All-solid-state dual-network ionic conductive elastomer as well as preparation method and application thereof

Abstract

The invention discloses an all-solid-state dual-network ionic conductive elastomer as well as a preparation method and application thereof. The preparation method comprises the following steps: uniformly stirring and mixing a first type of hydrogen bond donor, a hydrogen bond acceptor and a volatile polar solvent to obtain a polymerizable eutectic solvent of a first network; adding an initiator and a cross-linking agent into the polymerizable eutectic solvent to obtain a prepolymer solution of a first network; irradiating under ultraviolet light to obtain first network gel; uniformly stirring and mixing a second type of hydrogen bond donors and hydrogen bond acceptors at 50-80 DEG C to obtain a polymerizable eutectic solvent of a second network; adding an initiator into the polymerizable eutectic solvent of the second network, and continuously stirring uniformly to obtain a prepolymer solution of the second network; and putting the first network gel into the prepolymer solution of the second network, replacing for 96-120 hours, curing by ultraviolet irradiation, and drying to obtain the all-solid-state dual-network ionic conductive elastomer. The all-solid-state dual-network ionic conductive elastomer has excellent mechanical properties, electrical properties, light transmission and the like.

Description

Technical Field

[0001] The present invention relates to the field of eutectic polymers. Specifically, the present invention relates to an all-solid-state double-network ion-conductive elastomer and its preparation method and application. Background Art

[0002] Stretchable ion-conductive elastomers exhibit great application potential in the fields of intelligent manufacturing, wearable devices, and biomedicine due to their excellent bendability, light weight, high integration, and the ability to maintain mechanical and electrical stability in complex environments. As the core material of flexible electronic devices, the balance between the strength and tensile properties of intrinsically stretchable all-solid-state double-network ion-conductive elastomers is crucial for their long-term reliability in complex environments.

[0003] Supramolecular eutectic polymers show significant advantages in the structural design of all-solid-state double-network ion-conductive elastomers due to their unique designability and excellent ion conductivity. However, supramolecular eutectic polymer networks usually have high density, which makes it difficult to achieve the design goal of both networks being composed of supramolecular eutectic polymers. This limitation restricts the application of supramolecular eutectic polymers in double-network structures. Therefore, it is necessary to develop an all-solid-state ion-conductive elastomer in which both networks are composed of supramolecular eutectic polymers by optimizing the network structure design to improve the mechanical properties and expand its application potential in flexible electronic devices. Summary of the Invention

[0004] Based on this, the present invention aims to overcome at least one defect of the prior art and provides an all-solid-state double-network ion-conductive elastomer and its preparation method. Through the structural design of the double network, by utilizing the high chemical compatibility between two supramolecular eutectic polymers, the design goal of both networks being composed of supramolecular eutectic polymers is achieved, enabling the material to undergo synchronous deformation under stress, effectively alleviating the stress concentration problem, significantly improving the mechanical properties of the material, thereby achieving the balance between strength and tensile properties, and the all-solid-state double-network ion-conductive elastomer constructed by the supramolecular eutectic polymers also has excellent light transmittance, self-healing performance, and electrical properties.

[0005] The technical solution is as follows:

[0006] A preparation method of an all-solid-state double-network ion-conductive elastomer, comprising the following steps:

[0007] S1. Mix the first type of hydrogen bond donor, hydrogen bond acceptor, and volatile polar solvent evenly by stirring at room temperature to obtain a polymerizable eutectic solvent for the first network;

[0008] S2. Add an initiator and a crosslinking agent to the polymerizable deep eutectic solvent of the first network, and continue to stir evenly to obtain a prepolymer solution of the first network;

[0009] S3. Irradiate the obtained prepolymer solution of the first network with ultraviolet light to obtain a first network gel;

[0010] S4. Stir and mix evenly the second type of hydrogen bond donor and hydrogen bond acceptor at 50 - 80 °C to obtain a polymerizable deep eutectic solvent of the second network;

[0011] S5. Add an initiator to the polymerizable deep eutectic solvent of the second network, and continue to stir evenly to obtain a prepolymer solution of the second network;

[0012] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, displace for 96 - 120 h, cure it by ultraviolet light irradiation, and then dry the sample in an oven to obtain an all - solid double - network ionic conductive elastomer;

[0013] Among them, the first hydrogen bond donor includes a hard monomer containing a C = C double bond, the second type of hydrogen bond donor includes a soft monomer containing a C = C double bond, and the hydrogen bond acceptor is a quaternary ammonium salt;

[0014] The molar ratio of the first hydrogen bond donor, hydrogen bond acceptor, and volatile polar solvent is (2 - 3):1:(4 - 10), and the molar ratio of the second hydrogen bond donor and hydrogen bond acceptor is 2:(0.4 - 1);

[0015] Among them, in step S6, the amounts of the prepolymer solution of the second network and the first network gel satisfy that the first network gel is completely immersed in the prepolymer solution of the second network.

[0016] In one embodiment, the hard monomer containing a C = C double bond is one or more of N - hydroxyethyl acrylamide, N - hydroxymethyl acrylamide, and acrylamide.

[0017] In one embodiment, the soft monomer containing a C = C double bond is acrylic acid and / or itaconic acid.

[0018] In one embodiment, the quaternary ammonium salt is choline chloride and / or choline dihydrogen citrate.

[0019] In one embodiment, the volatile polar solvent is anhydrous ethanol and / or methanol.

[0020] In one embodiment, the photoinitiator is one or more of TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide), 2959 (2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone), 1173 (2-hydroxy-2-methyl-1-phenylpropanone), and 184 (1-hydroxycyclohexyl phenyl ketone). The dosage of the photoinitiator in step S2 is 0.5-2% of the mass of the first type of hydrogen bond donor, and the dosage of the photoinitiator in step S5 is 0.5-2% of the mass of the second type of hydrogen bond donor.

