states.
The testing method comprises the following steps:
1. mechanical testing
The mechanical measurements were performed using a universal mechanical tester (Hensgrand, WDW-02, china). The electrolyte tensile test was performed at room temperature and a cylinder of 6mm diameter and 40mm length was stretched at a stretching speed of 100mm min-1. The stretching cycle was performed by fixing the strain at 600% with an interval of 10 minutes after each cycle.
T-peel tests were performed at room temperature using a universal mechanical tester (Hensgrand, WDW-02, china). One electrode of the SC is clamped on a fixed clamp of a stretcher, and the other electrode is clamped on a movable clamp for stripping, wherein the stripping speed is 100mm min < -1 >. The coverage area is 4mm x 100mm.
2. Rheology test
Rheology tests were performed using an ARES-G2 rheometer using parallel plates 25mm in diameter. The sweep test was performed at a fixed 1% oscillatory strain of 0.1-100 rad s-1 at a frequency range of 25℃and-50℃respectively. The temperature sweep is performed at a fixed frequency of 6.28rad s-1 over a temperature range of-80 to 60 ℃. Alternate step strain (1 and 200%) sweeps of the electrolyte were recorded at a fixed angular frequency of 10rad s-1.
3. Water retention test of zwitterionic gel electrolytes
Two equal masses of polyAS-EG0 and polyAS-EG45 gel electrolytes were taken and the mass was recorded every 12 hours when exposed to air at room temperature.
4. Broadband Dielectric Spectrum (BDS)
Broadband dielectric measurements were made using the Novocontrol Concept80 system over a frequency range of 10-2 to 107 Hz. The electrolyte was placed between two electrode plates, whose dielectric data were measured at ambient temperatures of-30 ℃, -50 ℃ and-70 ℃, respectively. The electrolyte was equilibrated for 30 minutes at each temperature before the dielectric measurements were made.
5. Conductivity measurement of zwitterionic hydrogel electrolytes
The ionic conductivity (σ) of the hydrogel electrolyte was measured on the CHI 660E electrochemical workstation using the double probe method. The amphoteric hydrogel electrolyte was filled in the CR927 battery case, and after being stabilized at different temperatures for 1 to 2 hours, the conductivity was measured at the corresponding temperatures, respectively. Each group of samples was measured 3 to 5 times and the average value was taken. The ionic conductivity is calculated according to the formula.
Figure SMS_1
Where R is the resistance (Ω), S is the cross-sectional area (cm 2) of the electrolyte being measured, and L is the thickness (cm) of the sample being measured.
6. Measurement of electrochemical Performance of SC devices
Cyclic Voltammetry (CV), electrochemical Impedance Spectroscopy (EIS), and constant current charge-discharge (GCD) measurements were performed using a two electrode system on the CHI 660E workstation. CV is performed at different scan rates between 0 and 1V. EIS was performed at an amplitude of 10mV between 0.01Hz and 100 kHz. GCD is performed at different current densities between 0 and 1V. Cycle stability and coulombic efficiency were measured by 10000 GCD cycles. The mass specific capacitance (Csp, F g-1) of the single electrode was obtained from the discharge curve of GCD and calculated as follows.
Figure SMS_2
Wherein I is discharge current (mA), Δt is discharge time(s), m device The total mass (g) of the two electrodes of the supercapacitor, deltaV represents the discharge voltage (V).
7. Other characterization analysis
The Raman spectrum was recorded using a LabRAM tHR800 Raman spectrometer (HORIBA JY, france) with a laser excitation wavelength of 532nm and a laser intensity of 50%. Differential Scanning Calorimetry (DSC) was performed using a TA2500 instrument by first cooling the sample from room temperature to-80℃and then increasing the sample from-80℃to 40 ℃. The cooling and heating rates were 2.5℃min -1 The mass of the sample taken is between 5 and 10 mg. The test of the sample was performed under a nitrogen atmosphere. Fourier transform infrared spectroscopy (FTIR) was tested using an sisor fourier transform infrared spectrometer.
