Self-healing stretchable eutectic gel electrolyte and preparation method and application thereof

Abstract

The application discloses a self-healing stretchable eutectic gel electrolyte and a preparation method and application thereof. The preparation method comprises the following steps: heating a mixed reaction system comprising a supramolecular gel factor, an amphoteric polymer monomer, a crosslinking agent, a photoinitiator, a ternary eutectic solvent and a metal salt to complete dissolution, then cooling to room temperature to form a first heavy supramolecular gel network, and then performing a photoinitiated polymerization reaction to obtain the self-healing stretchable eutectic gel electrolyte. The eutectic gel electrolyte prepared by the application has excellent self-healing property, stretchability and wide temperature range resistance, and simultaneously has good conductivity and high metal ion transference number, so that the generation of metal dendrites can be avoided, and the eutectic gel electrolyte has a good application prospect in the field of flexible energy storage.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of gels, and relates to a self-healing stretchable eutectic gel electrolyte and a preparation method and application thereof, in particular to a supramolecular-polymer double network eutectic gel electrolyte based on amphoteric polymer ionic monomers and ternary eutectic solvents and a preparation method and application thereof. BACKGROUND

[0002] Eutectic solvents (DESs) are composed of hydrogen bond acceptors and hydrogen bond donors, have high structural designability, and have inherent properties such as easy preparation, low vapor pressure, high thermal stability, etc. They are a new type of electrolyte system. However, the viscosity of DESs is relatively large, the conductivity is relatively low, and the ion transmission capacity is relatively low, which limits their wide application. Current research mainly focuses on developing hydrated eutectic solvents to reduce the viscosity of DESs to improve their conductivity, and further developing their application in traditional rigid batteries or flow batteries. There is no report on the application of semi-solid eutectic gel electrolytes in flexible / stretchable batteries. It is extremely challenging to prepare liquid eutectic electrolytes with high viscosity into semi-solid electrolytes with higher viscosity and successfully apply them in flexible energy storage field. Therefore, it is crucial to develop a general eutectic electrolyte with high conductivity, high mechanical strength and toughness, and high stretchability to expand the application range of eutectic electrolytes.

[0003] In addition, for flexible energy storage devices, they are prone to cause battery damage during repeated mechanical deformation and electrochemical cycling. It is crucial to develop energy storage devices with self-healing properties to improve battery life and reduce replacement costs. The common self-healing batteries are mainly achieved by developing self-healing hydrogels or ionic liquid gel electrolytes. There is no report on a eutectic gel electrolyte that integrates high stretchability, self-healing, conductivity, and resistance to extreme temperatures. SUMMARY

[0004] To solve the problems in the prior art, the present application aims to provide a self-healing stretchable eutectic gel electrolyte and a preparation method and application thereof. The eutectic gel electrolyte provided by the present application has excellent stretchability, spontaneous self-healing, wide temperature tolerance, high conductivity and ion transference number, and can be applied to metal ion batteries, self-healing stretchable all-eutectic gel soft batteries and avoid the generation of metal dendrites. It has important theoretical and practical significance for expanding the material platform of flexible battery electrolytes.

[0005] To achieve the foregoing application purposes, the technical solutions adopted by the present application include:

[0006] The embodiment of the present application provides a preparation method of a self-healing stretchable eutectic gel electrolyte, which comprises: heating a mixed reaction system comprising a supramolecular gel factor, an amphoteric polymer monomer, a crosslinking agent, a photoinitiator, a ternary eutectic solvent and a metal salt to complete dissolution, and then cooling to room temperature to form a first heavy supramolecular gel network, and then performing a photoinitiated polymerization reaction to obtain the self-healing stretchable eutectic gel electrolyte.

[0007] The amphoteric polymer monomer comprises any one or a combination of two or more of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, N-carboxymethyl-N,N-bis(2-hydroxyethyl)-1-dodecylammonium inner salt, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate and 2-methacryloyloxyethylphosphocholine.

[0008] The embodiment of the present application further provides the self-healing stretchable eutectic gel electrolyte prepared by the preparation method.

