A solid-state ion-conducting elastomer and its preparation method

Abstract

This disclosure provides an all-solid-state ion-conductive elastomer and its preparation method. The all-solid-state ion-conductive elastomer has a three-dimensional interconnected nanostructure. Its raw materials include a polymer monomer, a first lithium salt, a eutectic solution, an initiator, and a crosslinking agent. The polymer monomer is a double-bonded monomer containing dopamine groups and a double-bonded monomer without dopamine groups. The eutectic solution is obtained by mixing a second lithium salt and succinate in a mass ratio of 5–30:34. Both the first lithium salt and the second lithium salt are bis(trifluoromethanesulfonyl)imide lithium salts. The mass ratio of the double-bonded monomer containing dopamine groups, the double-bonded monomer without dopamine groups, the first lithium salt, and the eutectic solution is 20–50:5–15:45–70. The elastomer of this disclosure has excellent conductivity, stability, adhesion, fracture toughness, and self-healing properties, and its ionic conductivity can reach up to 0.1 S / m.

Description

Technical Field

[0001] This disclosure relates to the field of polymer materials technology, and in particular to an all-solid-state ion-conducting elastomer and its preparation method. Background Technology

[0002] As core components of flexible electronic products used in human-computer interaction interfaces and machine sensing, soft conductor materials typically require high stretchability, transparency, rapid self-healing under both dry and wet conditions, stable high conductivity, and sensing properties. Furthermore, since these materials need to adhere closely to the substrate or directly contact the human body, they also require strong adhesion and biocompatibility. Additionally, these sensors are used in extreme environments (such as marine environments and low-temperature environments), so flexible sensor materials should possess certain stability and durability. Unfortunately, to date, no material reported in the literature can simultaneously meet all of these characteristics, which greatly limits the development of flexible sensors and wearable devices. Early research focused on electronically conductive flexible conductor materials with added conductive particles; however, these materials suffer from problems such as uneven filler dispersion, pathway disruption under large strain, and mismatch with the human body's ion-based signal transmission, significantly limiting their applications. However, flexible ionic conductors (i.e., hydrogels, ion-conductive elastomers) perfectly solve these problems and have become a new research hotspot. However, hydrogels are susceptible to performance degradation or failure during use due to the effects of low-temperature water solidification and high-temperature water evaporation. Ionic liquids in ionogels can largely overcome these two problems, but leakage of the ionic liquid occurs when ionogels are compressed, and the material's conductivity contradicts its mechanical properties, significantly impacting its applications. All-solid-state ion-conductive elastomers, however, which contain no liquid, effectively solve these problems, exhibiting excellent environmental stability and durability. However, existing all-solid-state ion-conductive elastomers suffer from weak adhesion, difficulty in underwater self-healing, and low ionic conductivity, limiting their application in flexible electronics. Therefore, endowing all-solid-state ion-conductive elastomers with strong adhesion, excellent underwater self-healing properties, and high ionic conductivity has become an urgent and challenging task. Summary of the Invention

[0003] This disclosure aims to address at least one of the technical problems existing in the prior art.

[0004] Therefore, the all-solid-state ion-conductive elastomer provided in the first aspect of this disclosure contains no solvent and has strong adhesion, excellent mechanical properties, rapid self-healing in dry / wet conditions, and conductivity, with its ion conductivity reaching up to 0.1 S / m.

[0005] The all-solid-state ion-conducting elastomer provided in the first aspect of this disclosure has a three-dimensional interconnected nanostructure. The raw materials of the all-solid-state ion-conducting elastomer include a polymer monomer, a first lithium salt, a eutectic solution, an initiator, and a crosslinking agent.

[0006] The polymer monomers are double-bonded monomers containing dopamine groups and double-bonded monomers that do not contain dopamine groups;

[0007] The eutectic solution is obtained by mixing a second lithium salt and succinic acid in a mass ratio of 5 to 30:34.

[0008] Both the first lithium salt and the second lithium salt are lithium bis(trifluoromethanesulfonyl)imide salts;

[0009] The mass ratio of the dopamine-containing double-bonded monomer, the dopamine-free double-bonded monomer, the first lithium salt, and the eutectic solution is 20–50: 5–15: 45–70.

