CN113193228B - Crosslinked solid electrolyte and preparation method and application thereof - Google Patents
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Abstract
The application discloses a cross-linked solid electrolyte and a preparation method and application thereof, belonging to the technical field of new energy. The crosslinked solid electrolyte is obtained by crosslinking reaction raw materials including sulfhydryl-modified graphene oxide, a monomer A and a monomer B. The solid electrolyte does not need to attach to a supporting material, has strong mechanical property, and has self-repairability and reworkability. In addition, the graphene oxide is used as a crosslinking point, so that the microphase separation degree can be improved, the crystallization performance of the polymer is reduced, the conductivity of lithium ions is improved, and the heat conduction performance is improved.
Description
Technical Field
The application relates to a cross-linked solid electrolyte and a preparation method and application thereof, belonging to the technical field of new energy.
Background
The electrolyte is one of the key materials of the lithium ion battery, and is arranged between the positive electrode and the negative electrode of the battery to play a role in transferring charges. However, most of the electrolytes used in the conventional lithium ion batteries are conventional combustible organic liquids. The liquid electrolyte has poor thermal stability, is inflammable and easy to leak, has low energy density, is easy to react with oxygen and water to lose efficacy, can react with electrode active substances, and has huge potential safety hazards in the repeated charging and discharging process, thereby hindering the further development of the lithium ion battery.
Compared with a liquid lithium ion battery using a liquid electrolyte, an all-solid battery has more significant advantages, such as high safety, wide electrochemical window, high energy density, and the like. The polymer solid electrolyte has become a research hotspot because of its advantages of light weight, good processability and the like. However, the current polymer solid electrolyte has the defects of poor mechanical property, poor reworkability and the like, and always restricts the large-scale application of the polymer solid electrolyte.
Disclosure of Invention
In order to solve the problems, the solid electrolyte does not need to be attached with a supporting material, has strong mechanical property, and has self-repairability and reworkability. In addition, the graphene oxide is used as a crosslinking point, so that the microphase separation degree can be improved, the crystallization performance of the polymer can be reduced, the conductivity of lithium ions can be improved, and the heat conduction performance can be improved.
According to one aspect of the present application, there is provided a crosslinked solid state electrolyte obtained by crosslinking reaction raw materials including a mercapto group-modified graphene oxide, a monomer a, and a monomer B;
wherein the monomer A is selected from at least one compound shown as a formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 Independently selected from H, C 1-5 Alkyl and C 1-5 One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;
the monomer B is selected from at least one of compounds shown in a formula II:
in formula II, R 5 、R 9 Independently selected from H, C 1-4 Alkyl and C 1-4 One of the alkylcarbonyl groups, R 6 、 R 8 Independently selected from H, C 1-4 Alkyl and C 1-4 One of thioalkyl radicals, R 7 Selected from H, C 1-4 Alkyl and C 2-5 One of an alkenyl group; m and n are independently selected from 1, 2, 3 or 4;
alternatively, R in the monomer A 1 Is selected from C 1-4 One of the alkyl-carbonyl groups is selected from the group consisting of,R 2 is selected from C 1-4 One of the alkyl radicals, R 3 Is selected from C 1-4 One of the alkylcarbonyl groups, R 4 Is selected from C 1-4 One of the alkyl groups.
Preferably, the structural formula of the monomer A is shown as formula III:
the carbon chain length of the monomer A shown as the structural formula III is moderate, the solid electrolyte obtained by crosslinking is good in mechanical property, and the acyloxy is used as an electron donating group, so that the transference number and the transference speed of cations in electrolyte salt are improved, and the ionic conductivity of the solid electrolyte is improved.
Alternatively, R in the monomer B 5 Is selected from C 1-4 One of the alkylcarbonyl groups, R 6 Is selected from C 1-4 One of thioalkyl radicals, R 7 Is selected from C 2-5 One of the alkenyl radicals, R 8 Is selected from C 1-4 One of thioalkyl radicals, R 9 Is selected from C 1-4 One of the alkylcarbonyl groups.