[0021] In one embodiment, the crosslinking agent is one or more of polyethylene glycol diacrylate, dipropylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol phthalate diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc. The dosage of the crosslinking agent in step S2 is 0.5-2% of the first type of hydrogen bond donor.

[0022] The all-solid-state double-network ion-conductive elastomer prepared by the preparation method.

[0023] In one embodiment, the all-solid-state double-network ion-conductive elastomer is a conductive elastomer with self-healing properties; and / or the all-solid-state double-network ion-conductive elastomer has a light transmittance greater than 90% in the wavelength range of 400-800 nm; and / or the solid-state double-network ion-conductive elastomer has a conductivity greater than 4×10 -3 S m -1 ; and / or the toughness of the solid-state double-network ion-conductive elastomer is greater than 150 MJ / m 3 ; and / or the Young's modulus of the solid-state double-network ion-conductive elastomer is greater than 10 MPa; and / or the strength of the solid-state double-network ion-conductive elastomer is greater than 13 MPa, and the fracture strain is greater than 2000%.

[0024] On the other hand, the present invention also discloses the application of the all-solid-state double-network ion-conductive elastomer in the fields of flexible electronic devices, wearable devices or sensors.

[0025] The beneficial effects of the present invention are as follows: The invention regulates the polymer network of the all-solid-state ion-conductive elastomer through a dual-network strategy, prepares the first network and the second network with specific hydrogen bond donors and hydrogen bond acceptors, and constructs a highly compatible hydrogen bond and cooperative cross-linking structure between the rigid network and the flexible network of the supramolecular eutectic polymer, significantly reducing the performance difference between the two phases and effectively reducing the stress concentration at the interface, thereby significantly improving the structural stability and overall mechanical properties of the material; both networks in the present invention are composed of supramolecular eutectic polymers, and their good chemical compatibility enables the material to deform synchronously under stress, avoiding local failure problems. This design not only achieves a balance of high strength, high stretchability and high toughness, but also endows the material with excellent environmental stability, providing an ideal material basis for the development of flexible electronic devices; the all-solid-state dual-network ion-conductive elastomer described in the present invention has excellent light transmittance, self-healing properties, excellent mechanical properties, electrical properties and environmental stability properties, and can be used to solve the contradiction between the strength and stretchability of all-solid-state ion-conductive elastomers, and is applicable to fields such as flexible electronic devices, wearable devices, and sensors. Description of the Drawings

[0026] Figure 1 For the synthesis and characterization of the single network in Example 1.

[0027] Figure 2 For the synthesis and characterization of the all-solid-state dual-network ion-conductive elastomer in Example 1.

[0028] Figure 3 For the optical photograph of the first network gel in Comparative Example 5, and this substance cannot polymerize.

[0029] Figure 4 For the headspace gas chromatogram of the all-solid-state dual-network ion-conductive elastomers in Examples 1 and 2.

[0030] Figure 5 For the optical property diagrams of the all-solid-state dual-network ion-conductive elastomers in Examples 1 to 4.

[0031] Figure 6 For the conductivity diagrams of the all-solid-state dual-network ion-conductive elastomers in Examples 1 to 4.

[0032] Figure 7 For the electrical self-healing property diagram of the all-solid-state dual-network ion-conductive elastomer in Example 1.

[0033] Figure 8 For the mechanical property diagrams of the all-solid-state dual-network ion-conductive elastomers in Examples 1 and 2. Detailed Embodiments

[0034] To make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the embodiments of the present invention in detail.

[0035] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0036] During the research process, the inventors found that: Conductive elastomers with high transparency can be prepared using eutectic solvents of a specific system. However, there are still deficiencies in the mechanical properties of the conductive elastomers, especially it is difficult to balance and achieve both strength and tensile properties simultaneously.

[0037] Based on the discovery and research of the above problems, this application is proposed.

[0038] In one embodiment of this application, the first aspect of this application provides a method for preparing an all-solid-state double-network ionic conductive elastomer, including the following steps:

[0039] S1. Mix a first type of hydrogen bond donor, a hydrogen bond acceptor, and a volatile polar solvent evenly by stirring at room temperature to obtain a polymerizable eutectic solvent for the first network;

[0040] S2. Add an initiator and a crosslinking agent to the polymerizable eutectic solvent for the first network, and continue to stir evenly to obtain a prepolymer solution for the first network;

[0041] S3. Irradiate the obtained prepolymer solution for the first network with ultraviolet light to obtain a first network gel;

[0042] S4. Mix a second type of hydrogen bond donor and a hydrogen bond acceptor evenly by stirring at 50-80 °C to obtain a polymerizable eutectic solvent for the second network;

[0043] S5. Add an initiator to the polymerizable eutectic solvent for the second network, and continue to stir evenly to obtain a prepolymer solution for the second network;

[0044] S6. Put the first network gel obtained in step S3 into the prepolymer solution for the second network prepared in step S5, place it in the dark, displace for 96-120 h, cure it by ultraviolet light irradiation, and then place the sample in an oven to dry to obtain an all-solid-state double-network ionic conductive elastomer;

[0045] Wherein, the first hydrogen bond donor includes a hard monomer containing a C═C double bond, the second type of hydrogen bond donor includes a soft monomer containing a C═C double bond, and the hydrogen bond acceptor is a quaternary ammonium salt;

[0046] The molar ratio of the first hydrogen bond donor, hydrogen bond acceptor, and volatile polar solvent is (2-3):1:(4-10), and the molar ratio of the second hydrogen bond donor to the hydrogen bond acceptor is 2:(0.4-1);

[0047] Among them, in step S6, the amounts of the prepolymer solution of the second network and the first network gel are such that the first network gel is completely immersed in the prepolymer solution of the second network.