[0009] The embodiment of the present application further provides an application of the self-healing stretchable eutectic gel electrolyte in the field of energy storage.

[0010] The embodiment of the present application further provides a metal ion battery comprising the self-healing stretchable eutectic gel electrolyte.

[0011] Compared with the prior art, the present application has the following beneficial effects:

[0012] (1) The present application adds an amphoteric ion polymer skeleton in a liquid DES, which not only gels the DES, but also provides more ion transmission channels, further improves the conductivity and ion transference number, and enables the prepared eutectic gel electrolyte to meet the requirements of electrochemical applications;

[0013] (2) The semi-solid eutectic gel electrolyte constructed by the present application has a supramolecular-polymer double network structure, the double network can effectively dissipate energy and dynamically reorganize, thereby endowing the prepared eutectic gel electrolyte with excellent mechanical stretchability and spontaneous self-healing property, and the eutectic gel electrolyte has a wide application prospect in the field of flexible energy storage;

[0014] (3) The semi-solid eutectic gel electrolyte constructed by the present application has excellent temperature resistance, and the temperature resistance range is from-60 DEG C to +80 DEG C, which provides an excellent material platform for constructing environment-adaptive energy storage devices;

[0015] (4) The eutectic gel electrolyte prepared based on the present application can avoid the generation of metal dendrites and has excellent cycle stability in the application of metal ion batteries. Attached Figure Description

[0016] 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.

[0017] Figure 1 Image of the self-healing, stretchable eutectic gel electrolyte prepared in Example 1 of this invention;

[0018] Figures 2a-2b XRD patterns of the amphoteric polymer eutectic gels prepared in Comparative Examples 1 and 3, the supramolecular eutectic gels, and the self-healing stretchable supramolecular-polymer dual-network eutectic gels prepared in Example 1 of this invention.

[0019] Figure 3 This is a uniaxial tensile diagram of the self-healing, stretchable eutectic gel electrolyte prepared in Example 1 of the present invention.

[0020] Figure 4 This is a biaxial tensile image of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present invention after self-healing for 4 hours under environmental conditions.

[0021] Figures 5a-5b The stress-strain curves of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present invention at low temperature and under different self-healing states are shown.

[0022] Figure 6 These are tensile images of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present invention and the PMAEDS polymer hydrogel electrolyte prepared in Comparative Example 2 at different temperatures.

[0023] Figure 7 This is a conductivity diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present invention under high and low temperature environments;

[0024] Figures 8a-8b Zn is the self-healing, stretchable eutectic gel prepared in Example 1 of this invention. 2+ Ion transport number analysis plot;

[0025] Figure 9 The graph shows the zinc deposition / stripping data of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present invention and the PMAEDS polymer hydrogel electrolyte prepared in Comparative Example 1 in a Zn / / Zn symmetric cell.

[0026] Figure 10 Figure 6 is a cycle performance chart of a Zn / / SS asymmetric battery prepared with the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer eutectic gel prepared in Example 1 as electrolyte;

[0027] Figure 11 Figure 7 is an XRD chart of the zinc anode of a Zn / / Zn symmetric battery prepared with the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer eutectic gel prepared in Example 1 as electrolyte after repeated deposition / peeling;

[0028] Figures 12a-12b Figure 8 is an electron microscope chart of the zinc anode of a Zn / / Zn symmetric battery prepared with the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer eutectic gel prepared in Example 1 as electrolyte after repeated deposition / peeling. DETAILED DESCRIPTION

[0029] In view of the defects of the prior art, the present inventors have long studied and practiced to propose the technical solution of the present application. The present application simultaneously introduces an amphoteric ion polymer network and a supramolecular network into a ternary eutectic solvent system, and designs and synthesizes a class of supramolecular-polymer double network eutectic gel electrolytes through synergistic interaction between the two, which exhibits good self-healing, stretchability, conductivity, ion transport and temperature tolerance, and shows broad application prospects in metal ion batteries, flexible electronic devices and other fields.