Preferably, the structural formula of the monomer B is shown as a formula IV:
the length of a carbon chain of the monomer B with the structural formula shown in the formula IV is moderate, and two ends of the monomer B contain double bonds, so that chemical bonds can be formed among all branched chains growing from graphene oxide at the crosslinking center, and the prepared crosslinked solid electrolyte has stronger mechanical properties.
Optionally, the mercapto-modified graphene oxide is modified by a mercapto silane coupling agent; and/or
The weight ratio of the mercapto-modified graphene oxide to the monomer A to the monomer B is as follows: 0.005-0.01: 0.96-0.98: 1.
preferably, the weight ratio of the mercapto-modified graphene oxide to the monomer a to the monomer B is: 0.008: 0.97: 1.
the functionalization of the surface of the graphene oxide by using the mercaptosilane coupling agent enables the graphene oxide to be used as a cross-linking point and directly participate in the construction of a dynamic chemical bond, so that the prepared solid electrolyte does not need to be attached to a supporting material and has strong mechanical property.
According to another aspect of the application, a preparation method of a crosslinked solid electrolyte is provided, raw materials including sulfhydryl-modified graphene oxide, a monomer A, a monomer B, an initiator and an electrolyte salt are added into an organic solvent I to obtain a mixed solution A, and the mixed solution A is polymerized into a film to obtain the crosslinked solid electrolyte;
wherein the monomer A is selected from at least one compound shown as a formula V:
in formula V, R 1 、R 2 、R 3 、R 4 Independently selected from H, C 1-5 Alkyl and C 1-5 One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;
the monomer B is selected from at least one compound shown in a formula VI:
in formula VI, R 5 、R 9 Independently selected from H, C 1-4 Alkyl and C 1-4 One of the alkylcarbonyl groups, R 6 、 R 8 Independently selected from H, C 1-4 Alkyl and C 1-4 One of thioalkyl radicals, R 7 Selected from H, C 1-4 Alkyl and C 2-5 One of alkenyl, m and n are independently selected from 1, 2, 3 or 4;
the electrolyte salt is selected from one of lithium salt, sodium salt and potassium salt.
Alternatively, the monomerIn A, R 1 Is selected from C 1-4 One of the alkylcarbonyl groups, R 2 Is selected from C 1-4 One of the alkyl radicals, R 3 Is selected from C 1-4 One of the alkylcarbonyl groups, R 4 Is selected from C 1-4 One of alkyl groups;
preferably, the structural formula of the monomer A is shown as the formula III:
alternatively, R in the monomer B 5 Is selected from C 1-4 One of the alkylcarbonyl groups, R 6 Is selected from C 1-4 One of thioalkyl radicals, R 7 Is selected from C 25 One of the alkenyl radicals, R 8 Is selected from C 1-4 One of thioalkyl radicals, R 9 Is selected from C 1-4 One of alkylcarbonyl groups;
preferably, the structural formula of the monomer B is shown as a formula IV:
optionally, the mercapto-modified graphene oxide is modified by a mercapto silane coupling agent; and/or
The weight ratio of the sulfydryl modified graphene oxide to the monomer A to the monomer B is as follows: 0.005-0.01: 0.96-0.98: 1.
preferably, the weight ratio of the mercapto-modified graphene oxide to the monomer a to the monomer B is: 0.008: 0.97: 1.
optionally, the thiol-modified graphene oxide is prepared by: mixing a mercaptosilane coupling agent and an organic solvent II to obtain a first dispersion system, and mixing graphene oxide and water to obtain a second dispersion system; mixing the first dispersion system and the second dispersion system to obtain a mixed solution B, adjusting the pH of the mixed solution B to 2-6, reacting at 20-90 ℃ for not less than 8h, washing, and drying to obtain the sulfhydryl modified graphene oxide;
wherein the volume ratio of the mercaptosilane coupling agent to the organic solvent II is 1: 3-5, the content of graphene oxide in the second dispersion system is 0.3-0.7 wt%, and the volume ratio of the first dispersion system to the second dispersion system is 1.5-2: 1. The arrangement mode can ensure that the mercaptosilane coupling agent fully functionalizes the graphene oxide, is favorable for forming a network structure taking the graphene oxide as a center when the crosslinking is initiated by light, forms a graphene oxide physical crosslinking network with high crosslinking degree, and improves the mechanical property of the solid electrolyte.
