A self-healing, stretchable eutectic gel electrode, its preparation method and application

Abstract

This invention discloses a self-healing, stretchable eutectic gel electrode, its preparation method, and its applications. The eutectic gel electrode comprises a eutectic gel positive electrode and / or a eutectic gel negative electrode; wherein the eutectic gel positive electrode is prepared by photopolymerization of polymer monomers, photoinitiator, crosslinking agent, eutectic solvent, conductive agent, and manganese dioxide, and the eutectic gel negative electrode is prepared by thermal polymerization of polymer monomers, crosslinking agent, eutectic solvent, thermal initiator, conductive agent, and zinc powder. The eutectic gel electrode prepared by this invention not only possesses excellent conductivity but also exhibits self-healing, stretchability, and wide temperature tolerance; simultaneously, the prepared fully eutectic gel soft battery possesses excellent omnidirectional intrinsic stretchability, full-cell self-healing, high and low temperature tolerance, and user customization, showing promising application prospects in the field of flexible energy storage.

Description

Technical Field

[0001] This invention belongs to the field of flexible energy storage device technology, and relates to a self-healing stretchable eutectic gel electrode, its preparation method and application, especially to a self-healing stretchable eutectic gel electrode and its preparation method, as well as the application of the self-healing stretchable eutectic gel electrode in a fully eutectic gel soft battery. Background Technology

[0002] Energy storage devices are one of the major bottlenecks limiting the rapid development of wireless wearable electronics, cordless robots, and the Internet of Things. To keep pace with the development of flexible electronics, it is crucial to produce energy storage devices that are flexible, stretchable, and temperature-resistant. Furthermore, for stretchable energy storage devices, self-healing properties are particularly important for restoring their mechanical integrity and electrochemical function when damaged during repeated bending, stretching, and electrochemical cycling. However, despite significant progress in the development of self-healing stretchable materials, most energy storage devices to date are typically rigid or non-self-healing due to limitations in the inherent stiffness of the materials themselves and the feasibility requirements of manufacturing processes.

[0003] Fabricating self-healing, intrinsically stretchable batteries requires the simultaneous development of five self-healing, intrinsically stretchable components: a positive electrode, a negative electrode, an electrolyte, a separator, and a substrate. Ensuring each layer possesses intrinsic self-healing properties, stretchability, and mechanical strength, while maintaining effective charge transport and excellent interfacial adhesion between multiple layers, is an extremely challenging task. Most reported self-healing batteries are not stretchable; they achieve partial self-healing only through self-healing electrodes or electrolytes, and have not yet achieved self-healing at the full-device level. Currently, there are no reports of intrinsically self-healing stretchable batteries capable of effectively restoring all original mechanical and electrochemical properties at the full-cell level. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a self-healing stretchable eutectic gel electrode and its application in a fully eutectic gel soft battery. This method enables the battery to exhibit excellent omnidirectional intrinsic stretchability, spontaneous full-cell self-healing, wide temperature tolerance, and user customizability, providing a new battery design for the integration of multifunctional flexible devices and the development of embedded energy technology.

[0005] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0006] This invention provides a self-healing, stretchable eutectic gel electrode, comprising a eutectic gel positive electrode and / or a eutectic gel negative electrode; wherein the eutectic gel positive electrode is prepared by photopolymerization of polymer monomers, photoinitiator, crosslinking agent, eutectic solvent, conductive agent, and manganese dioxide, and the eutectic gel negative electrode is prepared by thermal polymerization of polymer monomers, crosslinking agent, eutectic solvent, thermal initiator, conductive agent, and zinc powder.

[0007] This invention also provides a method for preparing the aforementioned self-healing stretchable eutectic gel electrode, comprising: heating a polymer monomer, a photoinitiator, a crosslinking agent, and a eutectic solvent until completely dissolved, then adding a conductive agent and manganese dioxide and mixing evenly, and then irradiating with ultraviolet light for 10-60 minutes to obtain a eutectic gel electrode; wherein the eutectic gel electrode is a eutectic gel positive electrode, and the eutectic gel positive electrode has a polymer single-network structure.