[0048] When the inventors explored and screened the hydrogen bond donors of the first network and the second network in the experiment, it was found that only when the network of the eutectic polymer formed by the hard monomer containing a C=C double bond and the quaternary ammonium salt was used as the first network to provide the basic skeleton support, and the network of the eutectic polymer formed by the soft monomer containing a C=C double bond and the quaternary ammonium salt was used as the second network to endow the material with excellent ductility and stretchability, could a highly compatible hydrogen bond and synergistic cross-linking structure be constructed between the rigid network and the flexible network composed of the two eutectic polymers, significantly reducing the performance difference between the two phases. Finally, the prepared all-solid-state double-network ion conductive elastomer has a strength far higher than that of the existing all-solid-state ion conductive elastomer with ultra-high stretchability (strain > 2000%), good environmental stability, and also has comprehensive other properties such as high transparency (light transmittance), ion conductivity, and self-healing properties.

[0049] In any embodiment, the hard monomer containing a C=C double bond is one or more of N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide, and acrylamide.

[0050] In any embodiment, the soft monomer containing a C=C double bond is acrylic acid and / or itaconic acid.

[0051] In any embodiment, the quaternary ammonium salt is choline chloride and / or choline dihydrogen citrate.

[0052] In any embodiment, the volatile polar solvent is anhydrous ethanol and / or methanol.

[0053] Furthermore, the photoinitiator is one or more of TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide), 2959 (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone), 1173 (2-hydroxy-2-methyl-1-phenylpropanone), 184 (1-hydroxycyclohexyl phenyl ketone). The amount of the photoinitiator in step S2 is 0.5-2% of the mass of the first type of hydrogen bond donor, and the amount of the photoinitiator in step S5 is 0.5-2% of the mass of the second type of hydrogen bond donor.

[0054] Further, the crosslinking agent is one or more of polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol phthalate diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc. The dosage of the crosslinking agent in step S2 is 0.5 - 2% of the mass of the first type of hydrogen - bond donor.

[0055] The second aspect of the present application provides a fully - solid - state double - network ion - conductive elastomer prepared by the above - mentioned preparation method.

[0056] More specifically, the fully - solid - state double - network ion - conductive elastomer is a conductive elastomer with self - healing properties.

[0057] More specifically, the light transmittance of the fully - solid - state double - network ion - conductive elastomer in the wavelength range of 400 - 800 nm is greater than 90%.

[0058] More specifically, the conductivity of the solid - state double - network ion - conductive elastomer is greater than 4×10 -3 S m -1 。

[0059] More specifically, the toughness of the solid - state double - network ion - conductive elastomer is greater than 150 MJ / m 3 。

[0060] More specifically, the Young's modulus of the solid - state double - network ion - conductive elastomer is greater than 10 MPa.

[0061] Particularly, the strength of the solid - state double - network ion - conductive elastomer is greater than 13 MPa, and the fracture strain is greater than 2000%.

[0062] More preferably, the molar ratio of the first hydrogen - bond donor, hydrogen - bond acceptor, and volatile polar solvent is (2 - 3):1:(4 - 8), for example, it can be 3:1:4, 3:1:6, 3:1:8, 2:1:8, 2.5:1:8, etc.

[0063] More preferably, the molar ratio of the second hydrogen - bond donor and hydrogen - bond acceptor is 2:(0.5 - 1), for example, it can be 2:0.5, 2:0.8, 2:1, etc.

[0064] The second aspect of the present application provides the application of the fully - solid - state double - network ion - conductive elastomer in the fields of flexible electronic devices, wearable devices, or sensors. Since the prepared fully - solid - state double - network ion - conductive elastomer has excellent light transmittance, self - healing performance, and electrical properties, and also has excellent mechanical properties, and can achieve the balance of high strength, high stretchability, and high toughness, the fully - solid - state double - network ion - conductive elastomer can be applied in the fields of flexible electronic devices, wearable devices, or sensors.

[0065] Example

[0066] The following examples more specifically describe the content disclosed in the present application. These examples are only for illustrative purposes, because various modifications and changes within the scope of the present application disclosure are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available. Example 1

[0067] A fully solid-state double-network ion-conductive elastomer is prepared as follows:

[0068] S1. Stir 6.9 g of N-hydroxyethylacrylamide as a hydrogen bond donor, 2.78 g of choline chloride as a hydrogen bond acceptor, and 5.52 g of absolute ethanol at room temperature for 20 min to mix evenly, obtaining a polymerizable deep eutectic solvent for the first network.

[0069] S2. Add 0.069 g of a photoinitiator (photoinitiator TPO) and 0.069 g of a crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent for the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network.

[0070] S3. Irradiate the prepolymer solution for the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel.

[0071] S4. Heat and stir 14.4 g of acrylic acid as a hydrogen bond donor and 13.9 g of choline chloride as a hydrogen bond acceptor at 60 °C for 60 min to mix evenly, obtaining a polymerizable deep eutectic solvent for the second network.

[0072] S5. Add 0.144 g of a photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent for the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution for the second network.