Preferably, the pH value of the mixed solution B is adjusted to 4-5, the mixed solution B reacts for 8-14 hours at the temperature of 40-70 ℃, and the sulfhydryl modified graphene oxide is obtained through washing and drying;
the volume ratio of the mercaptosilane coupling agent to the organic solvent II is 1:4, the content of graphene oxide in the second dispersion system is 0.5 wt%, and the volume ratio of the first dispersion system to the second dispersion system is 1.8: 1.
More preferably, the pH of the mixed solution B is adjusted to 4.5 by hydrochloric acid, the mixed solution B is reacted for 10 hours at 50 ℃, and the mercapto-modified graphene oxide is obtained by washing and drying.
Optionally, adding the sulfhydryl-modified graphene oxide, the monomer A, the monomer B and an electrolyte into an organic solvent I, then adding a photoinitiator to obtain a mixed solution A, coating the mixed solution A on a mold, irradiating with ultraviolet light, and polymerizing to form a film, thereby obtaining the crosslinked solid electrolyte.
Preferably, the mixed solution a is coated on the mold by a casting method.
Optionally, the mold is a glass plate. The mixed solution is coated on the die by adopting a tape casting method, and is polymerized into the solid electrolyte membrane through ultraviolet irradiation initiation, so that the solid electrolyte membrane can be cured in situ and rapidly formed into a membrane without a complex drying process, thereby avoiding the shrinkage or cracking of the electrolyte membrane caused by the drying process, ensuring the quality of the solid electrolyte and improving the production efficiency.
Optionally, the concentration of the monomer B in the mixed solution A is 0.05-0.15 g/mL;
the weight ratio of the mercapto-modified graphene oxide, the monomer A, the monomer B, the electrolyte salt and the photoinitiator in the mixed solution A is 0.005-0.01: 0.96-0.98: 1: 1.2-2: 0.015 to 0.03; and/or
The wavelength of the ultraviolet light is 350-380 nm, and the irradiation time is 20-50 min.
Preferably, the concentration of the monomer B in the mixed solution A is 0.1 g/mL.
Preferably, the weight ratio of the mercapto-modified graphene oxide, the monomer a, the monomer B, the electrolyte salt and the photoinitiator in the mixed solution a is 0.008: 0.97: 1: 1.6: 0.022.
preferably, the wavelength of the ultraviolet light is 365nm, and the irradiation time is 35 min.
Optionally, the organic solvent I is at least one selected from dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene and chlorobenzene;
the photoinitiator is at least one of 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, propiophenone and benzoin isobutyl ether;
the electrolyte salt is lithium salt;
the mercaptosilane coupling agent is at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane and mercaptopropylmethyldiethoxysilane; and/or
The organic solvent II is at least one of methanol, ethanol, acetone, dichloromethane and trichloromethane.
Preferably, the organic solvent I is selected from dichloromethane.
Preferably, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone. 2, 2-dimethoxy-2-phenylacetophenone is used as a photoinitiator, so that the photoinitiation speed is greatly increased, and the mixed solution A can be rapidly formed into a film under the irradiation of ultraviolet light.
Preferably, the lithium salt is at least one of lithium bistrifluoromethanesulfonylimide, lithium perchlorate, lithium chloride, lithium bromide, lithium trifluoromethanesulfonate, lithium hexafluorophosphate and lithium tetrafluoroborate.