[0008] This invention also provides a method for preparing the aforementioned self-healing, stretchable eutectic gel electrode, comprising: heating a polymer monomer, a crosslinking agent, and a eutectic solvent until completely dissolved, cooling to room temperature, adding a conductive agent, zinc powder, and a thermal initiator, and stirring thoroughly for 10–30 min to undergo in-situ thermal polymerization to obtain a eutectic gel electrode; wherein the eutectic gel electrode is a eutectic gel negative electrode, and the eutectic gel negative electrode has a polymer monolayer network structure.

[0009] The present invention also provides the use of the aforementioned self-healing stretchable eutectic gel electrode in the preparation of fully eutectic gel soft batteries.

[0010] This invention also provides a fully eutectic gel soft battery, which includes the aforementioned self-healing stretchable eutectic gel electrode.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0012] (1) The self-healing, stretchable eutectic gel electrode prepared by this invention has excellent electronic conductivity, with an electronic conductivity of 4–20 mS·cm. -1 ;

[0013] (2) The eutectic gel electrode prepared by the present invention has excellent omnidirectional intrinsic stretchability and outstanding self-healing properties. Its biaxial tensile area strain exceeds 1000%, and its uniaxial tensile fracture strain exceeds 1000%. Its electronic self-healing efficiency is 96% to 100%, its mechanical self-healing efficiency is 30% to 50%, and its uniaxial tensile rate after self-healing is 700% to 900%, and its biaxial tensile rate is greater than 500%.

[0014] (3) The eutectic gel electrode prepared by this invention has a wide temperature tolerance, and maintains its flexible mechanical properties and self-healing properties from low temperature -20℃ to high temperature 60℃. It not only solves the problems of traditional rigid electrodes that cannot be stretched and cannot self-heal, but also solves the bottleneck problem of hydrogel electrode materials that are prone to freezing at low temperature and water loss at high temperature, which leads to loss of function, thus improving the stability and temperature tolerance of flexible electronic devices;

[0015] (4) The eutectic gel electrode prepared by the present invention can be assembled with the eutectic gel electrolyte and substrate material through self-bonding interaction to form a fully eutectic gel soft battery with excellent interfacial compatibility, without the need for special surface engineering strategies and complex assembly processes.

[0016] (5) The fully eutectic gel soft battery provided by the present invention has each layer (positive electrode, negative electrode, electrolyte and substrate) as a eutectic gel material, containing the same eutectic solvent and similar supramolecular / polymer network structure. The layers are tightly self-bonded together through multiple non-covalent interactions, avoiding the relative sliding and separation between the layers of traditional energy storage devices, and ensuring the structural integrity and electrochemical functionality of the battery under stretching deformation.

[0017] (6) The eutectic gel soft battery provided by the present invention has omnidirectional intrinsic stretchability and wide temperature range tolerance (-20℃ to 60℃), and has spontaneous self-healing at the whole cell level. Its self-healing process does not require any external stimulation and can be carried out spontaneously at room temperature or even -20℃.

[0018] (7) The fully eutectic gel soft battery provided by the present invention has excellent crack propagation resistance and high user design freedom. It can be designed as a battery of any three-dimensional shape, which can fully meet the requirements of future wearable and soft robot related applications.

[0019] (8) The electrode preparation scheme of the present invention is simple, low in cost, easy to assemble, and has good economic benefits. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figures 1a-1b These are images of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1 of this invention;

[0022] Figure 2These are the XRD patterns of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1 of this invention;

[0023] Figures 3a-3b These are images of the self-healing process of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1 of this invention;

[0024] Figures 4a-4b This is a graph showing the resistance change during the self-healing and stretching process of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1 of this invention.

[0025] Figure 5 These are stress-strain curves of the composite eutectic gel positive electrode and the composite eutectic gel negative electrode prepared in Example 12 of the present invention before and after self-healing and at low temperature.

