CN116053609A - Double-network hydrogel electrolyte with wide temperature range, preparation method and application - Google Patents

Double-network hydrogel electrolyte with wide temperature range, preparation method and application Download PDF

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CN116053609A
CN116053609A CN202211390240.8A CN202211390240A CN116053609A CN 116053609 A CN116053609 A CN 116053609A CN 202211390240 A CN202211390240 A CN 202211390240A CN 116053609 A CN116053609 A CN 116053609A
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carrageenan
acrylamide
network hydrogel
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王贵宾
姜迪
李磊博
张号群
杨砚超
栾加双
张淑玲
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Jilin University
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Abstract

The invention provides a double-network hydrogel electrolyte with a wide temperature range, a preparation method and application. The preparation method comprises the following steps: the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel with a double-network structure is prepared from carrageenan, sulfobetaine methacrylate and acrylamide as raw materials, and then the concentration of the soaking solution is adjusted by a solution replacement method to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte with a wide temperature range. And then the double-network hydrogel electrolyte and MnO 2 @CNT electrode and zinc sheet electrode are assembled to obtain zinc ion battery, and prepared Zn-MnO 2 The battery can still keep stable energy output at the low temperature of 30 ℃ below zero and the high temperature of 60 ℃, and has application prospect in the aspect of flexible wearable devices.

Description

Double-network hydrogel electrolyte with wide temperature range, preparation method and application
Technical Field
The invention belongs to the technical field of conductive hydrogel materials, and particularly relates to a double-network hydrogel electrolyte with a wide temperature range, a preparation method and application.
Background
The rapid development of wearable and portable electronic products has driven the need for flexible energy storage devices such as water-based batteries. The liquid electrolyte is widely applied to energy storage equipment, is an ion conductor which plays a role in conduction between the anode and the cathode of the battery, plays a critical role in the aspects of energy density, power density, cycle life, safety performance and the like of the battery, but has unavoidable disadvantages such as dendritic corrosion and electrolyte leakage, and limits the application of the liquid electrolyte. Therefore, hydrogel electrolytes having solid-like mechanical properties and liquid-like ion transfer rates are becoming increasingly popular research sites, and their quality as one of the key components of flexible energy storage devices is a key factor in determining the performance of the energy storage devices. The ideal hydrogel electrolyte should combine good conductivity, excellent mechanical properties and a wide operating temperature range to suit the actual application environment.
Ion conductivity is an important performance index of the electrolyte, so whether the electrolyte has excellent ion transport performance under various use environments is an important factor affecting electrochemical performance of the battery, for example, foreign literature (Minfeng Chen, jizhang Chen, weijun Zhou, xiang Han, yagang Yao, and Ching-Ping Wong, realizing an All-Round Hydrogel Electrolyte toward Environmentally Adaptive Dendrite-Free Aque Zn-MnO) 2 Batteries, A.M.2021,33,2007559) indicates that hydrogel electrolytes, due to their relatively high water content, freeze at low temperatures and high temperaturesVolatilizing, causing deterioration of conductivity and thus affecting the performance of the battery is a current problem to be solved.
Meanwhile, the flexible energy storage device should have excellent mechanical properties and stability, and can still maintain stable energy output even under the influence of external environment, which is also a focus problem in research work. However, natural polymer hydrogels often lack excellent mechanical properties and possess undesirable and unstable electrochemical properties, such as a dramatic decrease in conductivity under low and high temperature conditions. The current design and preparation of hydrogel electrolytes with good mechanical properties, environmental stability and excellent electrochemical properties is a problem that current research efforts need to address.
Disclosure of Invention
In order to solve the technical problems, the invention provides a double-network hydrogel electrolyte with a wide temperature range, and the preparation method comprises the following steps:
(1) Dissolving carrageenan in aqueous solution, stirring for 60-90 min at 80-100 ℃, adding zwitterionic sulfobetaine methacrylate monomer, acrylamide monomer, cross-linking agent N, N-methylene bisacrylamide with the total mole number of 0.05-0.2% of the two monomers, initiator with the total mole number of 0.3-0.6% of the two monomers and zinc chloride, mixing and stirring for 60min, pouring into a mould, preserving heat for 1-2 h at-40-0 ℃, recovering to room temperature for 2-8 h at 0-25 ℃ to obtain gel-like mixture, and polymerizing under ultraviolet light to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel;
(2) Zinc chloride and lithium bromide are dissolved in water to obtain uniform mixed salt solution;
(3) And (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 5-360 min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte.
Specifically, the ratio of the mass of the carrageenan to the total mass of the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer in the step (1) is 1:6-1:35.