[0010] Optionally, the double-bonded monomer containing a dopamine group is dopamine methacrylamide, dopamine acrylamide, L-dopa methacrylamide, or L-dopa acrylamide.

[0011] Optionally, the double-bonded monomer that does not contain a dopamine group is an acrylate monomer, which is any one or a mixture of 2-(ethylaminoformyl)acrylate, 2-(butylamino)carbonyloxoacrylate, 2-methoxyethyl acrylate, trifluoroethyl acrylate, hexafluorobutyl acrylate, ethoxyethoxyethyl acrylate, and phenoxyacrylate.

[0012] Optionally, the initiator is photoinitiator 2959 or photoinitiator TPO.

[0013] Optionally, the molar number of the photoinitiator is 0.1% to 1% of the molar number of the polymer monomer.

[0014] Optionally, the crosslinking agent is N,N-bis(acryloyl)cysteine, polyethylene glycol diacrylate, or polyethylene glycol.

[0015] Optionally, the molar number of the crosslinking agent is 0.1% to 1% of the molar number of the polymer monomer.

[0016] Optionally, the eutectic solution is prepared according to the following steps: heating succinate to make it liquid, adding the second lithium salt to the liquid succinate, and ultrasonically mixing to obtain the eutectic solution.

[0017] Optionally, the all-solid-state ion-conductive elastomer has a conductivity as high as 0.1 S / m, an elongation at break of 400% to 700%, a stress-strain self-healing efficiency of 84% to 86% in air, a stress-strain self-healing efficiency of 70% to 171% underwater, and an electrical self-healing efficiency close to 100%.

[0018] The all-solid-state ion-conducting elastomer provided in the first aspect of this disclosure has the following characteristics and beneficial effects:

[0019] The all-solid-state ion-conductive elastomer provided in the first aspect of this disclosure exhibits excellent adhesion properties in both dry and wet states. Qualitative analysis reveals that it generally adheres to various materials such as plastics, carbon fibers, polyimide, and steel plates. The hypothesized mechanism is that phenolic hydroxyl groups, amino groups, -CF3 groups, and oxygen atoms in the material can form hydrogen bonds, π-π interactions, and metal coordination with surface groups, thereby generating the generalized adhesion behavior. Furthermore, the material exhibits excellent mechanical and electrical self-healing properties in both dry and wet states. The self-healing efficiency of the all-solid-state ion-conductive elastomer provided in this embodiment can reach over 70%, even exceeding 100%, while the self-healing efficiency of its electrical properties in the dry state (e.g., in air) is almost 100%. The self-healing mechanism is speculated to involve the formation of hydrogen bonds between the phenolic hydroxyl and amide groups in the dopamine acrylamide monomer and oxygen and fluorine atoms, as well as the formation of bidentate hydrogen bonds within the material structure. This is further supported by the stacking of π-π bonds between the benzene ring and lithium ions, the interaction between π-lithium cations, and the high-density ion-dipole and dipole-dipole interactions formed by the added succinic acrylonitrile group (-CN) with lithium cations, -CF3 groups, and itself. These complex interactions within the system contribute to the material's excellent self-healing properties. Furthermore, the all-solid-state ion-conductive elastomer provided in this embodiment exhibits a high ionic conductivity of up to 0.1 S / m. The speculated mechanism is that the addition of a high succinic acrylonitrile content results in a three-dimensional interconnected structure. The strong and complex interactions between succinic acrylonitrile and lithium salt promote lithium salt dissociation and allow most of the lithium salt to separate into the succinic acrylonitrile phase, forming conductive nanochannels, ultimately leading to the elastomer's high ionic conductivity. Due to its strong adhesion, excellent self-healing properties, and high ionic conductivity, this material is expected to have wide applications in flexible sensors, flexible electrodes, lithium batteries, and supercapacitors.

[0020] The method for preparing an all-solid-state ion-conducting elastomer provided in the second aspect of this disclosure includes:

[0021] The initiator, the crosslinking agent, the first lithium salt, and the eutectic solution are added to the polymer monomer and stirred evenly by ultrasonication to obtain a homogeneous precursor solution. The all-solid-state ion-conductive elastomer is then obtained through polymerization.