Preferably, the lithium salt is lithium bistrifluoromethanesulfonylimide. By adding lithium bis (trifluoromethanesulfonyl) imide as an electrolyte salt, an anion group of the electrolyte salt is more easily coordinated with lithium ions, so that a faster kinetic transmission interface is provided, and ion transmission is promoted.
Preferably, the mercaptosilane coupling agent is mercaptopropyltrimethoxysilane.
Preferably, the organic solvent II is ethanol.
Optionally, the preparation process is done in a glove box.
According to yet another aspect of the present application, there is provided a use of a solid electrolyte selected from at least one of the solid electrolyte described in any one of the above and the solid electrolyte prepared by the preparation method described in any one of the above in a battery.
Benefits of the present application include, but are not limited to:
1. the cross-linked solid electrolyte has the advantages of higher ionic conductivity, wider electrochemical working window, high energy density and excellent cycle performance, and can remarkably prolong the service life of a solid battery. In addition, the solid electrolyte does not need to attach to a supporting material, has strong mechanical property and reworkability, and has simple preparation process and low material cost.
2. According to the cross-linked solid electrolyte, the graphene oxide is used as a cross-linking point through functionalization of the surface of the graphene oxide, and directly participates in construction of a dynamic chemical bond to form a network structure, so that the network structure can improve the transfer efficiency of charges and improve the conductivity of the solid electrolyte; the addition of the graphene oxide can also improve the microphase separation degree, destroy the regularity of polymer chain segments and reduce the crystallization performance of the polymer, thereby improving the ionic conductivity of the solid electrolyte and enhancing the thermal stability and chemical stability of the solid electrolyte.
3. According to the crosslinked solid electrolyte, crosslinking reaction occurs among the mercapto-modified graphene oxide, the multi-mercapto compound monomer and the multi-alkenyl compound monomer, and due to the existence of a dynamic bond generated by the reaction of mercapto and double bonds, the solid electrolyte has excellent self-repairing performance, reworkability and plasticity, and can still maintain the initial mechanical property after being processed and formed for multiple times, so that the purposes of saving energy and reducing cost can be achieved.
4. According to the cross-linked solid electrolyte, the monomer A and the monomer B with electron-donating groups are introduced, so that the transference number of cations in electrolyte salt is improved; in addition, by adding the ethylenically unsaturated monomer, a sulfydryl-alkene click chemical reaction is generated, so that an amorphous region can be formed in the cross-linked polymer, the chain segment movement of the amorphous region causes the repeated 'decomplexation-recompplexing' process of cations in the electrolyte salt, and the conductivity of the polymer electrolyte is obviously improved; by adding lithium bis (trifluoromethanesulfonyl) imide as an electrolyte salt, an anion group of the electrolyte salt is more easily coordinated with lithium ions, so that a faster kinetic transmission interface is provided, and ion transmission is promoted.
5. According to the preparation method of the crosslinked solid electrolyte, the solid electrolyte is prepared by using clean and efficient ultraviolet light illumination to initiate crosslinking reaction, and the method does not need long-time high-temperature heating, is short in reaction period, high in production efficiency, strong in controllability of production links and small in environmental pollution, and enables large-scale industrial production to be possible.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a graph of ac impedance of a solid electrolyte in example 1 of the present application, in which real impedance is plotted on the abscissa and imaginary impedance is plotted on the ordinate.
Fig. 2 is a cyclic voltammogram of the solid electrolyte in example 1 of the present application, wherein the abscissa is voltage and the ordinate is current.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were purchased commercially.