[0026] Figure 6 This is a graph showing the change in conductivity of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1 of the present invention before and after self-healing.

[0027] Figure 7 This is a schematic diagram of the assembly process of the fully eutectic gel soft battery prepared in Example 12 of the present invention;

[0028] Figure 8 These are microscope images of the fully eutectic gel soft battery prepared in Example 12 of this invention;

[0029] Figure 9 This is an omnidirectional tensile image of the fully eutectic gel soft battery prepared in Example 12 of this invention;

[0030] Figure 10 This is a tensile image of the fully eutectic gel soft battery prepared in Example 13 of this invention;

[0031] Figure 11 These are images of the fully eutectic gel soft battery prepared in Example 14 of this invention spontaneously and self-healing under environmental conditions;

[0032] Figure 12 This is a graph showing the mechanical self-healing performance of the fully eutectic gel soft battery prepared in Example 14 of this invention.

[0033] Figure 13 This is a graph showing the electrochemical self-healing performance of the fully eutectic gel soft battery prepared in Example 14 of this invention at different temperatures.

[0034] Figure 14 These are images of fully eutectic gel soft batteries of different shapes prepared using molds of different animal shapes in Embodiment 12 of the present invention. Detailed Implementation

[0035] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0036] Specifically, as one aspect of the technical solution of the present invention, a self-healing stretchable eutectic gel electrode includes a eutectic gel positive electrode and / or a eutectic gel negative electrode; wherein, the eutectic gel positive electrode is obtained by photopolymerization of polymer monomers, photoinitiator, crosslinking agent, eutectic solvent, conductive agent and manganese dioxide, and the eutectic gel negative electrode is obtained by thermal polymerization of polymer monomers, crosslinking agent, eutectic solvent, thermal initiator, conductive agent and zinc powder.

[0037] In some preferred embodiments, the eutectic gel electrode has omnidirectional intrinsic stretchability and spontaneous self-healing properties. The electronic self-healing efficiency of the eutectic gel electrode is 96% to 100%, the mechanical self-healing efficiency is 30% to 50%, the uniaxial elongation after self-healing is 700% to 900%, and the biaxial elongation is greater than 500%.

[0038] In some preferred embodiments, the eutectic gel electrode has a wide temperature tolerance range of -20 to 60°C.

[0039] In some preferred embodiments, the polymer monomer includes, but is not limited to, nonionic polymer monomers.

[0040] Furthermore, the nonionic polymer monomer includes any one or a combination of two or more of acrylamide, N-(2-hydroxyethyl)acrylamide, acrylic acid, methacrylic acid and vinyl acetate, and is not limited thereto.

[0041] In some preferred embodiments, the photoinitiator includes, but is not limited to, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (Irgacure 2959) and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0042] In some preferred embodiments, the thermal initiator includes, but is not limited to, ammonium persulfate and / or azobisisobutyronitrile.

[0043] In some preferred embodiments, the crosslinking agent includes, but is not limited to, N,N'-methylenebisacrylamide (MBA) and / or 1,6-hexanediol diacrylate.

[0044] In some preferred embodiments, the conductive agent includes any one or a combination of two or more of carbon nanotubes, graphene, and carbon black, but is not limited thereto.

[0045] In some preferred embodiments, the eutectic solvent includes a hydrogen bond acceptor and a hydrogen bond donor; wherein the hydrogen bond acceptor includes choline chloride; and the hydrogen bond donor includes, but is not limited to, any one or a combination of two or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, sorbitol, glycerol, xylitol, and urea.

[0046] In some preferred embodiments, the content (mass fraction) of the conductive agent in the eutectic gel cathode is 1-5 wt%.

[0047] Furthermore, the manganese dioxide content (mass fraction) in the eutectic gel cathode is 1–5 wt%.

[0048] Furthermore, the mass ratio of the conductive agent to manganese dioxide in the eutectic gel cathode is 1 to 2:1.