[0073] S6. Place the first network gel obtained in step S3 into the prepolymer solution for the second network prepared in step S5 (the first network gel is completely immersed in the prepolymer solution for the second network), place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ion-conductive elastomer. Example 2

[0074] A fully solid-state double-network ionic conductive elastomer, and its preparation process is as follows:

[0075] S1. Mix 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor, and 7.36 g of absolute ethanol at room temperature with stirring for 20 min to obtain a polymerizable eutectic solvent for the first network;

[0076] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable eutectic solvent for the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network;

[0077] S3. Irradiate the prepolymer solution for the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0078] S4. Mix 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C with heating and stirring for 60 min to obtain a polymerizable eutectic solvent for the second network;

[0079] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable eutectic solvent for the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution for the second network.

[0080] S6. Place the first network gel obtained in step S3 into the prepolymer solution for the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ionic conductive elastomer. Example 3

[0081] A fully solid-state double-network ionic conductive elastomer, and its preparation process is as follows:

[0082] S1. Mix 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor, and 3.84 g of methanol at room temperature with stirring for 20 min to obtain a polymerizable eutectic solvent for the first network;

[0083] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable eutectic solvent for the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network;

[0084] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first network gel;

[0085] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix them evenly, obtaining the polymerizable deep eutectic solvent of the second network;

[0086] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0087] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C to dry for 12 hours to finally obtain the all-solid dual-network ion conductive elastomer. Example 4

[0088] An all-solid dual-network ion conductive elastomer, and its preparation process is as follows:

[0089] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor and 5.12 g of methanol at room temperature for 20 min to mix them evenly, obtaining the polymerizable deep eutectic solvent of the first network;

[0090] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain the prepolymer solution of the first network;

[0091] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first network gel;

[0092] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix them evenly, obtaining the polymerizable deep eutectic solvent of the second network;

[0093] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0094] S6. Place the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ion-conductive elastomer. Example 5

[0095] A fully solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0096] S1. Stir 4.2 g of acrylamide as a hydrogen bond donor, 2.78 g of choline chloride as a hydrogen bond acceptor, and 5.52 g of absolute ethanol at room temperature for 20 min to mix evenly to obtain a polymerizable deep eutectic solvent for the first network;

[0097] S2. Add 0.042 g of a photoinitiator (photoinitiator TPO) and 0.042 g of a crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue to stir for 20 min to obtain a prepolymer solution of the first network;

[0098] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0099] S4. Heat and stir 14.4 g of acrylic acid as a hydrogen bond donor and 13.9 g of choline chloride as a hydrogen bond acceptor at 60 °C for 60 min to mix evenly to obtain a polymerizable deep eutectic solvent for the second network;

[0100] S5. Add 0.144 g of a photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue to stir for 60 min to obtain a prepolymer solution of the second network.

[0101] S6. Place the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ion-conductive elastomer. Example 6

[0102] A fully solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0103] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as a hydrogen bond donor, 5.9 g of choline dihydrogen citrate as a hydrogen bond acceptor, and 5.12 g of methanol at room temperature for 20 min to mix evenly to obtain a polymerizable deep eutectic solvent for the first network;

[0104] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution of the first network;

[0105] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0106] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix evenly, obtaining a polymerizable deep eutectic solvent of the second network;

[0107] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution of the second network.

[0108] S6. Place the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ionic conductive elastomer. Example 7

[0109] A fully solid-state double-network ionic conductive elastomer is prepared as follows:

[0110] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor and 5.12 g of methanol at room temperature for 20 min to mix evenly, obtaining a polymerizable deep eutectic solvent of the first network;

[0111] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution of the first network;

[0112] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0113] S4. Heat and stir 19 g of itaconic acid as the hydrogen bond donor and 10.2 g of choline chloride at 60 °C for 60 min to mix evenly, obtaining a polymerizable deep eutectic solvent of the second network;

[0114] S5. Add 0.19 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0115] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain the all-solid-state double-network ion-conductive elastomer. Example 8

[0116] An all-solid-state double-network ion-conductive elastomer is prepared as follows:

[0117] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor, and 5.12 g of methanol at room temperature for 20 min to mix evenly to obtain the polymerizable deep eutectic solvent of the first network;

[0118] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain the prepolymer solution of the first network;

[0119] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first network gel;

[0120] S4. Heat and stir 19 g of itaconic acid as the hydrogen bond donor and 21.4 g of choline dihydrogen citrate as the hydrogen bond acceptor at 60 °C for 60 min to mix evenly to obtain the polymerizable deep eutectic solvent of the second network;

[0121] S5. Add 0.19 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0122] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain the all-solid-state double-network ion-conductive elastomer. Example 9

[0123] An all-solid-state double-network ion-conductive elastomer is prepared as follows:

[0124] S1. Mix 4.6 g of N - hydroxyethylacrylamide as the hydrogen - bond donor, 2.78 g of choline chloride as the hydrogen - bond acceptor, and 7.36 g of absolute ethanol evenly by stirring at room temperature for 20 min to obtain the polymerizable deep - eutectic solvent of the first network;

[0125] S2. Add 0.032 g of photo - initiator (photo - initiator 2959) and 0.032 g of cross - linker (tripropylene glycol diacrylate) to the polymerizable deep - eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain the prepolymer solution of the first network;

[0126] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first - network gel;

[0127] S4. Mix 14.4 g of acrylic acid as the hydrogen - bond donor and 13.9 g of choline chloride as the hydrogen - bond acceptor evenly by heating and stirring at 60 °C for 60 min to obtain the polymerizable deep - eutectic solvent of the second network;

[0128] S5. Add 0.072 g of photo - initiator (photo - initiator 2959) to the polymerizable deep - eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0129] S6. Put the first - network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain the all - solid double - network ionic conductive elastomer. Example 10

[0130] An all - solid double - network ionic conductive elastomer, and its preparation process is as follows:

[0131] S1. Mix 6.9 g of N - hydroxyethylacrylamide as the hydrogen - bond donor, 2.78 g of choline chloride as the hydrogen - bond acceptor, and 3.68 g of absolute ethanol evenly by stirring at room temperature for 20 min to obtain the polymerizable deep - eutectic solvent of the first network;

[0132] S2. Add 0.138 g of photo - initiator (photo - initiator TPO) and 0.138 g of cross - linker (polyethylene glycol diacrylate) to the polymerizable deep - eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain the prepolymer solution of the first network;

[0133] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first - network gel;

[0134] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix them evenly, obtaining a polymerizable deep eutectic solvent for the second network;

[0135] S5. Add 0.288 g of a photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent for the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution for the second network.