The following examples are further illustrative of the invention, but the invention is not limited thereto.
In the present application, poly (AM-SBMA) electrolyte, polyAS electrolyte, polyAS-EGx (when EG content is 45%, referred to as polyAS-EG) 45 Electrolyte), zwitterionic hydrogel electrolyte, polyamphogel electrolyte, and anti-freeze zwitterionic hydrogel electrolyte are referred to in the same sense, and different names are used to emphasize certain properties thereof.
Example 1 preparation of PolyAS hydrogel electrolyte and investigation of monomer proportions
The polyAS-EG gel electrolyte isObtained by random copolymerization of AM and SBMA. First, AM and SBMA (total mass: 2 g) in different molar ratios (1:0, 3:1, 1:1, 1:3, 0:1) were added to 5ml EG/H 2 To the O mixture, 1M H was added 2 SO 4 And 0.2mg mL -1 Then stirred in an ice bath for 1 hour. Subsequently, 0.02g of initiator APS (1 wt% relative to the total mass of the monomers) was added to the above solution and stirred for 30 minutes with ice bath stirring. Finally, the resulting precursor solution was sonicated for 10 minutes to remove bubbles, the precursor solution was injected into a mold, sealed and polymerized at 45 ℃ for 12 hours.
-SO in SBMA 3 - Are believed to promote proton conduction. First, density Function Theory (DFT) calculations were used to demonstrate the positive effect of SBMA on proton conductivity. Addition of H to poly (AM-SBMA) hydrogels 2 SO 4 Previously, the anions and cations within SBMA can interact to form internal salts with optimal configuration (E SBMA-SBMA :-1.378Kcal mol -1 ). At the introduction of H 2 SO 4 after-SO 3 - -H + (E SBMA-H+ :-172.967Kcal mol -1 ) Is lower than HSO 4 - -H + (E HSO4-H+ :-168.493Kcal mol -1 ) As shown in fig. 2, SBMA was shown to be advantageous for sulfuric acid dissociation.
Calculation of Density Functional Theory (DFT): 7 kinds of structures (H) 2 O,EG,SBMA,AM,H+,SO 4 2- ,HSO 4 - ) And 20 complexes thereof were first optimized using Density Functional Theory (DFT) at the B3LYP/def2-SVP level. All geometric optimizations (including solvent effects of PCM) were performed using Gaussian 09 package, revision b.01. The single point energies of the four complexes were then performed at the same level, subject to previous optimization, taking into account the base stack error (BSSE). Harmonic frequency calculations were performed at the same theoretical level to help verify that all structures did not have virtual frequencies.
The binding energy of the configuration (Ebind) is calculated by the following equation:
Eb=EAB-(EA+EB) (1)
where EA, EB and EAB represent the energy and total energy of a and B (each single structure), respectively, a negative value of EB indicates that the process is exothermic, a larger negative value indicates stronger interaction, indicating more heat release and a more stable sample.
Subsequently, ion conductivity of EG-free poly (AM-SBMA) electrolytes was tested, and the results of the test also show that SBMA content was proportional to the conductivity of the system (FIG. 3 a). However, the greater the number of SBMAs, the lower the modulus of the hydrogel electrolyte as shown in fig. 3 b. Considering ionic conductivity and mechanical properties, we selected an electrolyte with a molar ratio AM: sbma=3:1, and studied the anti-freezing properties by adding various amounts of EG (hereinafter abbreviated as polyAS-EGx, x representing the volume percentage of EG).