[0049] In some preferred embodiments, the content (mass fraction) of the conductive agent in the eutectic gel negative electrode is 5-10 wt%.

[0050] Furthermore, the zinc powder content (mass fraction) in the eutectic gel anode is 25-35 wt%.

[0051] Furthermore, the mass ratio of the conductive agent to zinc powder in the eutectic gel negative electrode is 1 to 2:5.

[0052] Another aspect of the present invention provides a method for preparing the aforementioned self-healing stretchable eutectic gel electrode, comprising: heating a polymer monomer, a photoinitiator, a crosslinking agent, and a eutectic solvent until completely dissolved, then adding a conductive agent and manganese dioxide and mixing evenly, and then irradiating with ultraviolet light for 10-60 minutes to obtain a eutectic gel electrode; wherein the eutectic gel electrode is a eutectic gel positive electrode, and the eutectic gel positive electrode has a polymer single-network structure.

[0053] Furthermore, the ultraviolet light used has a wavelength of 365nm.

[0054] In some preferred embodiments, the mass ratio of the polymer monomer to the eutectic solvent is 50 to 150:100.

[0055] Furthermore, the mass ratio of the crosslinking agent to the eutectic solvent is 0.01 to 1:100.

[0056] Furthermore, the mass ratio of the photoinitiator to the eutectic solvent is 1 to 10:100.

[0057] Another aspect of the present invention provides a method for preparing the aforementioned self-healing stretchable eutectic gel electrode, comprising: heating a polymer monomer, a crosslinking agent, and a eutectic solvent until completely dissolved, cooling to room temperature, adding a conductive agent, zinc powder, and a thermal initiator, and stirring thoroughly for 10-30 minutes to undergo in-situ thermal polymerization to obtain a eutectic gel electrode; wherein the eutectic gel electrode is a eutectic gel negative electrode, and the eutectic gel negative electrode has a polymer single-network structure.

[0058] In some preferred embodiments, the mass ratio of the polymer monomer to the eutectic solvent is 50 to 150:100.

[0059] Furthermore, the mass ratio of the crosslinking agent to the eutectic solvent is 0.01 to 1:100.

[0060] Furthermore, the mass ratio of the thermal initiator to the eutectic solvent is 1 to 10:100.

[0061] Another aspect of the present invention provides the use of the aforementioned self-healing stretchable eutectic gel electrode in the fabrication of fully eutectic gel soft batteries.

[0062] Another aspect of the present invention provides a fully eutectic gel soft battery comprising the aforementioned self-healing stretchable eutectic gel electrode.

[0063] The fully eutectic gel soft battery of this invention has full self-healing properties, omnidirectional intrinsic stretchability, and wide temperature range tolerance. Its self-healing process does not require any external stimulation. At the same time, it has excellent resistance to crack propagation and high user design freedom, and can be designed into batteries of any three-dimensional shape.

[0064] In some preferred embodiments, the temperature range of the fully eutectic gel soft battery is -20 to 60°C.

[0065] In some preferred embodiments, the fully eutectic gel soft battery can spontaneously heal at room temperature to -20°C.

[0066] In some preferred embodiments, the fully eutectic gel soft battery has a uniaxial elongation greater than 1000%, a biaxial elongation greater than 1000%, and a self-healed uniaxial elongation greater than 650% and a biaxial elongation greater than 500%.

[0067] In some preferred embodiments, the all-eutectic gel soft battery includes the aforementioned eutectic gel positive electrode, eutectic gel negative electrode, eutectic gel electrolyte, and eutectic gel substrate.

[0068] In some preferred embodiments, the method for preparing the all-eutectic gel soft battery includes: self-adheding eutectic gel positive and negative electrodes to the surface of a eutectic gel substrate to form a composite eutectic gel positive and negative electrode; placing a eutectic gel electrolyte between the two composite electrodes to assemble a sandwich-structured battery.