[0022] The method for preparing an all-solid-state ion-conducting elastomer provided in the second aspect of this disclosure has the following characteristics and excellent properties:

[0023] The preparation method provided in the second aspect of this disclosure synthesizes an all-solid-state ion-conducting elastomer exhibiting strong adhesion, excellent self-healing properties, and a conductivity up to 0.1 S / m in both dry and wet states. Based on the biomimetic principle of mussels and the complex interaction between plastic crystals and lithium salts, a large amount of acrylamide monomers containing dopamine groups are added to the system. Since a large amount of solid is difficult to dissolve, a eutectic solution of succinate and lithium salt is introduced. This promotes solid dissolution and forms a three-dimensional interconnected structure with the polymer matrix, acting as ion channels to significantly improve the ion conductivity of the material. Furthermore, the -CN groups in succinate can interact with -CF3, cations, etc., improving the self-healing efficiency of the material. The preparation method provided in the second aspect of this disclosure involves adding polymer monomers, lithium salts, and a eutectic solution to the system, followed by ultrasonic mixing to obtain a homogeneous and transparent precursor solution. After polymerization, the all-solid-state ion-conducting elastomer is obtained. The precursor solution preparation steps in the second aspect of this disclosure are simple, the polymerization time is short, and the resulting all-solid-state ion-conducting elastomer exhibits excellent mechanical properties and conductivity. Attached Figure Description

[0024] Figure 1 This is a qualitative adhesion characterization diagram of the all-solid-state ion-conductive elastomer prepared in Example 1 of this disclosure in air;

[0025] Figure 2 This is a qualitative self-healing characterization diagram of the all-solid-state ion-conductive elastomer prepared in Example 1 of this disclosure in water;

[0026] Figures 3-6 These are scanning electron microscope spectra of the all-solid-state ion-conducting elastomer prepared in Example 2 of this disclosure at different magnifications;

[0027] Figure 7 This is a characterization diagram of the conductivity of the all-solid-state ion-conductive elastomer material prepared by impedance method in Example 3 of this disclosure;

[0028] Figure 8 This is a qualitative self-healing characterization diagram of the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure in water;

[0029] Figure 9 This is the infrared spectrum of the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure;

[0030] Figure 10 This is an application of the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure in a capacitive strain sensor at the finger joint;

[0031] Figure 11 This is the application of the all-solid-state ion-conductive elastomer prepared in Embodiment 4 of this disclosure in a capacitive strain sensor at the elbow joint;

[0032] Figure 12 This is a characterization diagram of the conductivity of the all-solid-state ion-conductive elastomer material prepared by impedance method in Example 4 of this disclosure;

[0033] Figure 13 This is a quantitative characterization of the self-healing conductivity of the all-solid-state ion-conductive elastomer prepared in Example 5 of this disclosure in air;

[0034] Figure 14 This is a qualitative self-healing characterization diagram of the all-solid-state ion-conductive elastomer prepared in Example 9 of this disclosure in air; Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this application clearer, the application will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of this application.

[0036] Conversely, this application covers any alternatives, modifications, equivalent methods, and schemes made within the spirit and scope of this application as defined by the claims. Furthermore, to provide the public with a better understanding of this application, certain specific details are described in detail below. However, this application can be fully understood by those skilled in the art even without these detailed descriptions.

[0037] The embodiments of this application are described in detail below.

[0038] Example 1:

[0039] The method for preparing an all-solid-state ion-conducting elastomer provided in Embodiment 1 of this disclosure includes the following steps:

[0040] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 3.41g into a 10mL sample bottle and add 1g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0041] (2) Add 1.166g of dopamine acrylamide, 1mL of ethyl 2-(ethylaminoformyl)acrylate, 0.5mL of trifluoroethyl acrylate, 0.72g of LiTFSI salt, 0.0052g of photoinitiator TPO, 0.0116g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 3.47g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0042] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0043] Figure 1 This is a qualitative adhesion characterization diagram of the all-solid-state ion-conductive elastomer prepared in Example 1 of this disclosure in air. The sample exhibits strong adhesion to six materials in air: plastic, carbon fiber, polyimide, steel plate, polyethylene terephthalate, and glass.