Specifically, the molar ratio of the zwitterionic sulfobetaine methacrylate monomer to the acrylamide monomer in the step (1) is 1:5-1:30.
Specifically, the initiator in the step (1) is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or alpha-ketoglutarate.
Specifically, the molar concentration of the zinc chloride in the step (1) is 1 to 2mol L -1 。
Specifically, the molar concentration of zinc chloride in the mixed salt solution in the step (2) is 1-2 mol L -1 。
Specifically, the molar concentration of lithium bromide in the mixed salt solution in the step (2) is 4-12 mol L -1 。
The invention also provides application of the double-network hydrogel electrolyte with a wide temperature range in the field of energy storage devices or supercapacitors.
Specifically, the invention also provides application of the double-network hydrogel electrolyte with a wide temperature range in the field of zinc-manganese dioxide batteries.
The invention has the advantages that:
according to the invention, the double-network hydrogel electrolyte (-40 ℃ elongation at break up to 155% and tensile strength 117KPa,80 ℃ elongation at break up to 185% and tensile strength 119 KPa) with excellent performance and wide temperature range is obtained through the synergistic effect of the raw materials, the reaction proportion of the raw materials and the process. The carrageenan is selected as a first network of the double-network hydrogel electrolyte, the carrageenan has excellent toughness and an energy dissipation mechanism, and the zwitterionic monomer and the acrylamide monomer are selected to be copolymerized to serve as a second network, so that the energy of the hydrogel electrolyte is preferentially and effectively dissipated through a reversible hydrogen bond between the first heavy network and the two networks in the whole energy dissipation process, meanwhile, the second heavy copolymerization network can keep the integrity of the hydrogel, the ion transmission is not influenced by the outside, and the basis is provided for the double-network hydrogel with excellent mechanical property and electric conductivity. Introducing a salt solution into the hydrogel obtained by the above process by a solution substitution method, thereby widening the electrolyte temperatureThe degree of usage range (-20 ℃ C. Conductivity 20.8mS cm) -1 Conductivity at 50℃of 40.3mS cm -1 ). The introduction of the salt solution can not only destroy intermolecular hydrogen bonds among free water molecules in the hydrogel polymer electrolyte and strengthen interaction between the water molecules and a hydrogel network, but also can form strong interaction with the water molecules, thereby remarkably enhancing water retention and anti-freezing capability, further obtaining the double-network hydrogel electrolyte with wide temperature range, the performance of the double-network hydrogel electrolyte is superior to that of the double-network hydrogel electrolyte with wide temperature range, for example, the anti-freezing zwitterionic double-network hydrogel electrolyte reported by the prior art has the conductivity of only 10.38mS cm at the temperature of minus 20 DEG C -1 。
Drawings
FIG. 1 is a graph showing the tensile properties of the dual network hydrogel electrolytes prepared in examples 1, 6, 7, 8 and 9;
FIG. 2 is a graph of conductivity versus the dual network hydrogel electrolytes prepared in examples 1, 2 and 3;
FIG. 3 is a graph showing the tensile properties of the dual network hydrogel electrolyte prepared in example 1 at 80℃and-40 ℃;
FIG. 4 is a graph of the conductivity of the dual network hydrogel electrolyte prepared in example 1 at various temperatures;
FIG. 5 is a graph showing the compression properties of the dual network hydrogel electrolyte prepared in example 1;
FIG. 6 shows the Zn-MnO of example 11 2 Cyclic voltammogram of the cell;
FIG. 7 shows the Zn-MnO of example 11 2 Charge-discharge curve of the battery.
Detailed Description
The method of the invention is described below by way of specific examples, which are only illustrative of the claims of the invention, including but not limited to the examples. Reagents and materials described in the examples below are all commercially available unless otherwise specified; the test methods are conventional methods unless otherwise specified. The electrochemical workstation used in the examples was CHI604E type of Shanghai Chen Hua, the battery test system was CT2001A type of Wuhan City blue electric power electronics Co., ltd, and the universal material tester was SHIMADZUAG-I type of Shimadzu corporation.
Example 1: the hydrogel electrolyte 1 was prepared as follows:
the method comprises the following specific steps:
step 1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 60min at 95 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer mole ratio of 1:20, wherein the total mole number of the two monomers is 0.1 percent, the cross-linking agent N, N-methylene bisacrylamide cross-linking agent, and the initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl with the total mole number of the two monomers being 0.5 percent]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at-20 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under an ultraviolet lamp for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 6mol L -1 。
Step 3: and (3) soaking the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 360min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 1 with a wide temperature range.