[0069] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0070] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0071] Example 1

[0072] Preparation of DES: Weigh choline chloride, urea and ethylene glycol in a glass vial according to a molar ratio of 1:2:4. Heat and stir at 60°C for 2 hours to form a homogeneous and transparent solution. Then, cool naturally to room temperature to obtain the eutectic solvent.

[0073] Preparation of eutectic gel electrodes:

[0074] 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg eutectic solvent were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the mixture was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel cathode.

[0075] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA and 1000.0 mg eutectic solvent were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0076] Example 2

[0077] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel positive electrode.

[0078] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg azobisisobutyronitrile were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0079] Example 3

[0080] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) 1,6-hexanediol diacrylate and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel positive electrode.

[0081] 500.0 mg acrylamide, 50 μL (10 mg / mL) 1,6-hexanediol diacrylate, and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0082] Example 4

[0083] Preparation of eutectic gel electrode: 500.0 mg N-(2-hydroxyethyl)acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel positive electrode.

[0084] 500.0 mg N-(2-hydroxyethyl)acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0085] Example 5

[0086] Preparation of eutectic gel electrodes:

[0087] The eutectic solvent prepared in Example 1 was heated to completely dissolve 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg. 30 mg carbon black and 25 mg manganese dioxide powder were added to the solution. After thorough stirring, the solution was poured into a mold and then irradiated with a UV lamp at a wavelength of 365 nm for 20 min to obtain the eutectic gel cathode.

[0088] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon black, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0089] Example 6

[0090] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. 30 mg graphene and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a UV lamp with a wavelength of 365 nm for 20 min to obtain the eutectic gel positive electrode.

[0091] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 1 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg graphene, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0092] Example 7

[0093] Preparation of DES: Weigh choline chloride, urea and 1,3-propanediol in a glass vial according to a molar ratio of 1:2:4. Heat and stir at 60°C for 2 hours to form a homogeneous and transparent solution. Then, cool naturally to room temperature to obtain the eutectic solvent.

[0094] Preparation of eutectic gel electrodes:

[0095] 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg eutectic solvent were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the mixture was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel cathode.

[0096] 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA, and 1000.0 mg eutectic solvent were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0097] Example 8

[0098] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a UV lamp with a wavelength of 365 nm for 20 min to obtain the eutectic gel positive electrode.

[0099] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg azobisisobutyronitrile were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0100] Example 9

[0101] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) 1,6-hexanediol diacrylate and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a UV lamp with a wavelength of 365 nm for 20 min to obtain the eutectic gel positive electrode.

[0102] 500.0 mg acrylamide, 50 μL (10 mg / mL) 1,6-hexanediol diacrylate, and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0103] Example 10

[0104] Preparation of eutectic gel electrode: 500.0 mg N-(2-hydroxyethyl)acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. 30 mg carbon nanotubes and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a 365 nm ultraviolet lamp for 20 min to obtain the eutectic gel positive electrode.

[0105] 500.0 mg N-(2-hydroxyethyl)acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon nanotubes, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0106] Example 11

[0107] Preparation of eutectic gel electrode: 500.0 mg acrylamide, 90 mg Irgacure 2959, 50 μL (10 mg / mL) MBA and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. 30 mg carbon black and 25 mg manganese dioxide powder were added to the above solution. After thorough stirring, the solution was poured into a mold and then irradiated with a UV lamp with a wavelength of 365 nm for 20 min to obtain the eutectic gel positive electrode.

[0108] 500.0 mg acrylamide, 50 μL (10 mg / mL) MBA, and 1000.0 mg of the eutectic solvent prepared in Example 7 were heated until completely dissolved. After cooling to room temperature, 500 mg zinc powder, 160 mg carbon black, and 80 mg ammonium persulfate were added to the above solution. After stirring thoroughly for 15 min, the eutectic gel anode was obtained by in-situ thermal polymerization.

[0109] Example 12

[0110] Preparation of fully eutectic gel soft batteries: including preparation of eutectic gel electrolyte, preparation of eutectic gel substrate and battery assembly.