Example 2 EG content, mechanical Properties and anti-freeze Studies
The polyamphogel electrolyte is obtained by random copolymerization of AM and SBMA. First, H is contained in amounts of 0%, 30%, 45%, 60% and 100% (volume concentration) depending on the volume ratio of EG 2 And adding MBA and sulfuric acid into the binary solvent system to prepare the sulfuric acid with the concentration of 1mol/L, MBA and the concentration of 0.2g/L. The molar ratio was then set to 3:1 (AM: SBMA), the total mass of 2g (am=0.866 g, sbma=1.134, g) of monomer was added to the binary solvent system (5 ml) which had been prepared and stirred in an ice bath for 1 hour. Subsequently, initiator 0.02g APS (1 wt% relative to the total mass of the monomers) was added to the above solution with ice bath stirring and stirring was continued for 30min. Finally, the obtained precursor solution was subjected to ultrasonic treatment for 10min to remove bubbles, and the precursor solution was injected into a mold, sealed and placed in an environment of 45 ℃ for polymerization for 12 hours. The preparation process is shown in figure 1.
Sequence number AM and SBMA molar ratio EG/H 2 O(vol%) Freezing point (DEG C)
A1 3:1 0 -3
A2 3:1 30 -22.9
A3 3:1 45 <-70
A4 3:1 60 -
A5 3:1 100 -
Molecular Dynamics (MD): the model is built by Amorphous Cell modules of Materials Studio software, and the mole ratio of each component of the model 1 is AM:SBMA:H 2 O:EG:H 2 SO 4 =3:1:38:10:1, model 2 is AM: H 2 O:EG:H 2 SO 4 =3:38:10:1. Molecular Dynamics (MD) simulations were performed using a forceplus of material studio software (Biovia inc.). The temperature is NThe ose-over thermostat is controlled at 203K and 298K. To obtain reasonable densities, 100ps kinetics were performed using NPT ensembles. Then, a speed Verlet algorithm is used to apply canonical integration (NVT) to each system, with a time step set to 1fs. Van der Waals interactions are calculated by an atom-based method with a cut-off distance of
Figure SMS_3
The electrostatic interactions are calculated by the Ewald method, which requires a long time but is accurate for long-range interactions. Finally, each system simulates 500ps to reach equilibrium. Through simulation, we analyzed the stability of the foam system by its equilibrium configuration and dynamic process.
Mean Square Displacement (MSD) is calculated according to the following formula:
Figure SMS_4
where N is the number of target molecules and ri (t) is the position of molecule i at time t. The self-diffusion coefficient represents the mobility of the molecular migration. The diffusion coefficient (D) can then be obtained from the slope of the mean square displacement versus time curve using the well-known einstein relationship:
Figure SMS_5
where d is the dimension of the system and ri (t) and ri (0) are the centroid coordinates of the ith water molecule at times t and t=0, respectively.
The essence of water freezing is the phase change of disordered water molecules driven by hydrogen bonds to ordered ice. EG can be used as a hydrogen bond acceptor and a hydrogen bond donor, and can effectively compete with hydrogen and oxygen in water molecules, so that the original hydrogen bond network among the water molecules is destroyed, and the freezing point of the aqueous solution is effectively reduced. EG can interact with water at-4.084 Kcal mol -1 Below H 2 O- H 2 O system [ ]
Figure SMS_6
-3.557Kcal mol -1 ) And EG-EG System (+)>
Figure SMS_7
-3.498Kcal mol -1 ) (FIG. 4) shows EG-H 2 The hydrogen bond in the O system is more stable. In addition, poly (AM-SBMA) chains are associated with EG-H 2 O mixture (E) AM-SBMA-EG-H2O :-14.412Kcal mol -1 ) The interaction energy of the polymer chain with pure water (E) AM-SBMA-H2O :-9. 536Kcal mol -1 ) Or pure EG (E) AM-SBMA-EG :-10.069Kcal mol -1 ) (FIG. 4) shows EG-H 2 The O mixture may form a more stable hydrogel network than pure water or pure EG, thereby helping to limit freezing of the water.