Example 2: the hydrogel electrolyte 2 was prepared as follows:
step 1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 60min at 80 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer ratio of 1:10, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers of 0.1%, and an initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl with the total mole number of the two monomers of 0.5%]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring, pouring into a mold, cooling at-30deg.C for 1 hr, recovering at 10deg.C for 4 hr to room temperature, and polymerizing under ultraviolet light for 3 hrTo obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 5mol L -1 。
Step 3: and (3) soaking the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 240min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 2 with higher ionic conductivity, mechanical property and wide use temperature range.
Example 3: the hydrogel electrolyte 3 was prepared as follows:
step 1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 90min at 90 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer mole ratio of 1:30, wherein the cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers of 0.05 percent, and the initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl with the total mole number of the two monomers of 0.5 percent]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at 0 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 4mol L -1 。
Step 3: and (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 300min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 3 with a wide temperature range.
Example 4: the hydrogel electrolyte 4 was prepared as follows:
step (a)1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 60min at 90 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer mole ratio of 1:20, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of 0.08%, an initiator alpha-ketoglutaric acid with the total mole number of 0.3% of the two monomers and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at-20 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: zinc chloride and lithium bromide are dissolved in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 8mol L -1 。
Step 3: and (3) soaking the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 360min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 4 with a wide temperature range.
Example 5: the hydrogel electrolyte 5 was prepared as follows:
step 1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 60min at 90 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer mole ratio of 1:20, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of 0.05 percent, an initiator alpha-ketoglutaric acid with the total mole number of 0.3 percent and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at 0 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: zinc chloride and lithium bromide are dissolved in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 12mol L -1 。
Step 3: and (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 120min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 5 with higher ionic conductivity, mechanical property and wide use temperature range.
Example 6: the hydrogel electrolyte 6 was prepared as follows:
step 1: 0.17g of carrageenan was dissolved in 14mL of aqueous solution, and after stirring at 80℃for 60min, the monomer was further added in a molar ratio of 1:20, an acrylamide monomer, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.1 percent, and an initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxy ethoxy) phenyl with the total mole number of the two monomers being 0.5 percent]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at 0 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 4mol L -1 。
Step 3: and (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 240min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 6 with a wide temperature range.
Example 7: the hydrogel electrolyte 7 was prepared as follows:
step 1: 0.34g of carrageenan was dissolved in 14mL of aqueous solution, and after stirring at 90℃for 60min, the monomer was further added in a molar ratio of 1:20, an acrylamide monomer, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.1 percent, and an initiator 2-hydroxy-2-methyl-1 with the total mole number of the two monomers being 0.5 percent- [4- (2-hydroxyethoxy) phenyl ]]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at 0 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 4mol L -1 。
Step 3: and (3) soaking the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 360min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 7 with higher ionic conductivity, mechanical property and wide use temperature range.
Example 8: the hydrogel electrolyte 8 was prepared as follows:
step 1: 0.67g of carrageenan was dissolved in 14mL of aqueous solution, and after stirring at 95℃for 60min, the monomer was further added in a molar ratio of 1:20, an acrylamide monomer, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.08 percent, and an initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxy ethoxy) phenyl with the total mole ratio of the two monomers being 0.5 percent]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at-10 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 6mol L -1 。
Step 3: and (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 240min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 8 with a wide temperature range.
Example 9: the hydrogel electrolyte 9 was prepared as follows:
step 1: 0.84g of carrageenan was dissolved in 14mL of aqueous solution, and after stirring for 90min at 100℃the monomers were then mixed in a molar ratio of 1:20, an acrylamide monomer, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.05 percent, and an initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxy ethoxy) phenyl with the total mole number of the two monomers being 0.5 percent]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring uniformly, pouring into a mould, cooling at-20 ℃ for 1h, recovering to room temperature at 25 ℃ for 2h, and polymerizing under ultraviolet light for 3h to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 4mol L -1 。
Step 3: and (3) soaking the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 360min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 9 with a wide temperature range.
Example 10: the hydrogel electrolyte 10 was prepared as follows:
step 1: dissolving 0.5g carrageenan in 14mL of water solution, stirring for 60min at 95 ℃, and then mixing the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer with the monomer mole ratio of 1:20, wherein the cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.12%, and the initiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl with the total mole number of the two monomers being 0.5%]-1-propanone and 1mol L -1 Adding zinc chloride, mixing, stirring, pouring into a mold, cooling at 0deg.C for 1 hr, recovering at 25deg.C for 6 hr, and polymerizing under ultraviolet light for 3 hr to obtain carrageenan-poly (sulfobetaine methylpropyl)Acrylate/acrylamide) composite hydrogels.