[0136] S6. Place the first network gel obtained in step S3 into the prepolymer solution for the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C and dry it for 12 hours to finally obtain a fully solid dual-network ion conductive elastomer. Example 11

[0137] A fully solid dual-network ion conductive elastomer, and its preparation process is as follows:

[0138] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor and 9.2 g of absolute ethanol at room temperature for 20 min to mix them evenly, obtaining a polymerizable deep eutectic solvent for the first network;

[0139] S2. Add 0.069 g of a photoinitiator (photoinitiator TPO) and 0.069 g of a crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent for the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network;

[0140] S3. Irradiate the prepolymer solution for the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0141] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 6.95 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix them evenly, obtaining a polymerizable deep eutectic solvent for the second network;

[0142] S5. Add 0.144 g of a photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent for the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution for the second network.

[0143] S6. Place the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ion-conductive elastomer. Example 12

[0144] A fully solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0145] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as a hydrogen bond donor, 2.78 g of choline chloride as a hydrogen bond acceptor, and 7.36 g of absolute ethanol at room temperature for 20 min to mix evenly to obtain a polymerizable deep eutectic solvent for the first network;

[0146] S2. Add 0.069 g of a photoinitiator (photoinitiator TPO) and 0.069 g of a crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue to stir for 20 min to obtain a prepolymer solution of the first network;

[0147] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0148] S4. Heat and stir 14.4 g of acrylic acid as a hydrogen bond donor and 5.6 g of choline chloride as a hydrogen bond acceptor at 60 °C for 60 min to mix evenly to obtain a polymerizable deep eutectic solvent for the second network;

[0149] S5. Add 0.144 g of a photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue to stir for 60 min to obtain a prepolymer solution of the second network.

[0150] S6. Place the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ion-conductive elastomer. Comparative Example 1

[0151] A fully solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0152] S1. Stir 7.8 g of itaconic acid as a hydrogen bond donor, 2.78 g of choline chloride as a hydrogen bond acceptor, and 5.52 g of absolute ethanol at room temperature for 20 min to mix evenly to obtain a polymerizable deep eutectic solvent for the first network;

[0153] S2. Add 0.078 g of photoinitiator (photoinitiator TPO) and 0.078 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution of the first network;

[0154] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0155] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix evenly, and obtain a polymerizable deep eutectic solvent of the second network;

[0156] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution of the second network.

[0157] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, and perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain a fully solid-state double-network ionic conductive elastomer. Comparative Example 2

[0158] A fully solid-state double-network ionic conductive elastomer, and its preparation process is as follows:

[0159] S1. Stir 6.9 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor and 5.52 g of absolute ethanol at room temperature for 20 min to mix evenly, and obtain a polymerizable deep eutectic solvent of the first network;

[0160] S2. Add 0.069 g of photoinitiator (photoinitiator TPO) and 0.069 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution of the first network;

[0161] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first network gel;

[0162] S4. Heat and stir 14.2 g of acrylamide as the hydrogen bond donor and 13.9 g of choline chloride at 60 °C for 60 min to mix evenly, and obtain a polymerizable deep eutectic solvent of the second network;

[0163] S5. Add 0.142 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0164] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain the all-solid-state double-network ion-conductive elastomer. Comparative Example 3

[0165] An all-solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0166] S1. Stir 2.3 g of N-hydroxyethyl acrylamide as the hydrogen bond donor, 2.78 g of choline chloride as the hydrogen bond acceptor, and 5.52 g of absolute ethanol at room temperature for 20 min to mix evenly to obtain the polymerizable deep eutectic solvent of the first network;

[0167] S2. Add 0.023 g of photoinitiator (photoinitiator TPO) and 0.023 g of crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain the prepolymer solution of the first network;

[0168] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain the first network gel;

[0169] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen bond donor and 13.9 g of choline chloride as the hydrogen bond acceptor at 60 °C for 60 min to mix evenly to obtain the polymerizable deep eutectic solvent of the second network;

[0170] S5. Add 0.144 g of photoinitiator (photoinitiator TPO) to the polymerizable deep eutectic solvent of the second network obtained in step S4, and continue stirring for 60 min to obtain the prepolymer solution of the second network.

[0171] S6. Put the first network gel obtained in step S3 into the prepolymer solution of the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain the all-solid-state double-network ion-conductive elastomer. Comparative Example 4

[0172] An all-solid-state double-network ion-conductive elastomer, and its preparation process is as follows:

[0173] S1. Mix 6.9 g of N - hydroxyethylacrylamide as the hydrogen - bond donor, 2.78 g of choline chloride as the hydrogen - bond acceptor, and 5.52 g of absolute ethanol at room temperature with stirring for 20 min to obtain a polymerizable deep - eutectic solvent for the first network;

[0174] S2. Add 0.069 g of photoinitiator (TPO) and 0.069 g of cross - linker (polyethylene glycol diacrylate) to the polymerizable deep - eutectic solvent for the first network obtained in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network;

[0175] S3. Irradiate the prepolymer solution for the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first - network gel;

[0176] S4. Heat and stir 14.4 g of acrylic acid as the hydrogen - bond donor and 20.94 g of choline chloride as the hydrogen - bond acceptor at 60 °C for 60 min to obtain a polymerizable deep - eutectic solvent for the second network;

[0177] S5. Add 0.144 g of photoinitiator (TPO) to the polymerizable deep - eutectic solvent for the second network obtained in step S4, and continue stirring for 60 min to obtain a prepolymer solution for the second network.