[0044] Figure 2 These are qualitative self-healing characterization images of the all-solid-state ion-conductive elastomer prepared in Example 1 of this disclosure in water. In the images, 1 is a photograph of the material after it has been cut, and 2 is a tensile photograph of the cut material after underwater repair. As can be seen from the images, this elastomer exhibits excellent self-healing performance in water, achieving approximately 100% tensile strength within a 15-second repair time.

[0045] Example 2:

[0046] The preparation method of the all-solid-state ion-conducting elastomer provided in Embodiment 2 of this disclosure includes the following steps:

[0047] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 6.82g into a 20mL sample bottle and add 2g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0048] (2) Add 1.166g of dopamine acrylamide, 1mL of ethyl 2-(ethylaminoformyl)acrylate, 0.5mL of trifluoroethyl acrylate, 0.72g of LiTFSI salt, 0.0052g of photoinitiator TPO, 0.0116g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 4.62g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0049] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size is 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0050] Figures 3-6 The images show the scanning electron microscope spectra of the all-solid-state ion-conducting elastomer prepared in Example 2 of this disclosure at different magnifications. It can be seen from the images that the inorganic phase is uniformly dispersed in the system and the two phases form a bicontinuous structure with obvious ion channels, which provides the basis for the high ion conductivity of the material.

[0051] Example 3:

[0052] The method for preparing an all-solid-state ion-conductive elastomer provided in Embodiment 3 of this disclosure includes the following steps:

[0053] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 6.82g into a 20mL sample bottle and add 4g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0054] (2) Add 1.166g of dopamine acrylamide, 1mL of ethyl 2-(butylamino)carbonyl oxyacrylate, 0.5mL of trifluoroethyl acrylate, 0.72g of LiTFSI salt, 0.0052g of photoinitiator TPO, 0.0116g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 4.94g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to dissolve it and obtain a transparent homogeneous precursor solution.

[0055] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size is 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0056] Figure 7 This is a characterization graph of the conductivity of the all-solid-state ion-conducting elastomer prepared in Example 3 of this disclosure, measured by impedance method. Specifically, the ion-conducting elastomer material (10×5×3mm in size) was sandwiched between two spacers. 3 Afterwards, the two electrodes were clamped to the gasket and tested using the EIS potentiostatic program on an electrochemical workstation (VIONIC, AUTOLAB). The test results are as follows: Figure 7 As shown, according to the conductivity calculation formula σ=d / (R·A) (d-distance between the two electrodes, R-resistance, A-contact area), the ionic conductivity of the material is 0.1S / m, which is much higher than the ionic conductivity of existing all-solid-state ionic conductive elastomers, demonstrating the excellent electrical properties of the material.

[0057] Example 4:

[0058] The preparation method of the all-solid-state ion-conducting elastomer provided in Embodiment 4 of this disclosure includes the following steps:

[0059] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 3.41g into a 10mL sample bottle and add 1g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0060] (2) Add 1.112 g of dopamine acrylamide, 1 mL of ethyl 2-(butylamino)carbonyl oxyacrylate, 0.5 mL of trifluoroethyl acrylate, 0.72 g of LiTFSI salt, 0.0049 g of photoinitiator TPO, 0.0111 g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 2.89 g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0061] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0062] Figure 8These are qualitative self-healing characterization images of the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure in water. In the images, 1 is a photograph of the material being cut, 2 is a photograph of the material being repaired, and 3 is a tensile photograph of the material after repair. As can be seen from the images, the material exhibits very good tensile properties after repairing in water for approximately 15 seconds, demonstrating excellent underwater self-healing characteristics.

[0063] Figure 9 The image shows the infrared spectrum of the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure. As can be seen from the image, the material system has very strong hydrogen bonding, which is reflected in all added substances, demonstrating the excellent self-healing properties of this formulation material.