Step 2: dissolving zinc chloride and lithium bromide in deionized water to obtain uniform mixed salt solution, wherein the concentration of the zinc chloride is 1mol L -1 Lithium bromide concentration of 4mol L -1 。
Step 3: and (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 360min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 10 with a wide temperature range.
Example 11: the preparation of the zinc-manganese dioxide battery based on the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte 1 specifically comprises the following steps:
(1) Prior to electrochemical deposition, the carbon nanotube paper was immersed in a solution consisting of ethanol and deionized water for 3 minutes to obtain a more loose structure. Subsequently, the above CNT paper, platinum sheet and Ag/AgCl electrode were used as working electrode, counter electrode and reference electrode, respectively. Then in 0.1M Mn (CH 3 COO) 2 Electrodeposition was performed in solution under conditions of 1.0V for 900 seconds. After electrodeposition was completed, the prepared MnO was washed with deionized water 2 @cnt electrode and dried. The MnO 2 Is 1.2mg cm -2 ；
(2) Taking MnO prepared in the step (1) 2 CNT electrode, smooth zinc sheet and double network hydrogel electrolyte 1 prepared in example 1 (i.e. electrolyte obtained in example 1) were used as cathode material, anode material and electrolyte, respectively, and assembled by simple "sandwich" lamination to obtain Zn-MnO 2 A button cell. Here, all button cells used in the experiments were assembled by using a circular zinc plate having a diameter of 1cm and a circular MnO having a diameter of 1cm by a conventional method 2 The model of the button cell shell is CR2032, which is obtained by assembling the@CNT electrode and the corresponding hydrogel electrolyte;
(3) Zn-MnO obtained by assembling the step (2) 2 Electrochemical workstation for button cell testing its cyclic voltammetry performance (scan rate100mV s -1 The voltage window is 0.8-1.9V), and the constant current charge and discharge performance of the battery is tested by a blue battery test system.
The cyclic voltammetry and charge-discharge test curves of the battery are shown in FIGS. 6 and 7, and the battery capacity assembled in example 11 is 0.25A g -1 290mA h g at current density -1 Is superior to the prior art, such as AMP-Mn/PVA hydrogel electrolyte batteries (0.2A g -1 267mA h g at current density -1 The prior art comprises the following steps: Y.Hu, P.Shen, N.a.Zeng, L.Wang, D.i.Yan, L.Cui, K.Yang, C.Zhai, hybrid Hydrogel Electrolyte Based on Metal-Organic Supermolecular Self-Assembly and Polymer Chemical Cross-Linking for Rechargeable Aqueous Zn-MnO 2 Batteries,ACS Appl.Mater.Interfaces 12(37)(2020)42285–42293)。
Prepared Zn-MnO 2 The battery can still maintain stable energy output under the low temperature of-30 ℃ and the high temperature of 60 ℃.
Comparative example 1: antifreezing Zwitterionic-Based Hydrogel Electrolyte for Aqueous Zn Ion Batteries, chunmei Yuan, xin Zhong, peishu Tian, zhe Wang, guanghui Gao, lianfeng Duan, chunsheng Wang, and Fengwei Shi, ACS appl. Energy Mater.2022,5,7530-7537.
First, 1.25g sodium alginate was added to 40mL water and heated at 60℃for 1h. Then, 1.25g of acrylamide and 10g of zwitterionic sulfobetaine methacrylate monomer are added into the solution in sequence, and after being stirred uniformly, a cross-linking agent N, N-methylene bisacrylamide cross-linking agent with the total mole number of the two monomers being 0.03mol percent and an initiator potassium persulfate with the total mole number of the two monomers being 0.15mol percent are added. The resulting mixture was then poured into a mold and allowed to stand at 60 ℃ for 6 hours until the hydrogel film was completely formed. Then, the hydrogel was immersed in 5mol/L ZnCl 2 And 4mol/L LiCl for 12 hours to obtain a double-network hydrogel electrolyte.
The properties of the dual network hydrogel electrolytes of examples 1 to 10 and comparative example 1 are shown in table 1 below.