[0178] S6. Place the first - network gel obtained in step S3 into the prepolymer solution for the second network prepared in step S5, place it in the dark, perform solvent replacement for 96 - 120 h. After the replacement is completed, irradiate it with ultraviolet light (48 w) for 20 min for curing, and then place the sample in an oven at 60 °C for drying for 12 hours to finally obtain an all - solid dual - network ionic conductive elastomer. Comparative Example 5

[0179] An all - solid dual - network ionic conductive elastomer, and its preparation process is as follows:

[0180] S1. Mix 6.9 g of N - hydroxyethylacrylamide as the hydrogen - bond donor, 2.78 g of choline chloride as the hydrogen - bond acceptor, and 13.8 g of absolute ethanol at room temperature with stirring for 20 min to obtain a polymerizable deep - eutectic solvent for the first network;

[0181] S2. Add 0.069 g of photoinitiator (TPO) and 0.069 g of cross - linker (polyethylene glycol diacrylate) to the polymerizable deep - eutectic solvent for the first network obtained in step S1, and continue stirring for 20 min to obtain a prepolymer solution for the first network;

[0182] S3. Irradiate the prepolymer solution for the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min, and it remains in a solution state. Comparative Example 6

[0183] A fully solid single-network ion-conductive elastomer is prepared as follows:

[0184] S1. Mix 6.9 g of N-hydroxyethyl acrylamide as a hydrogen bond donor, 2.78 g of choline chloride as a hydrogen bond acceptor, and stir at room temperature for 20 min to obtain a polymerizable deep eutectic solvent for the first network;

[0185] S2. Add 0.069 g of a photoinitiator (photoinitiator TPO) and 0.069 g of a crosslinking agent (polyethylene glycol diacrylate) to the polymerizable deep eutectic solvent of the first network in step S1, and continue stirring for 20 min to obtain a prepolymer solution of the first network;

[0186] S3. Irradiate the prepolymer solution of the first network obtained in step S2 with UV ultraviolet light (48 W) for 10 min to obtain a first-network ion-conductive elastomer.

[0187] Performance testing

[0188] Perform the following performance tests on the products prepared in Examples 1 to 12 and Comparative Examples 1 to 6.

[0189] (1) Synthesis structure characterization of single-network PDES

[0190] The fully solid double-network ion-conductive elastomer uses N-hydroxyethyl acrylamide-choline chloride (HEAA-ChCl) type supramolecular deep eutectic polymer or acrylamide-choline chloride type supramolecular deep eutectic polymer or N-hydroxyethyl acrylamide-dihydrogen citrate choline type supramolecular deep eutectic polymer as the rigid first network to provide a high-strength support framework. At the same time, acrylic acid-choline chloride (AA-ChCl) type supramolecular deep eutectic polymer or itaconic acid-choline chloride supramolecular deep eutectic polymer or itaconic acid-dihydrogen citrate choline type supramolecular deep eutectic polymer is used as the flexible second network, which is rich in dense hydrogen bonds to enhance stretchability. The deep eutectic solvent (PDES) is used to obtain the supramolecular deep eutectic polymer by in-situ polymerization. To further confirm the synthesis of the two single-network PDES, taking Example 1 as an example, the two single-network PDES of the sample are characterized by infrared spectroscopy analysis, nuclear magnetic resonance testing, and DCS testing respectively. Among them Figure 1 (a) shows the optical pictures of AA-ChCl and HEAA-ChCl type PDES in Example 1. The two single-network PDES are clear and transparent liquids within a certain temperature range, without solid impurities, precipitation or insoluble substances. Figure 1 (c) is the infrared spectroscopy analysis curve of AA-ChCl type PDES. The curve shows that before and after the mixing of PDES, at 1640 cm -1The C=C double bond stretching vibration peak at 1717cm -1 is the stretching vibration peak of the carbonyl group of carboxylic acid, indicating that the AA component still exists in the form of carboxylic acid rather than molten salt in the PDES prepolymer. Figure 1 (b) is the infrared spectrum analysis curve of HEAA-ChCl type PDES. It can be seen that 1650cm -1 It is the carbonyl stretching vibration peak of secondary amide, 1630cm -1 The left and right sides are the stretching vibration of C=C, 1540cm -1 is the bending vibration of CNH, and the secondary amide is at 1300 cm -1 There is a characteristic peak "amide III peak" nearby, which includes a mixed peak of CN stretching vibration absorption and NH bending vibration absorption. Figure 1 (d) shows the H NMR spectra of AA-ChCl type PDES and HEAA-ChCl type PDES. The corresponding chemical shifts of each component in the PDES prepolymer can be found in the spectrum. Due to the influence of hydrogen bond interactions, the hydrogen chemical shifts of each component move toward the low field direction. Figure 1 e and 1f show that the melting point of HEAA-ChCl type PDES mixed solution is -50℃, which is lower than the melting points of single components N-hydroxyethyl acrylamide (-2℃) and choline chloride (305℃). The melting point of AA-ChCl type PDES mixed solution is -6.5℃, which is lower than the melting points of single components acrylic acid (13.5℃) and choline chloride (305℃). Therefore, both the appearance and internal performance can prove that two single-network supramolecular PDES prepolymers have been successfully prepared.