[0111] Preparation of eutectic gel electrolyte: Accurately weigh 30.0 mg of 12-hydroxystearyl hydrazine, 300 mg of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 44.8 mg of Irgacure 2959, 1 mg of MBA, and 1000 mg of the eutectic solvent prepared in Example 1 into a glass vial. Heat until completely dissolved, then allow to cool naturally to room temperature and stand for 30 min to form the first supramolecular gel network. Irradiate under a 365 nm UV lamp for 20 min to obtain the supramolecular-polymer dual-network eutectic gel electrolyte. The ionic conductivity of this supramolecular-polymer dual-network eutectic gel electrolyte is 4.26 mS / cm. -1 The zinc ion transference number is 0.77, which provides a strong guarantee for charge transport between the multiple layers of the gel soft battery.

[0112] Preparation of the eutectic gel substrate: Accurately weigh 40.0 mg of 12-hydroxystearyl hydrazide, 500 mg of acrylamide, 22.4 mg of Irgacure 2959, 50 μL (10 mg / mL) of MBA, and 1000 mg of eutectic solvent into a glass vial. Heat until completely dissolved, then allow to cool naturally to room temperature and stand for 30 min to form the first supramolecular gel network. Irradiate under a 365 nm UV lamp for 30 min to obtain the supramolecular-polymer dual-network eutectic gel substrate. This eutectic gel substrate exhibits excellent mechanical strength, toughness, and crack propagation resistance, with a fracture stress of 37.64 kPa and a tear energy of 175.14 J·m, respectively. –2 This provides effective protection and support for gel soft batteries.

[0113] Battery Assembly: The eutectic gel positive and negative electrodes prepared in Example 1 were self-adheded to the surface of the aforementioned eutectic gel substrate to form composite eutectic gel positive and negative electrodes. Then, the aforementioned eutectic gel electrolyte was placed between two identical composite electrodes and sequentially bonded together to assemble a sandwich-structured all-eutectic gel soft battery. Each layer of this battery is a eutectic gel material containing the same eutectic solvent and a similar supramolecular / polymer network structure. The layers are tightly self-bonded together through multiple non-covalent interactions, requiring no special surface engineering strategies or complex assembly processes.

[0114] Example 13

[0115] Preparation of porous eutectic gel soft battery: The eutectic gel soft battery prepared in Example 7 was further drilled with two holes in the center of the battery using a hole puncher to obtain a porous eutectic gel soft battery.

[0116] Example 14

[0117] Preparation of self-healing eutectic gel soft battery: The eutectic gel soft battery prepared in Example 7 was further cut in half with Teflon scissors, and then the two halves were joined together and left to stand for 4 hours to obtain a self-healing eutectic gel soft battery.

[0118] Performance characterization:

[0119] Figures 1a-1b The images are of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1, respectively.

[0120] Figure 2 These are the XRD patterns of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1.

[0121] Figures 3a-3b These are images of the self-healing process of the eutectic gel positive electrode and the eutectic gel negative electrode prepared in Example 1.

[0122] Figures 4a-4b This is a graph showing the resistance changes of the eutectic gel positive and negative electrodes prepared in Example 1 during the self-healing and stretching process. The resistance changes of the eutectic gel electrode before and after self-healing and during subsequent stretching after self-healing are not significant, demonstrating the stability of the eutectic gel electrode. After only 4 hours of self-healing, the electrode can recover a biaxial elongation of more than 500%, further confirming the excellent elongation and self-healing properties of the electrode itself.

[0123] Figure 5 These are the stress-strain curves of the composite eutectic gel positive electrode and the composite eutectic gel negative electrode prepared in Example 12 before and after self-healing and at low temperature. The mechanical self-healing efficiency of the eutectic gel electrode is 30% to 50%, and the uniaxial tensile rate after self-healing is 700% to 900%, which shows the excellent self-healing properties of the prepared eutectic gel electrode.