[0030] The technical solution of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0031] Specifically, as one aspect of the technical solution of the present application, the preparation method of a self-healing stretchable eutectic gel electrolyte includes: heating a mixed reaction system containing a supramolecular gel factor, an amphoteric polymer monomer, a crosslinking agent, a photoinitiator, a ternary eutectic solvent and a metal salt to complete dissolution, then cooling to room temperature to form a first heavy supramolecular gel network, and then performing a photoinitiated polymerization reaction to obtain a self-healing stretchable eutectic gel electrolyte.

[0032] The amphoteric polymer monomer includes any one of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt (MAEDS), N-carboxymethyl-N,N-bis(2-hydroxyethyl)-1-dodecylammonium inner salt, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate, 2-methacryloyloxyethylphosphocholine, or a combination of two or more thereof, and is not limited thereto.

[0033] In some preferred embodiments, the supramolecular gelator has a structure as shown in formula (I):

[0034]

[0035] wherein n is selected from 0-10, and R is selected from H or OH.

[0036] Further, n is 0, 2, 6, or 10; and R is OH.

[0037] In some preferred embodiments, the ternary deep eutectic solvent includes a first ternary deep eutectic solvent and / or a second ternary deep eutectic solvent; the first ternary deep eutectic solvent includes choline chloride, ethylene glycol, and urea; and the second ternary deep eutectic solvent includes choline chloride, 1,3-propanediol, and urea.

[0038] Further, the molar ratio of choline chloride, ethylene glycol, and urea in the first ternary deep eutectic solvent is 1:2:1-8.

[0039] Further, the molar ratio of choline chloride, 1,3-propanediol, and urea in the second ternary deep eutectic solvent is 1:2:1-8.

[0040] In some preferred embodiments, the crosslinking agent includes N,N'-methylenebisacrylamide (MBA) and / or 1,6-hexanediol diacrylate, and is not limited thereto.

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

[0042] In some preferred embodiments, the metal salt includes any one of zinc chloride, zinc triflate, lithium bistrifluoromethanesulfonimide, lithium perchlorate, sodium chloride, aluminum chloride, magnesium bromide, or a combination of two or more thereof, and is not limited thereto.

[0043] In some preferred embodiments, the mass ratio of the supramolecular gelator to the ternary deep eutectic solvent is 1-10:100.

[0044] Further, the mass ratio of the amphoteric polymer monomer to the ternary eutectic solvent is 10-100:100.

[0045] Further, the mass ratio of the crosslinking agent to the ternary eutectic solvent is 0.01-1:100.

[0046] Further, the mass ratio of the photoinitiator to the ternary eutectic solvent is 1-10:100.

[0047] Further, the concentration of the metal salt in the mixed reaction system is 0.1-2 mol·L -1 .

[0048] In some preferred embodiments, the wavelength of the light used for the photoinitiated polymerization is 365 nm, and the light exposure time is 5-60 min.

[0049] Another aspect of the embodiments of the present application also provides a self-healing stretchable eutectic gel electrolyte prepared by the above preparation method, wherein the eutectic gel electrolyte has a supramolecular-polymer double network structure.

[0050] The self-healing stretchable eutectic gel electrolyte in the present application is a semi-solid eutectic gel electrolyte.

[0051] In some preferred embodiments, the conductivity of the eutectic gel electrolyte is 3-10 mS·cm -1 , the metal ion transference number is 0.5-0.8, and the temperature resistance range is -60-80℃.

[0052] In some preferred embodiments, the uniaxial stretchability of the eutectic gel electrolyte is greater than 1000%, and the biaxial stretchability is greater than 1000%.

[0053] In some preferred embodiments, the self-healing temperature range of the eutectic gel electrolyte is -60-80℃, and the electronic healing efficiency is 95%-100%.

[0054] In some preferred embodiments, the mechanical healing efficiency of the eutectic gel electrolyte is 30%-50%, the uniaxial stretchability after healing is 300%-500%, and the biaxial stretchability is greater than 500%.

[0055] Another aspect of the embodiments of the present application also provides an application of the above self-healing stretchable eutectic gel electrolyte in the field of energy storage.