[0191] (2) Synthesis and structural characterization of double network all-solid-state ion-conducting elastomers

[0192] To further confirm the successful preparation of the all-solid-state double network ion conductive elastomer, the prepared all-solid-state double network ion conductive elastomer was characterized by infrared spectroscopy analysis, nuclear magnetic resonance testing, DCS testing, AFM, and SEM. Taking Example 1 as an example, as shown in Figure 2(a), the infrared spectroscopy characterization results of the all-solid-state double network ion conductive elastomer prepared in Example 1 further prove the successful formation of the double network structure. 1650cm -1 It is the carbonyl stretching vibration peak of the secondary amide of N-hydroxyethyl acrylamide, 1540 cm -1 is the bending vibration of CNH, 1717cm -1 It is the characteristic peak of the stretching vibration of the C=O bond of acrylic acid. In the prepared all-solid-state double network ion conductive elastomer, the peaks at 1540 cm -1 、1650cm- 1Characteristic peaks at 1717 cm-1 indicate that these two supramolecular eutectic polymers successfully coexist in the same network structure. The coexistence and intensity distribution of the characteristic peaks clearly demonstrate the successful integration of these two components and their effective crosslinking in the double-network structure. As Figure 2 (b) shows the glass transition temperatures (T g ) of Examples 1 and 2. This trend is jointly caused by the increased chain segment flexibility, enhanced molecular chain freedom, reduced internal stress, and adjustment of the network structure. As Figure 2 (c) shows the thermogravimetric curves of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 and 2, indicating that the prepared all-solid-state double-network ion-conductive elastomers can be safely used up to 200 °C and have good thermal stability. As Figure 2 (d) The X-ray diffraction pattern (XRD) shows that the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 and 2 have a broad diffraction peak at 2θ ≈ 21°, proving that this type of elastomer is a non-crystalline material. As Figure 2 (e) The phase image of the atomic force microscope (AFM) shows that the phase diagram of the all-solid-state double-network ion-conductive elastomer prepared in Example 1 presents an obvious boundary between the hard (poly(HEAA-ChCl) type supramolecular deep eutectic polymer; bright area) network and the soft (poly(AA-ChCl) type supramolecular deep eutectic polymer; dark area) network. As Figure 2 (f) Scanning electron microscope (SEM) imaging shows that it can indicate the uniformity of the all-solid-state double-network ion-conductive elastomer prepared in Example 1. As Figure 3 shown, for Comparative Example 5, since the content of ethanol in the prepared first network is too high to polymerize to form a gel, the final all-solid-state double-network ion-conductive elastomer cannot be formed.

[0193] (3) No volatile solvents (methanol, ethanol)

[0194] Testing method: To further confirm that the samples do not contain ethanol and methanol, headspace internal standard gas chromatography was used to characterize the samples. After testing, no ethanol peak or methanol peak was observed in the products obtained in Examples 1-12, and no ethanol or methanol signal was detected, proving that the ethanol and methanol contents are almost zero, indicating that there is no methanol or ethanol residue in these samples. Therefore, the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 to 12 do not contain methanol or ethanol. Taking Examples 1 and 2 as examples, as Figure 4 shown is the ethanol content test of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 and 2. The three curves of 100 mg / L, 200 mg / L, and 300 mg / L represent three different concentrations of ethanol standard solutions, and the peak intensity increases with the increase in ethanol concentration because the higher the ethanol concentration, the stronger the signal.

[0195] (4) Transparency

[0196] Test method: The light transmittance (transmittance) was recorded on an ultraviolet-visible (UV-vis) spectrometer. A spline with a transmission thickness of 1.5 mm was measured, and the wavelength range of the transmitted light was 400 - 800 nm. After testing, the transmittance of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 to 12 was greater than 90%, and they were all transparent elastomers. When placed on a piece of paper with printed characters, the characters on the paper could be clearly seen. As Figure 5 shown in the optical property diagrams of the all-solid-state double-network ion-conductive elastomers of Examples 1 to 4, where Figure 5 (a) is the digital optical photo of the all-solid-state double-network ion-conductive elastomer of Example 1 and the paper with printed characters, Figure 5 (b) is the optical transmittance diagram of the all-solid-state double-network ion-conductive elastomers of Examples 1 to 4. The same transmittance test was carried out on Comparative Examples 1 - 4 and Comparative Example 6. The transmittance of the ion-conductive elastomers prepared in Comparative Examples 1 - 4 and Comparative Example 6 was also greater than 90%.

[0197] (5) Conductivity test

[0198] The all-solid-state double-network ion-conductive elastomers prepared by the present invention have excellent conductivity and electrical self-healing properties. The electrochemical impedance spectroscopy method was used to measure its ionic conductivity. The 10×10×1 mm 3 all-solid-state double-network ion-conductive elastomer was sandwiched between two copper electrodes, and an AC impedance test was carried out on an electrochemical workstation, and then its conductivity was calculated. The test results show that the conductivity performance of the all-solid-state double-network ion-conductive elastomers of Examples 1 to 12 changed little overall, and the conductivity was greater than 4×10 -3 S m -1 . During the test process, it was also found that with the same preparation raw materials, different amounts of volatile polar solvents would affect the mass ratio of the first network and the second network. The conductivity of Example 2 was greater than that of Example 1, and the conductivity of Example 4 was greater than that of Example 3. As Figure 6 shown in the conductivity comparison diagram of the all-solid-state double-network ion-conductive elastomers of Examples 1 to 4. In addition, a self-healing performance test was also carried out during the experiment: The all-solid-state double-network ion-conductive elastomers prepared in Examples 1 to 12 were cut with a blade, and then the cut all-solid-state double-network ion-conductive elastomers were spliced together. The experimental results showed that the two spliced all-solid-state double-network ion-conductive elastomers would immediately bond together by themselves, and the circuit would be reconnected to emit light, indicating that the prepared all-solid-state double-network ion-conductive elastomers have excellent electrical self-healing properties. As Figure 7The optical photo shows that the all-solid-state double-network ion-conductive elastomer prepared in Example 1 can still make the circuit emit light again after being cut and reconnected. The same electrochemical performance tests were carried out on Comparative Examples 1-4 and Comparative Example 6, and the conductivities of the prepared ion-conductive elastomers were all less than 2×10 -3 S m -1 .