Example 1 solid electrolyte 1#
The solid electrolyte 1# is obtained by crosslinking reaction raw materials including sulfhydryl-modified graphene oxide, a monomer A and a monomer B, wherein:
the structural formula of the monomer A is as follows:
CAS numbers are 22504-50-3,
the structural formula of the monomer B is as follows:
CAS number 905955-60-4;
the preparation method of the solid electrolyte 1# comprises the following steps:
dispersing 7.2mL of mercaptopropyl trimethoxy silane in 28.8mL of ethanol to obtain a solution containing a mercaptosilane coupling agent, adding 20mL of graphene oxide dispersion liquid with the graphene oxide content of 0.5 wt% into the solution, ultrasonically mixing uniformly to obtain a first mixed solution, adjusting the pH of the mixed solution A to 4.5 by using hydrochloric acid, heating in a water bath at 50 ℃ for reaction for 10 hours, naturally cooling to room temperature, centrifugally washing, and drying at 60 ℃ to obtain mercapto-modified graphene oxide powder (hereinafter referred to as GO-SH powder).
The following operations were all performed in the glove box: dispersing 0.008g of GO-SH powder in 5ml of dichloromethane to obtain GO-SH dispersion liquid; dissolving 0.97g of monomer A, 1g of monomer B and 1.6g of lithium bistrifluoromethanesulfonylimide (LiTFSI for short) in 10mL of dichloromethane, uniformly mixing, adding a pre-dispersed GO-SH dispersion liquid, adding 0.022g of 2, 2-dimethoxy-2-phenylacetophenone into the mixed solution, uniformly mixing by shading and ultrasonic treatment to obtain a second mixed solution, coating the second mixed solution on a glass plate by adopting a tape casting method, irradiating for 35min by using ultraviolet rays with the wavelength of 365nm, and polymerizing to form a film to obtain the solid electrolyte No. 1.
Example 2 solid electrolyte 2#
The solid content of the added graphene oxide dispersion was 0.3%, and the rest of the conditions were the same as in example 1.
Example 3 solid electrolyte 4#
The lithium salt added was lithium hexafluorophosphate, and the other conditions were the same as in example 1.
Example 4 solid electrolyte 5#
The mixture was irradiated with ultraviolet rays having a wavelength of 365nm for 20min under the same conditions as in example 1.
Example 5 solid electrolyte 6#
The monomer B added was ethylene glycol diacrylate, and the other conditions were the same as in example 1.
Comparative example 1 solid electrolyte D1#
The solid electrolyte 1# is obtained by crosslinking reaction raw materials including sulfhydryl-modified graphene oxide, a monomer A and a monomer B, wherein:
the structural formula of the monomer A is as follows:
the CAS number is 22504-50-3,
the structural formula of the monomer B is as follows:
CAS number 905955-60-4;
the preparation method of the solid electrolyte 1# comprises the following steps:
dispersing 2mL of mercaptopropyl trimethoxy silane in 8mL of ethanol to obtain a solution containing a mercaptosilane coupling agent, adding 20mL of graphene oxide dispersion liquid with the graphene oxide content of 0.5 wt% into the solution, ultrasonically mixing uniformly to obtain a first mixed solution, adjusting the pH value of the mixed solution A to 4.5 by using hydrochloric acid, heating in a water bath at 50 ℃ for reaction for 10 hours, and performing suction filtration to obtain a mercapto-modified graphene oxide membrane (hereinafter referred to as GO-SH membrane).
The following operations were all performed in the glove box: cutting a GO-SH film with the weight of 0.008g, placing the GO-SH film on a glass plate, dissolving 0.97g of monomer A, 1g of monomer B and 1.6g of lithium bis (trifluoromethanesulfonylimide) (hereinafter abbreviated as LiTFSI) in 10mL of dichloromethane, uniformly mixing, dropwise coating the GO-SH film, dropwise coating 0.022g of 2, 2-dimethoxy-2-phenylacetophenone, and irradiating for 35min by using ultraviolet rays with the wavelength of 365nm to obtain a solid electrolyte D1 #.
Comparative example 2 solid electrolyte D2#
The monomer A added was dimercaptoethylsulfide, and the other conditions were the same as in example 1.
Comparative example 3 solid electrolyte D3#
The reaction was carried out under the same conditions as in example 1 except that the monomer B was not added to the starting materials.