Raman spectroscopy also confirmed hydrogen bond formation between water and EG molecules. As shown in FIG. 5a, two broad peaks of polyAS-EG0 are concentrated at 3205cm-1 and 3445cm -1 This is caused by O-H stretching vibrations of hydrogen bonds of water molecules. After the addition of EG, 3445cm of polyAS-EG30 -1 The peak was blue shifted to 3424cm -1 ,polyAS-EG 100 The peak of the blue shift was further shifted to 3386cm -1 Indicating that in EG-H 2 The hydrogen bonding interactions between water molecules in the O system are weakened, thereby inhibiting ice crystal formation at low temperatures. Differential Scanning Calorimetry (DSC) was used to observe the effect of different EG levels on the freezing point of the electrolyte. As shown in FIG. 5b, the freezing points of polyAS-EG0 and polyAS-EG30 were-3℃and-22.9℃when the EG content was 0vol% and 30vol%, respectively. At 45vol%, 60vol% and 100vol% EG, no internal thermal peaks were observed in the DSC curve, indicating no change in heat flow in the electrolyte.
On the other hand, the different content of EG also affects the mechanical properties of the gel electrolyte. As shown in FIG. 6a, the mechanical properties of gel electrolytes of different EG contents were measured by a universal tensile tester at room temperature. As the EG content increases, the stress of the gel electrolyte decreases and the strain increases. For example, stress and strain are derived from polyAS-EG 0 38.1KPa and 736% of (A) were changed to polyAS-EG 60 17.8KPa and 1840%. When the EG content is 45%, the gel can better achieve both strain and stress, the strain is 1390.1%, and the stress is 21.3kPa. When EG containsAt 30%, the strain was 1042.2% and the stress was 24.4kPa. Preferably, the EG content is 30 to 60 percent, the strain is 1042.2 to 1840 percent, and the stress is 17.8 to 24.4kPa. (FIG. 6 a).
To further understand the internal structure of the electrolyte at low temperatures, a rheological temperature sweep was performed. Temperature scanning shows that polyAS-EG 0 The storage modulus G' of (c) starts to increase sharply after the ambient temperature is below-30 c, indicating that the entire electrolyte has been frozen. In contrast, polyAS-EG 45 And polyAS-EG 100 The storage modulus G' of (C) is exceptionally stable over a wide temperature range of-60 to 60℃as shown in FIG. 6 b. Furthermore, the Tandelta curve shows that polyAS-EG 0 Shows a broad peak at about 0c due to freezing of free water inside the gel (fig. 6 c), which is consistent with DSC results. Surprisingly, all three electrolytes exhibited a peak around-38 ℃ independent of solvent (fig. 6 c), which is believed to be the glass transition temperature (Tg) of the poly (AM-SBMA) chains in the electrolyte. In addition, polyAS-EG 45 The electrolyte has a weak shoulder centered at-60℃and polyAS-EG 0 And polyAS-EG 100 There is no one. This peak may be caused by crystallization of a portion of weakly bound water. Thus, polyAS-EG 45 The electrolyte should be a two-phase system containing a trace of ice and liquid strongly bound water at-60 ℃. The two-phase system was further confirmed by frequency scanning at a low temperature of-50 ℃. As the frequency increases, the loss modulus is progressively higher than the storage modulus, as shown in fig. 6d, indicating the phase change of the electrolyte from solid to liquid. Although a trace amount of ice was present in the electrolyte, polyAS-EG was present 45 Still shows flexibility at-60 ℃ and can be easily stretched to more than ten times the original one (figure 6 e). But does not contain EG's polyAS-EG 0 And polyAS-EG containing pure EG 100 Mechanical flexibility has been lost at extremely low temperatures.
EXAMPLE 3 PolyAS-EG 45 Conduction study of electrolyte
The conductivities of electrolytes of different EG contents measured at different temperatures using the antifreeze hydrogel electrolyte prepared in example 2 are shown in fig. 7 a. With increasing EG content, electricityThe conductivity of the electrolyte is first increased and then decreased, mainly because an increase in EG content has a conductive effect on freezing resistance, but too high EG content is detrimental to ion migration. polyAS-EG 45 Exhibits the highest ionic conductivity of 1.51mS cm at-50 DEG C -1 (Table 1), is antifreeze 2M NaClO 4 Aqueous DMSO solution (-0.11 mS cm at 50 ℃ C.) -1 Q.Nian, J.Wang, S.Liu, T.Sun, S.Zheng, Y.Zhang, Z.Tao, J.Chen, angew.Chem.Int.Ed.2019,58,16994) further demonstrates the advantages of proton conduction. The ultra-low temperature conductivity of our hydrogel electrolyte is also the head level in the reported antifreeze hydrogel electrolyte, even for montmorillonite/polyvinyl alcohol hydrogel electrolyte and 2M H 2 SO 4 (C.Lu, X.Chen, nano Lett.2020,20,1907).