[0199] (6) Mechanical property test

[0200] Tensile tests were carried out using a universal material testing machine at a test rate of 10 mm / min. It was found experimentally that the mechanical properties of the all-solid-state double-network ion-conductive elastomers of Examples 1 to 12 were greatly improved. The strength of the obtained all-solid-state double-network ion-conductive elastomers was greater than 13 MPa, the tensile strain was greater than 2000%, and the toughness was greater than 150 MJ / m 3 , and the Young's modulus was greater than 10 MPa. As Figure 8 shows the mechanical properties of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1-2. As Figure 8 (a) is the stress-strain curve of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 and 2. As Figure 8 (b) is the statistical chart of the toughness and Young's modulus of the all-solid-state double-network ion-conductive elastomers prepared in Examples 1 and 2. The above mechanical property tests were carried out on Comparative Examples 1-4 and Comparative Example 6. The strength of Comparative Examples 1-4 was less than 7 MPa, the fracture strain was less than 1200%, the toughness was less than 70 MJ / m 3 , and the Young's modulus was less than 10 MPa. The strength of Comparative Example 6 was 15 MPa, but the fracture strain was less than 800%. Although the Young's modulus was greater than 10 MPa, the toughness was less than 90 MJ / m 3 .

[0201] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the technical solutions of the present invention, rather than limitations on the specific implementation manners of the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the claims of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A method for preparing an all-solid-state double-network ion-conductive elastomer, characterized in that: The steps include: S1, stirring and mixing the first type of hydrogen bond donor, hydrogen bond acceptor and volatile polar solvent at room temperature to obtain a polymerizable low eutectic solvent of the first network; S2, adding an initiator and a cross-linking agent to the polymerizable low eutectic solvent of the first network, and continuing to stir evenly to obtain a prepolymer solution of the first network; S3, irradiating the obtained first network prepolymer solution under ultraviolet light to obtain a first network gel; S4, stirring and mixing the second type of hydrogen bond donor and hydrogen bond acceptor at 50-80° C. to obtain a polymerizable low eutectic solvent of the second network; S5, adding an initiator to the polymerizable low eutectic solvent of the second network, and continuing to stir evenly to obtain a prepolymer solution of the second network; S6, placing the first network gel obtained in step S3 into the second network prepolymer solution prepared in step S5, placing it away from light, replacing it for 96-120 hours, curing it under ultraviolet light, and then placing the sample in an oven to dry, to obtain a fully solid double network ion conductive elastomer; wherein the first hydrogen bond donor comprises a hard monomer containing a C=C double bond, the second type of hydrogen bond donor comprises a soft monomer containing a C=C double bond, and the hydrogen bond acceptor is a quaternary ammonium salt; The molar ratio of the first hydrogen bond donor, the hydrogen bond acceptor, and the volatile polar solvent is (2-3):1:(4-10), and the molar ratio of the second hydrogen bond donor and the hydrogen bond acceptor is 2:(0.4-1); Wherein, in step S6, the amounts of the second network prepolymer solution and the first network gel are such that the first network gel is completely immersed in the second network prepolymer solution.

2. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The hard monomer containing a C=C double bond is one or more of N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide and acrylamide.

3. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The soft monomer containing a C=C double bond is acrylic acid and / or itaconic acid.

4. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The quaternary ammonium salt is choline chloride and / or choline dihydrogen citrate.

5. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The volatile polar solvent is anhydrous ethanol and / or methanol.

6. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone. The amount of the photoinitiator in step S2 is 0.5-2% of the mass of the first type of hydrogen bond donor, and the amount of the photoinitiator in step S5 is 0.5-2% of the mass of the second type of hydrogen bond donor.

7. The method for preparing the all-solid-state double network ion conductive elastomer according to claim 1, characterized in that: The crosslinking agent is one or more of tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol phthalate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. The amount of the crosslinking agent used in step S2 is 0.5-2% of the first type hydrogen bond donor.

8. An all-solid-state double-network ion-conductive elastomer prepared by the preparation method according to any one of claims 1 to 7.

9. The all-solid double network ion conductive elastomer according to claim 8, characterized in that: The all-solid-state double-network ion-conductive elastomer is a conductive elastomer with self-healing properties; And / or the all-solid-state double-network ion-conductive elastomer has a light transmittance of greater than 90% in the wavelength range of 400 to 800 nm; and / or the electrical conductivity of the solid double network ion conductive elastomer is greater than 4×10 -3 Sm -1 ; And / or the toughness of the solid double network ion conductive elastomer is greater than 150MJ / m 3 ; and / or the Young's modulus of the solid double network ion conductive elastomer is greater than 10 MPa; And / or the strength of the solid double network ion conductive elastomer is greater than 13 MPa, and the fracture strain is greater than 2000%.

10. Application of the all-solid-state dual-network ion-conductive elastomer according to claim 8 or 9 in the field of flexible electronic devices, wearable devices or sensors.

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