[0064] Figure 10 and Figure 11 This invention relates to the application of the all-solid-state ion-conducting elastomer prepared in Embodiment 4 of this disclosure in capacitive strain sensors at finger joints and elbow joints. Specifically, it describes the use of two strip-shaped ion-conducting elastomers (60×10×3mm in size). 2 A PDMS dielectric layer is sandwiched in the middle to form a sandwich structure, and copper wires are used to lead out electrodes at both ends. The simple capacitive sensor is then tightly attached to the finger and elbow joints, and repeated bending movements are performed. A digital bridge (TH2834 Tonghui) is used to detect the signal. Figure 10 and Figure 11 The data shows that the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure has excellent signal repeatability, as well as excellent signal strength and signal sensitivity. Therefore, the all-solid-state ion-conductive elastomer prepared in Example 4 of this disclosure has excellent capacitive sensing performance, and the sensing signal has excellent repeatability, sensitivity, and intensity, ensuring a continuous and stable output sensing signal during use.

[0065] Figure 12 This is a characterization graph of the conductivity of the all-solid-state ion-conducting elastomer prepared in Example 4 of this disclosure, measured by impedance method. Specifically, the ion-conducting elastomer material (9×9×1mm in size) was sandwiched between two spacers. 3 Afterwards, the two electrodes were clamped to the gasket and tested using the EIS potentiostatic program on an electrochemical workstation (VIONIC, AUTOLAB). The test results are as follows: Figure 12 As shown, according to the conductivity calculation formula σ=d / (R·A) (d - distance between the two electrodes, R - resistance, A - contact area), the ionic conductivity of the material is found to be 0.015 S / m. This is a very high conductivity for an all-solid-state ionic conductive elastomer, demonstrating the material's excellent electrical properties.

[0066] Example 5:

[0067] The method for preparing an all-solid-state ion-conductive elastomer provided in Embodiment 5 of this disclosure includes the following steps:

[0068] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 3.41g into a 10mL sample bottle and add 1g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0069] (2) Add 0.36g of dopamine acrylamide, 1mL of 2-oxoethyl acrylate, 1mL of trifluoroethyl acrylate, 0.574g of LiTFSI salt, 0.006g of photoinitiator TPO, 0.0228g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 3.47g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0070] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0071] Figure 13 This paper presents a quantitative characterization of the self-healing conductivity of the all-solid-state ion-conductive elastomer prepared in Example 5 of this disclosure in air. The figures show that the material can rapidly repair its electrical properties, with a repair efficiency approaching 100%. The self-healing efficiency is expressed as the ratio of the current value after self-healing to the original current value. The specific test steps are as follows:

[0072] The prepared long strip (60×10×1mm) 2 Copper wires were connected to both ends of the sample, and then the copper wires were connected to an electrochemical workstation (CHI706E, Chenhua). The change in current passing through the sample over time was measured using IT mode. After the experiment started, the sample was cut with a blade, then aligned and repaired. This process was repeated, and the current change was recorded.

[0073] Example 6:

[0074] The method for preparing an all-solid-state ion-conducting elastomer provided in Embodiment 6 of this disclosure includes the following steps:

[0075] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 6.82g into a 20mL sample bottle and add 2g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0076] (2) Add 0.7g of dopamine acrylamide, 1.74mL of trifluoroethyl acrylate, 1.74mL of 2-methoxyethyl acrylate, 1g of LiTFSI salt, 0.046g of photoinitiator TPO, 0.07g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 5.78g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0077] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to obtain an all-solid-state ion-conducting elastomer in the form of a cuboid.

[0078] Example 7:

[0079] The method for preparing an all-solid-state ion-conductive elastomer provided in Embodiment 7 of this disclosure includes the following steps:

[0080] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 6.82g into a 20mL sample bottle and add 2g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0081] (2) Add 0.52g of dopamine acrylamide, 1.2mL of 2-methoxyethyl acrylate, 1.2mL of trifluoroethyl acrylate, 0.97g of LiTFSI salt, 0.03g of photoinitiator TPO, 2.3g of crosslinking agent polyethylene glycol (Mw=20000) and 4.05g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0082] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2Photopolymerization was carried out by irradiation for 10 minutes to prepare an all-solid-state ion-conducting elastomer in the form of a cuboid strip.