[0056] Further, the application is in the preparation of metal ion batteries, self-healing stretchable all-eutectic gel soft batteries or flexible electronic devices.

[0057] The application of the eutectic gel electrolyte in the metal ion battery can avoid the generation of metal dendrites, for example, zinc ion battery.

[0058] Another aspect of the embodiments of the present application also provides a metal ion battery comprising the self-healing stretchable eutectic gel electrolyte described above.

[0059] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0060] The experimental materials used in the following examples are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0061] Example 1

[0062] Preparation of eutectic solvent: according to the molar ratio of 1:2:4, choline chloride, urea and ethylene glycol were weighed in a glass vial, heated and stirred at 60℃ for 2h, and then naturally cooled to room temperature to obtain a homogeneous transparent solution, which was the ternary eutectic solvent (DES). The obtained ternary eutectic solvent was dissolved in 1mol·L -1 of zinc chloride (ZnCl2) to obtain ZnCl2-DES.

[0063] Preparation of supramolecular gelator: a mixture of 5.0g (R)-12-hydroxystearic acid methyl ester and 5.0g of hydrazine hydrate was placed in 45mL of ethanol and heated to reflux for 24 hours, then the reaction mixture was placed in 250mL of water to obtain a light yellow precipitate. 5.0g of the crude product was refluxed in 100g of n-hexane for 30 minutes. The filter cake was washed with a small amount of n-hexane, and then recrystallized twice with a mixture of ethyl acetate and methanol (1:1) to obtain the supramolecular gelator (0-HSAH).

[0064] Preparation of self-healing stretchable eutectic gel electrolyte: accurately take 30.0 mg of 0-HSAH, 300 mg of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt (MAEDS), 44.8 mg of Irgacure 2959, 1 mg of MBA, 1000 mg of ZnCl2-DES solution prepared in Example 1 into a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / PMAEDS supermolecular-polymer double network eutectic gel electrolyte. In the supermolecular-polymer double network eutectic gel electrolyte, the mass of 0-HSAH accounts for 3% of the mass of ZnCl2-DES solution, and the mass of MAEDS accounts for 30% of the mass of ZnCl2-DES solution.

[0065] Example 2

[0066] Preparation of self-healing stretchable eutectic gel electrolyte: accurately take 30.0 mg of 0-HSAH, 300 mg of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt (MAEDS), 44.8 mg of Irgacure 2959, 1 mg of MBA, 1000 mg of ZnCl2-DES solution prepared in Example 1 into a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / PMAEDS supermolecular-polymer double network eutectic gel electrolyte. In the supermolecular-polymer double network eutectic gel electrolyte, the mass of 0-HSAH accounts for 3% of the mass of ZnCl2-DES solution, and the mass of MAEDS accounts for 30% of the mass of ZnCl2-DES solution.

[0067] Example 3

[0068] Preparation of self-healing stretchable eutectic gel electrolyte: accurately take 30.0 mg of 0-HSAH, 300 mg of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt (MAEDS), 44.8 mg of Irgacure 2959, 1 mg of MBA, 1000 mg of ZnCl2-DES solution prepared in Example 1 into a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / PMAEDS supermolecular-polymer double network eutectic gel electrolyte. In the supermolecular-polymer double network eutectic gel electrolyte, the mass of 0-HSAH accounts for 3% of the mass of ZnCl2-DES solution, and the mass of MAEDS accounts for 30% of the mass of ZnCl2-DES solution.

[0069] Example 4

[0070] Preparation of self-healing stretchable deep eutectic gel electrolyte: 30.0 mg of 0-HSAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA and 1000 mg of ZnCl2-DES solution prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular deep eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / MAEDS supermolecular-polymer double network deep eutectic gel electrolyte. In the supermolecular-polymer double network deep eutectic gel electrolyte, the mass of 0-HSAH accounted for 3% of the mass of the ZnCl2-DES solution, and the mass of MAEDS accounted for 30% of the mass of the ZnCl2-DES solution.