Comparative example 4 solid electrolyte D4#
The weight of the monomer A charged was 1.5g, and the other conditions were the same as in example 1.
Comparative example 5 solid electrolyte D5#
The solid content of the added graphene oxide dispersion was 1.2%, and the rest of the conditions were the same as in example 1.
Experimental example 1
The solid electrolytes 1# to 5# and D1# to D5# were tested for maximum load, maximum strength, breaking load and breaking strength, ion conductivity and interfacial stability, and the test results are shown in Table 1:
TABLE 1
From the above results, it can be seen that: the cross-linked solid electrolyte prepared by the embodiment of the application does not need to be attached with a supporting material, has excellent mechanical property and stronger mechanical property and reworkability.
In addition, the solid electrolyte 1# was subjected to an ionic conductivity test and sweep voltammetry, respectively, as follows:
ionic conductivity: the prepared solid electrolyte membrane is assembled into a (steel sheet/electrolyte membrane/steel sheet) cell by using round steel sheets, an alternating current impedance test is carried out at room temperature by using an electrochemical workstation, and the ionic conductivity sigma of the electrolyte membrane is calculated by using an alternating current impedance spectrum obtained by the test and a formula sigma which is t/RA. Where t is the thickness of the electrolyte membrane, R is the resistance value of the electrolyte membrane, and a is the cross-sectional area of the electrolyte membrane.
Interface stability: the prepared solid electrolyte membrane is assembled into a (stainless steel sheet/electrolyte membrane/lithium metal sheet) battery by using a circular stainless steel sheet and a lithium metal sheet, and scanning volt-ampere test is carried out by using an electrochemical workstation to obtain interface stability.
The test results are shown in fig. 1 and fig. 2, respectively. As can be calculated from FIG. 1, solid electrolyte 1# has excellent ionic conductivity of 2.3X10 -4 S/cm; fig. 2 shows that the solid electrolyte has better electrochemical stability.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (12)
1. The cross-linked solid electrolyte is characterized by being obtained by cross-linking reaction raw materials comprising sulfhydryl-modified graphene oxide, a monomer A and a monomer B;
wherein the monomer A is selected from at least one compound shown as a formula I:
In the formula I, R 1 Is selected from C 1-4 One of the alkylcarbonyl groups, R 2 Is selected from C 1-4 One of the alkyl radicals, R 3 Is selected from C 1-4 One of the alkyl radicals, R 4 Is selected from C 1-4 One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;
the monomer B is selected from at least one of compounds shown in a formula II:
In the formula II, R 5 Is selected from C 1-4 One of the alkyl carbonyl groups, R 6 Is selected from C 1-4 One of thioalkyl radicals, R 7 Is selected from C 2-5 One of the alkenyl radicals, R 8 Is selected from C 1-4 One of thioalkyl radicals, R 9 Is selected from C 1-4 One of alkylcarbonyl groups; m and n are independently selected from 1, 2, 3 or 4;
the preparation method of the cross-linked solid electrolyte comprises the following steps: adding raw materials including sulfydryl modified graphene oxide, a monomer A, a monomer B, an initiator and electrolyte salt into an organic solvent I to obtain a mixed solution A, and polymerizing the mixed solution A to form a film to obtain the cross-linked solid electrolyte, wherein the electrolyte salt is selected from one of lithium salt, sodium salt and potassium salt.
2. The crosslinked solid electrolyte according to claim 1,
the structural formula of the monomer A is shown as a formula III:
3. The crosslinked solid electrolyte according to claim 1,
the structural formula of the monomer B is shown as the formula IV:
4. The crosslinked solid electrolyte of claim 1, wherein the mercapto-modified graphene oxide is modified with a mercapto silane coupling agent; and/or
The weight ratio of the mercapto-modified graphene oxide to the monomer A to the monomer B is as follows: 0.005-0.01: 0.96-0.98: 1.