TABLE 1 conductivity and activation energy at-50℃of different electrolytes
Figure SMS_8
The relationship between the ionic conductivity of the electrolyte and the inverse of the absolute temperature shows a linear relationship, obeying the Arrhenius law. The activation energies (Ea) of the different electrolytes are shown in table 1. The lower the activation energy, the more favorable the ion migration. polyAS-EG 45 The Ea of the electrolyte is the lowest, 0.276eV, which is also consistent with the highest conductivity at-50 ℃.
From this, our hydrogel electrolyte also shows excellent conductivity at low temperatures.
Protons are converted in aqueous solution to hydronium ions (H 3 O + ) Is present in the form of (c). At 1720cm -1 A shoulder is formed from H 3 O + As shown in fig. 7d, indicating the presence of H in the system 3 O + . The high ionic conductivity may be due to H 3 O + Jump migration on SBMA sulfonate is similar to the migration mechanism of metal ions in zwitterionic electrolytes. To prove this, H was measured 2 SO 4 And interactions with polymer chains. First, for the presence and absence of H 2 SO 4 polyAS-EG of (E) 45 The electrolyte was subjected to laser confocal raman spectroscopy. As shown in fig. 7c, for the absence of H 2 SO 4 electrolyte-N+ (CH) 3 ) 2 Is 2983cm -1 And 2940cm -1 Peak at the point of H 2 SO 4 When added to the hydrogel, the gel was moved to 2981cm -1 And 2937cm -1
indicating-SO 4 2- and-N + (CH 3 ) 2 There is an interaction between them. In addition, add H 2 SO 4 After that, SBMA-SO 3 - In (a) S=O stretching vibration is from 1041cm -1 Move to 1043cm -1 (FIG. 7 d). The variation of the characteristic peaks indicates that the static balance of anions and cations in SBMA is destroyed, H + And SO 4 2- Easy to overcome SBMA-SO 3 - and-N + (CH 3 ) 2 Electrostatic attraction of the groups. To further prove H 3 O + Jump migration over sulfonate we performed root mean square ion shift (MSD). As shown in fig. 7e, H 3 O + In polyAM and polyAS-EG 45 The displacement in the electrolyte shows a linear relationship with time interval, and polyAS-EG 45 H in (1) 3 O + Is larger than in a poly am electrolyte. This indicates polyAS-EG 45 The diffusion rate in the electrolyte was faster than in the polyAM electrolyte (table 2).
TABLE 2 polyAS and polyAS-EG 45 Middle H 3 O + Diffusion coefficient in MSD at different temperatures
Figure SMS_9
Based on the findings, H 3 O + In polyAS-EG 45 In (c) faster diffusion and-SO 3 - And H is + The lower interaction energy indicates that-SO on the polymer chain 3 - Channels which should provide proton conduction, H 3 O + Possibly at room temperatureover-SO on poly (AM-SBMA) chain 3 - Successive recombination and de-recombination at the sites jump (FIG. 7 f), similar to Li + Transport mechanisms in amphiphilic polymer electrolytes. However, at an extremely low temperature of-70 ℃, the MSD curve shows H 3 O + In polyAM and polyAS-EG 45 Has been significantly reduced as shown in fig. 7 e. This is consistent with the low temperature scan of rheology (FIG. 6 c), where the Tg of the poly (AM-SBMA) chain in the electrolyte is about-38deg.C, polyAS-EG 45 The chain should be in a glassy state at temperatures below-38 ℃. Therefore, at such low temperatures, the jumping migration of protons on the molecular chain may be limited. Thus, 1.51mS cm measured at-50 ℃ -1 Indicating that another efficient proton transfer mechanism may be employed at sub-zero temperatures.