[0083] Example 8:

[0084] The method for preparing an all-solid-state ion-conductive elastomer provided in Embodiment 8 of this disclosure includes the following steps:

[0085] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 3.41g into a 10mL sample bottle and add 1g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0086] (2) Add 0.484 g of dopamine acrylamide, 1 mL of phenoxy acrylate, 1 mL of 2-methoxyethyl acrylate, 0.574 g of LiTFSI salt, 0.0056 g of photoinitiator TPO, 0.0126 g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 3.47 g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0087] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to prepare an all-solid-state ion-conducting elastomer in the form of a cuboid strip.

[0088] Example 9:

[0089] The method for preparing the all-solid-state ion-conductive elastomer provided in Embodiment 9 of this disclosure includes the following steps:

[0090] (1) Preparation of eutectic solution: First, put the succinate in the bottle into a water bath at 70°C. After the succinate is completely melted, measure 3.41g into a 10mL sample bottle and add 1g of LiTFSI salt. Then, mix it evenly with sonication to obtain a clear and transparent eutectic solution for later use.

[0091] (2) Add 0.4g of dopamine acrylamide, 1mL of ethoxyethoxyethyl acrylate, 1mL of 2-(butylamino)carbonyloxyethyl acrylate, 0.574g of LiTFSI salt, 0.0043g of photoinitiator TPO, 0.0097g of crosslinking agent N,N-bis(acryloyl)cysteine ​​and 2.89g of the eutectic solution prepared in step (1) to the sample bottle respectively, and fill it with inert gas for protection. Sonicate the mixture to obtain a transparent homogeneous precursor solution.

[0092] (3) Pour the homogeneous precursor solution obtained in step (2) into a strip-shaped silicone rubber mold (mold size 60×10×3mm). 3 In the ultraviolet lamp (wavelength 365nm, intensity 675mw / cm²), 2 Photopolymerization was carried out by irradiation for 10 minutes to prepare an all-solid-state ion-conducting elastomer in the form of a cuboid strip.

[0093] Figure 14 These are qualitative self-healing characterization images of the all-solid-state ion-conductive elastomer prepared in Example 9 of this disclosure in air. Image 1 is a photograph of the material being cut, image 2 is a photograph of the material being joined and repaired, and image 3 is a tensile photograph of the material after repair. The images show that the material can be stretched after 15 seconds of repair in air, exhibiting significant air self-healing properties.

[0094] Examples 10-25

[0095] To simplify the description, the specific raw materials and their mass ratios used in Examples 10-25 of this disclosure are shown in tabular form, see Tables 1-4. The specific preparation steps of Examples 10-25 are shown in Example 1.

[0096] Table 1

[0097]

[0098] Table 2

[0099]

[0100] Table 3

[0101]

[0102] Table 4

[0103]

[0104] The principle behind the self-healing and high ionic conductivity of the all-solid-state ion-conductive elastomer prepared by the method provided in this disclosure is as follows:

[0105] When severed all-solid-state ion-conductive elastomers are joined together, bidentate hydrogen bonds form between the dopamine groups within the elastomer. Furthermore, hydrogen bonds form between the phenolic hydroxyl groups in dopamine, the amide groups, oxygen atoms, and fluorine atoms in the system. The lithium salt added to the system forms cation-π interactions with the benzene rings, as well as π-π stacking of the benzene rings. Additionally, the -CF3 groups, cyano groups, and oxygen atoms in the system form dipole-dipole interactions, and ion-dipole interactions with the ions in the system. It is precisely because of these complex and high-density dynamic interactions that when the material fractures and reconnects, these dynamic interactions can rapidly reassemble, thereby achieving self-repair of the material's electrical and mechanical properties. The high ionic conductivity of the elastomer depends on the structural design of the material's ion channels. The added lithium salt facilitates ion conduction through dissociation; however, excessive lithium salt will not dissociate completely, thus affecting the material's conductivity. Therefore, the lithium salt ratio should be controlled within a certain range. Succinate provides ion channels for rapid ion transport, requiring good connectivity of the succinate phase within the elastomer. Therefore, the mass ratio of succinate must exceed 45%. However, excessive succinate not only impairs the material's mechanical properties but also bends the conductive pathways, failing to significantly improve conductivity. Thus, the mass ratio of succinate must be controlled within a specific range. Only by carefully adjusting the proportions of the polymer monomer, lithium salt, and eutectic solution can an ion-conducting elastomer with excellent mechanical and self-healing properties and high ionic conductivity be obtained.