Table 1 various properties of the dual network hydrogel electrolytes of examples 1 to 10 and comparative example 1
Figure BDA0003931729720000081
To sum up:
as can be seen from table 1: compared with the comparative example 1 and the prior art, the electrolyte obtained by the invention has the most excellent mechanical and electrochemical properties; the materials, the ratios of the materials, and the process parameters are different in all examples, wherein the gel electrolyte obtained in example 1 is most excellent in performance, thus indicating that the present invention is to obtain the most excellent performance of the materials by the synergistic effect of the materials, the ratios of the materials, and the process. In addition, the dual-network hydrogel electrolyte 1 obtained by the invention has the tensile strength of 117KPa at minus 40 ℃, the tensile strength of 165KPa at minus 20 ℃ and the tensile strength of 119KPa at 80 ℃, and the mechanical properties of the electrolyte obtained by the example 1 are better than those of the electrolyte obtained by the comparative example 1 (131.2 KPa at room temperature and 133.4KPa at minus 20 ℃) under the conditions of room temperature (280 KPa), low temperature (-165 KPa at 20 ℃) and high temperature (119 KPa at 80 ℃), and the like. Meanwhile, the double-network hydrogel electrolyte 1 obtained by the invention has excellent compression performance, the area enclosed by two curves in the compression curve in fig. 5 represents energy loss in the compression-decompression process, the energy loss coefficient can be seen to be very small by comparing the enclosed area with the area enclosed by the compression curve, meanwhile, the deformation amount of the abscissa is close to 0 when the pressure is 0 in the decompression process, which means that almost no irreversible plastic deformation is generated after gel is subjected to the compression-decompression process, thereby indicating that the material obtained by the invention has good restorability. To sum up: according to the invention, through the structural design of the hydrogel, the multi-hydrogen bond interaction and the reversible electrostatic interaction are introduced into the double-network hydrogel electrolyte through the synergistic effect of the monomer, the monomer reaction proportion and the process, so that the hydrogel electrolyte is endowed with excellent mechanical property and ion conductivity, and the comprehensive performance of the conventional hydrogel serving as the electrolyte is better improved under the synergistic effect. The hydrogel electrolyte obtained by the invention has excellent ionic conductivity maintained in a wider temperature range and excellent mechanical properties under high and low temperature conditions, in Zn-MnO 2 Battery middle utensilHas better application. The flexible energy storage device of the hydrogel electrolyte can have excellent use prospect in wearable electronic equipment.

Claims (9)

1. A wide temperature range dual network hydrogel electrolyte characterized by: the preparation method comprises the following steps:
(1) Dissolving carrageenan in aqueous solution, stirring for 60-90 min at 80-100 ℃, adding zwitterionic sulfobetaine methacrylate monomer, acrylamide monomer, cross-linking agent N, N-methylene bisacrylamide with the total mole number of 0.05-0.2% of the two monomers, initiator with the total mole number of 0.3-0.6% of the two monomers and zinc chloride, mixing and stirring for 60min, pouring into a mould, preserving heat for 1-2 h at-40-0 ℃, recovering to room temperature for 2-8 h at 0-25 ℃ to obtain gel-like mixture, and polymerizing under ultraviolet light to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel;
(2) Zinc chloride and lithium bromide are dissolved in water to obtain uniform mixed salt solution;
(3) And (3) immersing the carrageenan-poly (sulfobetaine methacrylate/acrylamide) composite hydrogel obtained in the step (1) in the mixed salt solution obtained in the step (2) for 5-360 min to obtain the carrageenan-poly (sulfobetaine methacrylate/acrylamide) double-network hydrogel electrolyte.
2. The broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the ratio of the mass of the carrageenan in the step (1) to the total mass of the zwitterionic sulfobetaine methacrylate monomer and the acrylamide monomer is 1: 6-1: 35.
3. the broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the molar ratio of the zwitterionic sulfobetaine methacrylate monomer to the acrylamide monomer in the step (1) is 1:5 to 1:30.
4. the broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the initiator in the step (1) is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or alpha-ketoglutarate.
5. The broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the molar concentration of the zinc chloride in the step (1) is 1 to 2mol L -1 。
6. The broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the molar concentration of zinc chloride in the mixed salt solution in the step (2) is 1-2 mol L -1 。
7. The broad temperature range dual network hydrogel electrolyte of claim 1, wherein: the molar concentration of lithium bromide in the mixed salt solution in the step (2) is 4-12 mol L -1 。
8. Use of a wide temperature range dual network hydrogel electrolyte according to any of claims 1-7 in the field of energy storage devices or supercapacitors.
9. Use of a wide temperature range dual network hydrogel electrolyte according to any of claims 1-7 in the field of zinc-manganese dioxide batteries.
CN202211390240.8A 2022-11-08 2022-11-08 Double-network hydrogel electrolyte with wide temperature range, preparation method and application Pending CN116053609A (en)

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