[0124] Figure 6 This is a graph showing the conductivity changes of the eutectic gel positive and negative electrodes prepared in Example 1 before and after self-healing. Under optimized conditions, the room temperature conductivity of the eutectic gel cathode and anode reached as high as 4.88 and 4.50 mS·cm, respectively. -1 This indicates that it has good electronic transport capabilities.

[0125] Figure 7 This is a schematic diagram of the assembly process of the fully eutectic gel soft battery prepared in Example 12.

[0126] Figure 8 This is a microscopic image of the all-eutectic gel soft battery prepared in Example 12. The optical image shows the five-layer structure of the all-eutectic gel soft battery, which are tightly bonded together by self-bonding interactions and have very good interfacial compatibility.

[0127] Figure 9 This is an omnidirectional tensile diagram of the fully eutectic gel soft battery prepared in Example 12. Strong interfacial adhesion enables seamless multilayer integration of the fully eutectic gel soft battery and prevents it from sliding or delaminating during stretching. Therefore, the assembled fully eutectic gel soft battery exhibits good structural stability under tensile strain and can be omnidirectionally stretched at the full-cell level, with an area strain exceeding 1000%.

[0128] Figure 10 This is a tensile diagram of the fully eutectic gel soft battery prepared in Example 13. Even under mechanical perforation, it can still maintain high tensile strength, which intuitively demonstrates that the battery has excellent crack resistance.

[0129] Figure 11 The image shows the spontaneous self-healing of the fully eutectic gel soft battery prepared in Example 14 under environmental conditions, demonstrating that the self-healed battery can still withstand an area strain of more than 500%.

[0130] Figure 12 This is a graph showing the mechanical self-healing performance of the fully eutectic gel soft battery prepared in Example 14. The experiment shows that the cut battery has excellent self-healing performance. After 4 hours of self-healing at room temperature, the fracture strain recovers to 650%, and the healing efficiency is as high as 55%.

[0131] Figure 13 This is a graph showing the electrochemical self-healing performance of the fully eutectic gel soft battery prepared in Example 14 at different temperatures; compared with the initial battery, the capacity and coulombic efficiency are almost completely recovered. Even under restretching conditions (200% areal strain), the repaired capacity and coulombic efficiency are still as high as 237.78 mAh·g. -1 The battery achieved 100% recovery after relaxation, which further confirms its excellent structural stability. Furthermore, it also exhibited such excellent electrochemical self-healing performance at -20℃ and 60℃, demonstrating its superior temperature resistance and setting a new record for self-healing batteries.

[0132] Figure 14 These are images of fully eutectic gel soft batteries of different shapes prepared using molds of different animal shapes, as shown in Example 12. These batteries can operate stably for one week at different temperatures, clearly demonstrating that the prepared batteries have excellent temperature tolerance and 3D customizability.

[0133] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0134] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A self-healing, stretchable eutectic gel electrode, characterized in that: The eutectic gel electrode includes a eutectic gel positive electrode and / or a eutectic gel negative electrode; wherein, the eutectic gel positive electrode is prepared by photopolymerization of polymer monomers, photoinitiator, crosslinking agent, eutectic solvent, conductive agent and manganese dioxide, and the eutectic gel negative electrode is prepared by thermal polymerization of polymer monomers, crosslinking agent, eutectic solvent, thermal initiator, conductive agent and zinc powder; The polymer monomers include nonionic polymer monomers; the nonionic polymer monomers include any one or a combination of two or more of acrylamide, N-(2-hydroxyethyl)acrylamide, and vinyl acetate; the crosslinking agent includes N,N'-methylenebisacrylamide and / or 1,6-hexanediol diacrylate; the eutectic solvent includes hydrogen bond acceptors and hydrogen bond donors; wherein the hydrogen bond acceptor includes choline chloride; and the hydrogen bond donors include any one or a combination of two or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, sorbitol, glycerol, xylitol, and urea.

2. The eutectic gel electrode according to claim 1, characterized in that: The eutectic gel electrode has an electronic self-healing efficiency of 96%~100%, a mechanical self-healing efficiency of 30%~50%, a uniaxial tensile strength of 700%~900% after self-healing, and a biaxial tensile strength greater than 500%.