[0071] Example 5

[0072] Preparation of deep eutectic solvent: Choline chloride, urea and ethylene glycol were weighed according to the molar ratio of 1:2:4 in a glass vial, heated and stirred at 60°C for 2 h to form a homogeneous transparent solution, and then naturally cooled to room temperature to obtain a ternary deep eutectic solvent (DES). 1 mol·L -1 of sodium chloride (NaCl) was dissolved in the obtained ternary deep eutectic solvent to obtain a NaCl-DES.

[0073] Preparation of self-healing stretchable deep eutectic gel electrolyte: 30.0 mg of 0-HSAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA and 1000 mg of ZnCl2-DES solution prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular deep eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / MAEDS supermolecular-polymer double network deep eutectic gel electrolyte. In the supermolecular-polymer double network deep eutectic gel electrolyte, the mass of 0-HSAH accounted for 3% of the mass of the ZnCl2-DES solution, and the mass of MAEDS accounted for 30% of the mass of the ZnCl2-DES solution.

[0074] Example 6

[0075] Preparation of deep eutectic solvent: Choline chloride, urea, 1,3-propanediol were weighed according to the molar ratio of 1:2:4 in a glass vial, heated at 60 ℃ and stirred for 2 h, and then a homogeneous transparent solution was formed. The ternary deep eutectic solvent (DES) was obtained after natural cooling to room temperature. 1 mol·L -1 of zinc chloride (ZnCl2) was dissolved in the obtained ternary deep eutectic solvent to obtain ZnCl2-DES.

[0076] Preparation of self-healing stretchable deep eutectic gel electrolyte: 30.0 mg of 0-HSAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA, and 1000 mg of ZnCl2-DES solution were accurately weighed in a glass vial. After heating to complete dissolution, the solution was naturally cooled to room temperature and left to stand for 30 min to form a first heavy supramolecular deep eutectic gel network. Then, the solution was irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 0-HSAH / PMAEDS supramolecular-polymer double network deep eutectic gel electrolyte. In the supramolecular-polymer double network deep eutectic gel electrolyte, the mass of 0-HSAH accounted for 3% of the mass of ZnCl2-DES solution, and the mass of MAEDS accounted for 30% of the mass of ZnCl2-DES solution.

[0077] Example 7

[0078] Preparation of supramolecular gelator: 2.0 g of 0-HSAH and 1.7 g of acetaldehyde were dissolved in 7.0 g of methanol at 0 ℃, and 0.8 g of glacial acetic acid was added as a catalyst. The product was cooled after stirring at 70 ℃ for 5 h, and then 30 g of methanol was added for filtration and recrystallization to obtain (R)-N'-ethylidene-12-hydroxyoctadecane hydrazine. 0.43 g of (R)-N'-ethylidene-12-hydroxyoctadecane hydrazine was dissolved in 5 mL of methanol, and stirred at room temperature for 30 min. 156 mg of sodium cyanoborohydride and 156 mg of glacial acetic acid were dissolved in 1 mL of methanol, and then the methanol solution was added dropwise under a nitrogen atmosphere for more than 10 min, followed by stirring at 0 ℃ for 5 h and stirring at room temperature for 45 min. The filtrate was washed with water and recrystallized with ethyl acetate. (The filtrate was added with 1N aqueous sodium bicarbonate solution). The crude product was extracted with chloroform, vacuum dried, and then recrystallized twice with a mixture of 200 g of ethyl acetate and 100 g of methanol to obtain a supramolecular gelator (2-HSAH).

[0079] Preparation of self-healing stretchable eutectic gel electrolyte: 50.0 mg of 10-HSAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA, and 1000 mg of ZnCl2-DES solution prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 10-HSAH / PMAEDS supermolecular-polymer double network eutectic gel electrolyte. In the supermolecular-polymer double network eutectic gel, the mass of 10-HSAH accounted for 5% of the mass of the ZnCl2-DES solution, and the mass of MAEDS accounted for 30% of the mass of the ZnCl2-DES solution.