In general, protons typically employ a typical Grotthus transport mechanism, in which a given proton is transferred between two adjacent hydrogen-bonded molecules in an aqueous system. It is believed that the gel electrolyte of the present invention employs a Grothuss transport mechanism and is dominant below the Tg (-38 ℃) of the poly (AM-SBMA) chain in the electrolyte. We performed Broadband Dielectric Spectroscopy (BDS) in an external electric field at frequencies from millihertz to megahertz and a low temperature range of-30 to-70 ℃. The electrode polarization process is shown in fig. 8 a. The maximum frequency can be considered as the onset of electrode polarization, and the structural/segmental relaxation time of the electrolyte can be determined by the maximum frequency (1/2 pi f mas ) Obtained. With decreasing temperature, the structural/segmental relaxation time of the electrolyte is from-30 ℃ to 4.61x10 -7 s is increased to 3.66x10 at-70 DEG C -5 s (fig. 8 a). In contrast, the electrolyte has a conductivity relaxation time at-70℃of about 1.59x10, calculated from the reciprocal frequency of the crossing point of the dielectric modulus (M ') and the dielectric loss modulus (M') -8 s (FIG. 8 b), which is much faster than the structure/segment relaxation time at-70℃and even faster than the structure/segment relaxation time at-30 ℃. The time scale of conductivity relaxation is significantly faster than the time scale of structure/segment relaxation, typically due to the proton transfer mechanism through the hydrogen bond network (i.e., the Grotthus transport mechanism), without the need for diffusion of the entire molecular unit. Furthermore, polyAS-EG 45 Proton conductivity at-50 ℃ gives Ea of 0.276eV, where Ea values less than 0.4eV are also considered to follow the grotthus theory, where protons are transferred through adjacent water molecules by bond vibration of h.o hydrogen bonds and H-O covalent bonds, as shown in fig. 8 c.
TABLE 3 structural relaxation and conductivity relaxation times of electrolytes at 130℃and-70 DEG C
Figure SMS_10
EXAMPLE 4 PolyAS-EG 45 Mechanical fatigue and adhesion of electrolyte
polyAS-EG 45 The electrolyte may be compressed and released to its original state. An electrolyte short rod with a diameter of 6mm can withstand a load of 50g, as shown in fig. 9 a. polyAS-EG 45 The stress strain experiments of (2) showed that after 35 draw cycles the curve almost coincides with the curve of the first cycle, indicating polyAS-EG 45 The electrolyte has little energy loss in multiple cycles and good mechanical fatigue resistance (fig. 9 b). On the other hand, stress-strain cycle tests of different strains were performed on the same electrolyte, and the stress-strain cycle curves of the electrolytes of different strains were substantially identical in trend, indicating that the internal structure of the electrolyte was very stable (fig. 9 d). Even at-50 ℃, the strain was maintained at 200% oscillation for 100s, 200s and 400s, respectively, and then immediately recovered to 1% strain, G' and G "were rapidly recovered to the original values, as shown in fig. 9 c.
In addition to good mechanical strength, polyAS-EG 45 The polar and zwitterionic groups of the electrolyte may enhance interfacial adhesion between the substrate and the electrolyte. As shown in FIG. 10a, polyAS-EG 45 The electrolyte may adhere to the surface of various materials including metal, glass, plastic, PTFE, and the like. In addition, polyAS-EG 45 The adhesive strength of the electrolyte to the carbon cloth can reach 180N m -1 (FIG. 10 b), which is a better than the electrolytes reported in our previous work (D.Li, Z.Xu, X.Ji, L.Liu, G.Gai, J.Yang, J. Wang, J. Mater. Chem. A2019,7,16414) and work by others (X.Liu, Q.Zhang, G.Gao, ACS Nano 2020,14,13709)Much higher, sufficient adhesion can be provided to bond the two electrodes together. More importantly, polyAS-EG 45 The electrolyte showed excellent water retention, and 81% water retention was still obtained after seven days of exposure to air, as shown in fig. 10 c.