3. The eutectic gel electrode according to claim 1, characterized in that: The temperature range of the eutectic gel electrode is -20 to 60 ℃.

4. The eutectic gel electrode according to claim 1, characterized in that: The photoinitiator includes 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

5. The eutectic gel electrode according to claim 1, characterized in that: The thermal initiator includes ammonium persulfate and / or azobisisobutyronitrile.

6. The eutectic gel electrode according to claim 1, characterized in that: The conductive agent includes any one or a combination of two or more of carbon nanotubes, graphene, and carbon black.

7. The eutectic gel electrode according to claim 1, characterized in that: The conductive agent in the eutectic gel cathode has a mass percentage content of 1-5 wt%; And / or, the mass percentage of manganese dioxide in the eutectic gel cathode is 1~5 wt%.

8. The eutectic gel electrode according to claim 1, characterized in that: The mass ratio of conductive agent to manganese dioxide in the eutectic gel cathode is 1~2:

1.

9. The eutectic gel electrode according to claim 1, characterized in that: The conductive agent in the eutectic gel negative electrode has a mass percentage content of 5-10 wt%. And / or, the zinc powder content in the eutectic gel anode is 25~35wt%.

10. The eutectic gel electrode according to claim 1, characterized in that: The mass ratio of conductive agent to zinc powder in the eutectic gel negative electrode is 1~2:

5.

11. A method for preparing the self-healing, stretchable eutectic gel electrode according to any one of claims 1-10, characterized in that... include: Polymer monomers, photoinitiators, crosslinking agents, and eutectic solvents are heated until completely dissolved. Then, conductive agents and manganese dioxide are added and mixed evenly. The mixture is then irradiated with ultraviolet light for 10-60 minutes to obtain a eutectic gel electrode. The eutectic gel electrode is a eutectic gel positive electrode with a polymer single-network structure.

12. The preparation method according to claim 11, characterized in that: The mass ratio of the polymer monomer to the eutectic solvent is 50~150:100; And / or, the mass ratio of the crosslinking agent to the eutectic solvent is 0.01 to 1:100; And / or, the mass ratio of the photoinitiator to the eutectic solvent is 1~10:

100.

13. A method for preparing the self-healing, stretchable eutectic gel electrode according to any one of claims 1-10, characterized in that... include: Polymer monomers, crosslinking agents, and eutectic solvents are heated until completely dissolved. After cooling to room temperature, conductive agents, zinc powder, and thermal initiators are added. After stirring thoroughly for 10-30 minutes, in-situ thermal polymerization occurs to obtain a eutectic gel electrode. The eutectic gel electrode is a eutectic gel negative electrode with a polymer mononetwork structure.

14. The preparation method according to claim 13, characterized in that: The mass ratio of the polymer monomer to the eutectic solvent is 50~150:100; And / or, the mass ratio of the crosslinking agent to the eutectic solvent is 0.01 to 1:100; And / or, the mass ratio of the thermal initiator to the eutectic solvent is 1~10:

100.

15. Use of the self-healing stretchable eutectic gel electrode according to any one of claims 1-10 in the preparation of a fully eutectic gel soft battery.

16. A fully eutectic gel soft battery, characterized in that... Includes the self-healing stretchable eutectic gel electrode according to any one of claims 1-10.

17. The fully eutectic gel soft battery according to claim 16, characterized in that: The temperature range of the fully eutectic gel soft battery is -20 to 60 ℃.

18. The fully eutectic gel soft battery according to claim 16, characterized in that: The fully eutectic gel soft battery spontaneously heals at room temperature to -20 °C.

19. The fully eutectic gel soft battery according to claim 16, characterized in that: The fully eutectic gel soft battery has a uniaxial elongation greater than 1000%, a biaxial elongation greater than 1000%, and a uniaxial elongation greater than 650% and a biaxial elongation greater than 500% after self-healing.

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