[0080] Example 8

[0081] Preparation of a supermolecular gelator: A mixture of 1.0 g of 0-HSAH and 0.7 g of decanal was heated in 10 mL of methanol. 0.3 g of glacial acetic acid was used as a catalyst. Refluxed under N2atmosphere for 2 h, after cooling, filtered and recrystallized with methanol to obtain (R)-N'-decylidene-12-hydroxyoctadecanehydrazine. 0.20 g of (R)-N'-decylidene-12-hydroxyoctadecanehydrazine was dissolved in 20 mL of methanol at room temperature, and stirred for 30 min. 0.06 g of sodium cyanoborohydride and 0.06 g of glacial acetic acid were dissolved in 10 mL of methanol, and then added dropwise into the methanol solution under a nitrogen atmosphere for more than 30 min, and then stirred at room temperature for 5 h. The filtrate was added with 1 N aqueous sodium bicarbonate solution). The crude product was extracted with chloroform, vacuum dried, and recrystallized with methanol to obtain a supermolecular gelator (10-HSAH).

[0082] Preparation of a supermolecular-polymer double network eutectic gel electrolyte: 50.0 mg of 10-HSAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA, and 1000 mg of ZnCl2-DES solution prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first supermolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a 10-HSAH / PMAEDS supermolecular-polymer double network eutectic gel electrolyte. In the supermolecular-polymer double network eutectic gel, the mass of 10-HSAH accounted for 5% of the mass of the ZnCl2-DES solution, and the mass of MAEDS accounted for 30% of the mass of the ZnCl2-DES solution.

[0083] Example 9

[0084] Preparation of supramolecular gelator: A mixture of 5.0 g of methyl stearate and 5.0 g of hydrazine hydrate was heated to reflux in 45 mL of ethanol for 24 h. The reaction mixture was then diluted in 250 mL of water to obtain a light yellow crude product. The crude product was washed under reflux with hexane and then recrystallized twice from a mixture of ethyl acetate and methanol (1:1) to obtain the supramolecular gelator (SAH).

[0085] Preparation of supramolecular-polymer dual network eutectic gel electrolyte: 40.0 mg of SAH, 300 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA and 1000 mg of ZnCl2-DES solution prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled to room temperature for 30 min to form a first heavy supramolecular eutectic gel network, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a SAH / PMAEDS supramolecular-polymer dual network eutectic gel electrolyte. In the supramolecular-polymer dual network eutectic gel, the mass of SAH accounts for 4% of the mass of the ZnCl2-DES solution, and the mass of MAEDS accounts for 30% of the mass of the ZnCl2-DES.

[0086] Comparative Example 1

[0087] 400 mg of MAEDS, 44.8 mg of Irgacure 2959, 1 mg of MBA and 1000 mg of ZnCl2-DES prepared in Example 1 were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a polymer single network eutectic gel electrolyte. In the eutectic electrolyte, the mass of MAEDS accounts for 40% of the mass of the ZnCl2-DES solution.

[0088] Comparative Example 2

[0089] 400 mg of MAEDS, 44.8 mg of Irgacure 2959, 1.5 mg of MBA and 1000 mg of an aqueous zinc chloride solution (1 mol L -1 ) were accurately weighed in a glass vial, heated to complete dissolution, and then naturally cooled, and then irradiated under a UV lamp with a wavelength of 365 nm for 20 min to obtain a polymer single network hydrogel electrolyte. In the hydrogel electrolyte, the mass of MAEDS accounts for 40% of the mass of the aqueous solution.

[0090] Comparative Example 3

[0091] Accurately weigh 30.0 mg of 0-HSAH prepared in Example 1 and 1000 mg of ZnCl2-DES prepared in Example 1 into a glass vial, heat to complete dissolution, and then naturally cool to form a supramolecular single network eutectic gel sample. In the sample, the mass of 0-HSAH accounts for 3% of the mass of ZnCl2-DES.

[0092] Performance characterization:

[0093] Figure 1 Picture of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application;

[0094] Figures 2a-2b XRD patterns of the amphoteric polymer eutectic gel prepared in Comparative Example 1 and Comparative Example 3, the supramolecular eutectic gel, and the self-healing stretchable supramolecular-polymer double network eutectic gel prepared in Example 1 of the present application.