5. the preparation method of the cross-linked solid electrolyte is characterized by adding raw materials comprising sulfydryl modified graphene oxide, a monomer A, a monomer B, an initiator and electrolyte salt into an organic solvent I to obtain a mixed solution A, and polymerizing the mixed solution A to form a film to obtain the cross-linked solid electrolyte;
wherein the monomer A is selected from at least one compound shown as a formula V:
in formula V, R 1 Is selected from C 1-4 One of the alkylcarbonyl groups, R 2 Is selected from C 1-4 One of the alkyl radicals, R 3 Is selected from C 1-4 One of the alkyl radicals, R 4 Is selected from C 1-4 One of alkyl carbonyl, x and y are independently selected from 1, 2, 3 or 4;
the monomer B is selected from at least one compound shown in a formula VI:
in formula VI, R 5 Is selected from C 1-4 One of the alkylcarbonyl groups, R 6 Is selected from C 1-4 One of thioalkyl radicals, R 7 Is selected from C 2-5 One of the alkenyl radicals, R 8 Is selected from C 1-4 One of thioalkyl radicals, R 9 Is selected from C 1-4 One of alkyl carbonyl, m and n are independently selected from 1, 2, 3 or4；
The electrolyte salt is selected from one of lithium salt, sodium salt and potassium salt.
6. The method according to claim 5, wherein the thiol-modified graphene oxide is prepared by: mixing a mercaptosilane coupling agent with an organic solvent II to obtain a first dispersion system, and mixing graphene oxide with water to obtain a second dispersion system; mixing the first dispersion system and the second dispersion system to obtain a mixed solution B, adjusting the pH of the mixed solution B to 2-6, reacting at 20-90 ℃ for not less than 8h, centrifugally washing, and drying to obtain the sulfhydryl-modified graphene oxide;
wherein the volume ratio of the mercaptosilane coupling agent to the organic solvent II is 1: 3-5, the content of graphene oxide in the second dispersion system is 0.3-0.7 wt%, and the volume ratio of the first dispersion system to the second dispersion system is 1.5-2: 1.
7. The preparation method according to claim 6, wherein the thiol-modified graphene oxide, the monomer A, the monomer B and the electrolyte salt are added into the organic solvent I, then the photoinitiator is added to obtain a mixed solution A, and the mixed solution A is coated on a mold and irradiated by ultraviolet light to polymerize into a film, so as to obtain the crosslinked solid electrolyte.
8. The preparation method according to claim 5, wherein the thiol-modified graphene oxide, the monomer A, the monomer B and the electrolyte salt are added into the organic solvent I, then the photoinitiator is added to obtain a mixed solution A, and the mixed solution A is coated on a mold and irradiated by ultraviolet light to polymerize into a film, so as to obtain the crosslinked solid electrolyte.
9. The preparation method according to claim 7, wherein the concentration of the monomer B in the mixed solution A is 0.05-0.15 g/mL;
the weight ratio of the mercapto-modified graphene oxide, the monomer A, the monomer B, the electrolyte salt and the photoinitiator in the mixed solution A is 0.005-0.01: 0.96-0.98: 1: 1.2-2: 0.015 to 0.03; and/or
The wavelength of the ultraviolet light is 350-380 nm, and the irradiation time is 20-50 min.
10. The method according to claim 7, wherein the organic solvent I is at least one selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene, and chlorobenzene;
the photoinitiator is at least one of 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, propiophenone and benzoin isobutyl ether;
the electrolyte salt is lithium salt;
the mercaptosilane coupling agent is at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane and mercaptopropylmethyldiethoxysilane; and/or
The organic solvent II is at least one of methanol, ethanol, acetone, dichloromethane and chloroform.
11. The method of claim 10, wherein the lithium salt is lithium bistrifluoromethanesulfonylimide.
12. Use of a solid electrolyte in a battery, wherein the solid electrolyte is selected from at least one of the solid electrolyte according to any one of claims 1 to 4 and the solid electrolyte prepared by the preparation method according to any one of claims 5 to 11.
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