EXAMPLE 5 PolyAS-EG 45 Resistance responsiveness of electrolyte
polyAS-EG 45 The electrolyte also has excellent resistance responsiveness. As shown in FIG. 11, a polyAS-EG is immobilized 45 And then pulling the other end to change its strain and record its resistance change. Different strains exhibit different resistive responsivity. While when the strain is kept unchanged, the resistance correspondingly remains unchanged, indicating that the internal structure of the electrolyte is stable. More importantly, due to the excellent freezing resistance, the electrolyte also showed a stable resistance change when the ambient temperature was below zero (fig. 11 b), which suggests that the hydrogel electrolyte is likely to function as a temperature sensor even at extremely low temperatures, unlike most reported hydrogel sensors that only operate above 0 ℃.
Thus, polyAS-EG 45 The electrolyte may be a component of a deformation sensor and/or a temperature sensor. The method can be used as a wearable device to detect the action amplitude and the deformation amplitude; can be used as a component of a temperature detector to detect the change of temperature.
Example 6 PolyAS-EG based 45 Electrolyte antifreezing supercapacitor
polyAS-EG 45 The electrolyte is assembled into a Supercapacitor (SC) using carbon cloth with activated carbon as an electrode. The hydrogel electrolyte having a thickness of about 0.2mm can directly replace the liquid electrolyte and the separator to avoid leakage of the electrolyte, as shown in fig. 12 a. First, at 100mV s -1 The scan speed of SC was tested. The Cyclic Voltammetry (CV) curve of SC showed an almost perfect rectangle in the electrochemical window of 1V (fig. 12 b). At room temperature, the CV curve of SC is between 10 and 500mV s at different scanning speeds -1 The lower part shows a rectangular shape, even at 500mV s -1 Is based on polyAS-EG at a large sweep rate 45 The CV curve of the SC of the electrolyte is also maintainedRectangular. The constant current charge-discharge (GCD) curves at different current densities also show a standard triangle and negligible voltage drop, indicating that SC exhibits ideal electric double layer capacitive behavior at room temperature (fig. 12 c).
In addition, when the temperature is reduced below zero, based on polyAS-EG 45 The electrolyte still shows good electrochemical properties. Electrochemical Impedance Spectroscopy (EIS) at different temperatures showed that the resistance of SC increased from 4.9 at 25 c to 25 at-50 c,
surprisingly, at-50 ℃, SC still showed good rate performance, as demonstrated by CV (fig. 13 a). At 25℃62.5mA g -1 The mass specific capacitance at the time of this process was 93.5F g -1 ,1A g -1 72.7 to 68.0. 68.0F g% retention -1 (FIG. 13 a). When the temperature is reduced to-50 ℃, the mass specific capacitance is 62.5mA g -1 Time change to 62.0F g -1 (66.3% at 25 ℃ C.) at 1A g -1 While maintaining 64.5%, which are all indicative of polyAS-EG based 45 The SC of the electrolyte has good electrochemical properties at extremely low temperatures.
More importantly, polyAS-EG 45 Assembled SCs were stored at-30℃to test their long-term low temperature resistance. After four months of storage at-30 ℃, the area of the CV curve is slightly changed, and the charge-discharge time is slightly reduced. Even if the SC is stored at-30 ℃ for eight months, the SC can still work normally, and the capacitance is reduced to 92.0% only, which indicates that the polyAS-EG 45 The electrolyte has the ability to operate for a long period of time at low temperatures. In practical applications, higher voltages and higher energy densities can be achieved by connecting several SCs in parallel and in series. In our example, two serially connected SCs show an electrochemical window of 2V in both CV and GCD tests, compared to a single SC; on the other hand, the current density of two parallel SCs increases to twice that of a single SC.