[0095] Figure 3 Uniaxial stretching diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application; the diagram clearly shows that the uniaxial stretchability of the self-healing stretchable eutectic gel electrolyte at room temperature is greater than 1000%.

[0096] Figure 4 Biaxial stretching diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application after self-healing; the electrolyte can still maintain a biaxial stretchability greater than 500% after self-healing for 4 h under ambient conditions, which illustrates the excellent self-healing property of the self-healing stretchable eutectic gel electrolyte.

[0097] Figures 5a-5b Stress-strain curve diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application at low temperature and under different self-healing states; the diagram clearly shows that the electrolyte not only has excellent self-healing property but also has wide temperature tolerance.

[0098] Figure 6 Stretching diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application and the PMAEDS polymer hydrogel electrolyte prepared in Comparative Example 2 at different temperatures; the diagram shows that the self-healing stretchable eutectic gel electrolyte has very excellent temperature tolerance (60°C to +80°C) compared with the polymer hydrogel prepared in Comparative Example 2, and again confirms the excellent stretchability of the electrolyte at extreme temperatures.

[0099] Figure 7 Conductivity diagram of the self-healing stretchable eutectic gel electrolyte prepared in Example 1 of the present application before and after self-healing under high and low temperature environments; the electrolyte has a conductivity greater than 1 mS·cm1 1The conductivity of the electrolyte can be seen to be excellent even under extreme conditions.

[0100] Figures 8a-8b Zn 2+ ion transference number analysis plot; this data indicates that the self-healing stretchable eutectic gel electrolyte prepared in Example 1 is able to achieve a Zn 2+ transference number of up to 0.77.

[0101] Figure 9 is the zinc deposition / stripping data plot of Zn / / Zn symmetric cells using the self-healing stretchable eutectic gel electrolyte prepared in Example 1 and the PMAEDS polymer hydrogel electrolyte prepared in Comparative Example 2. By comparison, it can be seen that the Zn / / Zn symmetric cell using the eutectic gel electrolyte exhibits good cycling performance, low and stable overpotential of 0.4 V, and is able to maintain a high coulombic efficiency of 100% for 300 cycles at a current density of 1 mA cm -2 and a plating capacity of 1 mAh cm -2

[0102] Figure 10 is the cycling performance plot of Zn / / SS asymmetric cells using the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer eutectic gel prepared in Example 1 as electrolyte. By comparison, it can be seen that the Zn / / SS asymmetric cell using the eutectic gel electrolyte is able to achieve a highly reversible zinc deposition / stripping for 150 hours (150 cycles) at a current density of 1 mA cm -2 with a coulombic efficiency close to 100%; while the coulombic efficiency of the Zn / / SS asymmetric cell using the PMAEDS polymer hydrogel electrolyte fluctuates and disappears after only 35 cycles, demonstrating the good cycling stability of the self-healing stretchable eutectic gel electrolyte.

[0103] Figure 11 is the XRD plot of the zinc anode of Zn / / Zn symmetric cells using the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer eutectic gel prepared in Example 1 as electrolyte after multiple repeated deposition / stripping; by comparison, it can be seen that the composition of the zinc anode of the cell based on the eutectic gel electrolyte remains unchanged during the repeated deposition / stripping cycles, while the zinc anode of the cell based on the polymer hydrogel electrolyte generates a byproduct Zn5(OH)8Cl2H2O on the surface.

[0104] Figures 12a-12b ​The Zn / / Zn symmetric batteries prepared by using the amphoteric polymer hydrogel prepared in Comparative Example 2 and the supramolecular-polymer deep eutectic gel prepared in Example 1 as electrolytes were repeatedly deposited / peeled, and the electron microscope images of the zinc anodes were obtained.

[0105] It was found by comparison that the zinc anode surface of the battery based on the deep eutectic gel electrolyte still presented a smooth, dense and dendrite-free morphology after repeated deposition / peeling, indicating that the zinc deposition was very uniform. The zinc anode surface of the battery based on the polymer hydrogel electrolyte grew a large number of needle-shaped and sheet-shaped zinc dendrites.