[0106] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative expressions of the above terms must refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0107] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A fully solid-state ion-conducting elastomer, characterized in that, The all-solid-state ion-conducting elastomer has a three-dimensional interconnected nanostructure, and the raw materials of the all-solid-state ion-conducting elastomer include polymer monomers, a first lithium salt, a eutectic solution, an initiator, and a crosslinking agent. The polymer monomers are double-bonded monomers containing dopamine groups and double-bonded monomers that do not contain dopamine groups; The eutectic solution is obtained by mixing a second lithium salt and succinic acid in a mass ratio of 5 to 30:

34. Both the first lithium salt and the second lithium salt are lithium bis(trifluoromethanesulfonyl)imide salts; The ratio of the dopamine-containing double-bonded monomer, the dopamine-free double-bonded monomer, the first lithium salt, and the eutectic solution is 1.166g:1.5ml:0.72g:3.47g, or 1.166g:1.5ml:0.72g:4.62g, or 1.166g:1.5ml:0.72g:4.94g, or 1.112g:1.5ml:0.72g:2.89g, or 0.36g:2ml:0.574g:3.47g, or 0.7g:3.48ml:1g:5.78g, or 0.52g:2.4ml:0.97g:4.05g, or 0.484g:2ml:0.574g:3.47g, or 0.4g:2ml:0.574g:2.89g; The all-solid-state ion-conductive elastomer has a conductivity as high as 0.1 S / m, an elongation at break of 400%~700%, a stress-strain self-healing efficiency of 84%-86% in air, a stress-strain self-healing efficiency of 70%-171% underwater, and an electrical self-healing efficiency close to 100%. The double-bonded monomers containing dopamine groups are dopamine methacrylamide and dopamine acrylamide; The double-bonded monomers that do not contain dopamine groups are acrylate monomers.

2. The all-solid-state ion-conducting elastomer according to claim 1, characterized in that, The acrylate monomers are any one or a mixture of 2-(ethylaminoformyl)acrylate, 2-(butylamino)carbonyloxoacrylate, 2-methoxyethyl acrylate, trifluoroethyl acrylate, hexafluorobutyl acrylate, ethoxyethoxyethyl acrylate, and phenoxyacrylate.

3. The all-solid-state ion-conducting elastomer according to claim 1, characterized in that, The initiator is photoinitiator 2959 or photoinitiator TPO.

4. The all-solid-state ion-conducting elastomer according to claim 3, characterized in that, The molar number of the photoinitiator 2959 or photoinitiator TPO is 0.1% to 1% of the molar number of the polymer monomer.

5. The all-solid-state ion-conducting elastomer according to claim 1, characterized in that, The crosslinking agent is N,N-bis(acryloyl)cysteine, polyethylene glycol diacrylate, or polyethylene glycol.

6. The all-solid-state ion-conducting elastomer according to claim 1, characterized in that, The molar number of the crosslinking agent is 0.1% to 1% of the molar number of the polymer monomer.

7. The all-solid-state ion-conducting elastomer according to claim 1, characterized in that, The eutectic solution is prepared according to the following steps: heating succinate to make it liquid, adding the second lithium salt to the liquid succinate, and ultrasonically mixing to obtain the eutectic solution.

8. A method for preparing an all-solid-state ion-conducting elastomer according to any one of claims 1 to 7, characterized in that, include: The initiator, the crosslinking agent, the first lithium salt, and the eutectic solution are added to the polymer monomer and stirred evenly by ultrasonication to obtain a homogeneous precursor solution. The all-solid-state ion-conductive elastomer is then obtained through polymerization.

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