Based on polyAS-EG 45 The SC of the electrolyte also shows very strong performance in practical applications. Four serially connected SCs can light 12 LED lamps at-50deg.C for more than 10min, and even if the temperature is reduced to-70deg.C, only the brightness of the LED lamps becomes dark, and the lamp can last for 10minThe above. This indicates that polyAS-EG 45 Electrolytes have great potential for use in a variety of electrochemical devices, particularly when the electrochemical devices are used in extremely low temperature environments.

Claims (10)

1. A method for preparing a PolyAS hydrogel electrolyte, comprising the steps of:
1) Configuration of H containing 2 An O/EG binary solvent system, so that the two solvent systems are uniformly mixed; the H is 2 The volume concentration of EG in the O/EG binary solvent system is 30-60%;
2) To H 2 Sulfuric acid and MBA are added into an O/EG binary solvent system, the concentration of the prepared sulfuric acid is 0.8-1.5 mol/L, and the concentration of the MBA is 0.15-0.25 g/L, so that the sulfuric acid and the MBA are uniformly mixed;
3) AM: monomers with SBMA molar ratios of 3:1, 1:1, 1:3, respectively, are added to the H already prepared 2 The O/EG binary solvent system is stirred in ice bath for 0.5 to 1.5 hours;
4) Adding initiator APS to the above solution under ice bath agitation; the addition amount of APS is 1-2 wt% relative to the total mass of the monomers, so as to obtain a precursor solution;
5) Performing ultrasonic treatment on the obtained precursor solution for 10 minutes to remove bubbles;
6) The precursor solution is injected into a mould, sealed and polymerized for 10 to 14 hours at a temperature of between 40 and 50 ℃.
2. The method for preparing a PolyAS hydrogel electrolyte according to claim 1, wherein in the step 2), the concentration of sulfuric acid is 1mol/L and the concentration of MBA is 0.2g/L.
3. The method of preparing a PolyAS hydrogel electrolyte according to claim 1, wherein in step 3), the total mass of AM and SBMA is equal to EG/H 2 The volume ratio of the O mixture is 2:4-2:7.
4. The method of preparing a PolyAS hydrogel electrolyte according to claim 1, wherein in step 3), stirring is performed in an ice bath for 1 hour; total mass of AM and SBMA with EG/H 2 The volume ratio of the O mixture is 2:5-2:6.
5. The method for preparing a PolyAS hydrogel electrolyte according to claim 1, wherein in step 4), APS is added in an amount of 1wt% relative to the total mass of monomers; in step 6), the mixture was sealed and polymerized at 45℃for 12 hours.
6. A PolyAS hydrogel electrolyte synthesized according to the method of any one of claims 1-5.
7. The PolyAS hydrogel electrolyte of claim 6 wherein the two broad peaks of polyAS-EG0 are concentrated at 3205cm -1 And 3445cm -1 3445cm of polyAS-EG30 -1 The peak was blue shifted to 3424cm -1 30 represents the volume percent of EG.
8. The PolyAS hydrogel electrolyte of claim 6, wherein the PolyAS hydrogel electrolyte has a conductivity of 0.32 to 1.51mS cm at-50 °c -1 The activation energy is 0.276-0.566 eV.
9. The PolyAS hydrogel electrolyte of claim 6, wherein PolyAS-EG 45 The adhesive strength of the electrolyte to the carbon cloth can reach 180N m -1 81% water retention capacity after seven days of exposure to air; 45 represents the volume percent of EG;
when the EG content is 30-60%, the strain is 1042.2-1840% and the stress is 17.8-24.4 kPa.
10. Use of the PolyAS hydrogel electrolyte according to any one of claims 6-9, or the PolyAS hydrogel electrolyte prepared by the method according to any one of claims 1-5, as a component of a deformation sensor and/or a temperature sensor, or for a supercapacitor.
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