[0106] In addition, the inventors of the present application also carried out tests with other raw materials, process operations and process conditions described in the present specification in reference to the foregoing examples, and all obtained relatively ideal results.

[0107] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.

Claims

1. A method for preparing a self-healing stretchable eutectic gel electrolyte, characterized by The application relates to a self-healing and stretchable low eutectic gel electrolyte. The amphoteric polymer monomer comprises any one of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, N-carboxymethyl-N,N-bis(2-hydroxyethyl)-1-dodecylammonium inner salt, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate and 2-methacryloyloxyethylphosphocholine or a combination of two or more thereof. The supramolecular gel factor has a structure as shown in formula (I). n is selected from 0-10, and R is selected from H or OH. ； The ternary eutectic solvent comprises a first ternary eutectic solvent and / or a second ternary eutectic solvent; the first ternary eutectic solvent comprises choline chloride, ethylene glycol and urea; and the second ternary eutectic solvent comprises choline chloride, 1,3-propanediol and urea. The metal salt comprises any one of zinc chloride, zinc triflate, lithium bistrifluoromethanesulfonimide, lithium perchlorate, sodium chloride, aluminum chloride and magnesium bromide or a combination of two or more thereof. In the structure shown in formula (I), n is 0, 2, 6 or 10, and R is OH. The conductivity of the eutectic gel electrolyte is 3-10 mS·cm -1 The metal ion transference number is 0.5-0.8, and the temperature resistance range is -60-80 ℃.

2. The production method according to claim 1, characterized by, In the first ternary eutectic solvent, the molar ratio of choline chloride, ethylene glycol and urea is 1:2:1-8.

3. The method of claim 1, wherein: In the second ternary eutectic solvent, the molar ratio of choline chloride, 1,3-propanediol and urea is 1:2:1-8.

4. The method of claim 1, wherein: The crosslinking agent comprises N,N'-methylenebisacrylamide and / or 1,6-hexanediol diacrylate.

5. The method of claim 1, wherein: The photoinitiator comprises 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and / or phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide. The mass ratio of the supramolecular gel factor to the ternary eutectic solvent is 1-10:

100.

6. The method of claim 1, wherein: The mass ratio of the amphoteric polymer monomer to the ternary eutectic solvent is 10-100:

100. The mass ratio of the crosslinking agent to the ternary eutectic solvent is 0.01-1:

100. The mass ratio of the photoinitiator to the ternary eutectic solvent is 1-10:

100. The photopolymerization reaction adopts a light wavelength of 365 nm and a light irradiation time of 5-60 min. And / or, the concentration of the metal salt in the mixed reaction system is 0.1-2 mol·L -1 .

7. The method of claim 1, wherein: The low eutectic gel electrolyte has a supramolecular-polymer double network structure.

8. The self-healing stretchable eutectic gel electrolyte produced by the method of any one of claims 1-7, characterized by: The uniaxial stretchability of the low eutectic gel electrolyte is greater than 1000%, and the biaxial stretchability is greater than 1000%.

9. The eutectic gel electrolyte of claim 8, wherein: The self-healing temperature range of the low eutectic gel electrolyte is -60-80 DEG C, and the electronic healing efficiency is 95%-100%. The mechanical healing efficiency of the low eutectic gel electrolyte is 30%-50%, the uniaxial stretchability after healing is 300%-500%, and the biaxial stretchability is greater than 500%. ​ 10. Use of the self-healing stretchable eutectic gel electrolyte according to claim 8 or 9 in the field of energy storage.

11. Use according to claim 10, characterized in that: The use is the use of the self-healing stretchable eutectic gel electrolyte in the preparation of a metal-ion battery, a self-healing stretchable all-eutectic gel soft battery or a flexible electronic device.

12. A metal-ion battery, characterized in that comprising the self-healing stretchable eutectic gel electrolyte according to claim 8 or 9.

Images