Gel electrolytes, their preparation methods, applications, modified electrodes, modified separators, and solid-state batteries

Abstract

This invention belongs to the field of batteries, specifically relating to gel electrolytes and their preparation methods, applications, modified electrodes, modified separators, and solid-state batteries. The preparation method of the gel electrolyte involves polymerizing a mixed solution containing a basic electrolyte, a composite monomer, an initiator, and a crosslinking agent. The basic electrolyte includes a solvent and a conductive electrolyte. The composite monomer includes formulas 1 and 2. Research in this invention shows that using formulas 1 and 2 together as monomers can achieve synergy, optimize the gel network, and thus endow the prepared gel electrolyte with excellent safety, ion conductivity, and interfacial fusion ability of its electrodes. This improves the overall oxidation stability of the material, reduces the interfacial reactivity of the electrolyte under high-temperature conditions, and enhances the performance of high-temperature batteries.

Description

Technical Field

[0001] This invention relates to the field of electrolytes, and more specifically to the field of gel polymer electrolytes. Background Technology

[0002] With the increasing popularity of portable electronic devices and the rapid development of electric vehicles, energy storage devices, represented by lithium batteries, have experienced rapid development and widespread application. However, the use of flammable and unstable organic liquid solvents can easily lead to problems such as battery leakage, combustion, weakened battery structural strength, and low safety performance, severely restricting the development of lithium batteries. Electrolyte solidification is an important approach to solving battery safety issues. Among these, in-situ thermally initiated gel polymer electrolytes have broad application prospects due to their leak-proof nature, high ionic conductivity, improved mechanical properties, and interfacial compatibility.

[0003] The preparation of gel electrolytes via monomer polymerization is currently a mainstream research direction. For example, patent document CN113717328A discloses a gel electrolyte composition comprising a first polymerizing monomer, a second polymerizing monomer, a lithium salt, an initiator, and a solvent; the first polymerizing monomer includes at least one selected from methyl methacrylate, styrene, vinyl acetate, acrylonitrile, fluoroacrylate, polyethylene glycol diacrylate, and polyethylene glycol acrylate; the second polymerizing monomer includes phosphate esters containing carbon-carbon double bonds and / or carbon-nitrogen triple bonds. As another example, patent document CN115403701A discloses a gel electrolyte precursor, a gel electrolyte, and an electrochemical device; the gel electrolyte precursor has multiple monomers; the monomers include at least two selected from acid anhydride monomers containing double bonds, ester monomers containing double bonds, or acrylate monomers. Patent document CN120600902A discloses a gel electrolyte precursor and its preparation method, a gel electrolyte, and a secondary battery, belonging to the technical field of methods or devices for directly converting chemical energy into electrical energy. The gel electrolyte precursor of the present invention comprises a polymeric monomer, a catalyst, an initiator, and a lithium salt; the polymeric monomer comprises monomer A and monomer B; monomer B comprises at least one of a polyether compound, a polysiloxane compound, boric acid, and its derivatives.

[0004] In summary, although existing technologies have reported numerous methods for forming solid electrolytes through in-situ polymerization, the performance of solid electrolytes varies depending on the monomers, polymerization behavior, and polymer network. Existing technologies also suffer from problems such as poor mechanical flexibility of the highly cross-linked network structure, susceptibility to microcracks, and inability to protect the interface from degradation and regeneration, especially at high temperatures. Furthermore, existing polymer backbones exhibit poor oxidative stability, leading to severe interfacial reactions at high temperatures and rapid degradation of battery performance. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the first objective of the present invention is to provide a method for preparing a gel electrolyte, which aims to improve the safety, ion conductivity and interfacial compatibility of the prepared gel electrolyte.

[0006] A second objective of this invention is to provide the gel electrolyte prepared by the aforementioned method, its applications, and a modified electrode.

[0007] A third objective of this invention is to provide a modified electrode, a modified separator, and a solid-state battery comprising the gel electrolyte.

[0008] A method for preparing a gel electrolyte involves polymerizing a mixed solution comprising a base electrolyte, a composite monomer, an initiator, and a crosslinking agent; wherein the base electrolyte comprises a solvent and a conductive electrolyte; and the composite monomer comprises Formula 1 and Formula 2.

[0009] Formula 1;

[0010] Formula 2;

[0011] In Formula 1, R1 to R4 are individually H, C1 to C4 alkyl, C1 to C4 alkoxy or halogen;

[0012] In Formula 2, X is a C1-C4 alkyl (alkylene) or oxaalkyl (oxaalkylene or oxacarbon chain); R5-R7 are individually C1-C4 alkyl or alkoxy groups; R8 is a vinyl or acrylate group.

[0013] The present invention demonstrates that using Formula 1 and Formula 2 together as monomers can achieve synergy and optimize the gel network. This can endow the prepared gel electrolyte with excellent safety, ion conductivity and interfacial fusion ability of its electrodes, thereby improving the overall oxidation stability of the material, reducing the interfacial reactivity of the electrolyte under high temperature conditions, and improving the performance of high-temperature batteries.

[0014] In this invention, the mass ratio of Formula 1 to Formula 2 in the composite monomer is 1~5:1; preferably 1.5~4.5:1.

[0015] In this invention, in Formula 1, R1 and R4 are individually H; R2 and R3 are preferably C1-C4 alkyl or haloalkyl, more preferably methane. The preferred combination of Formula 1 and Formula 2 helps to further optimize the polymerization and polymerization structure, and helps to further improve the high-temperature performance of the electrolyte.

[0016] Studies have shown that the preferred monomer of Formula 1, when combined with Formula 2, can achieve synergy and further enhance the high-temperature, long-cycle performance of the electrolyte at high rates.

[0017] Formula 2 includes at least one of Formula 2A and Formula 2B;

[0018] Formula 2A;

[0019] Formula 2B;

[0020] Preferably, Formula 2 is Formula 2B. Studies have shown that Formula 2B is preferably used as monomer 2, which, in combination with monomer 1, can further synergistically enhance the interfacial stability and mechanical repair capability of the prepared electrolyte, and can further synergistically enhance the high-rate, high-temperature, long-cycle stability of the battery.

[0021] In this invention, the solvent in the basic electrolyte includes at least one of ether solvents and ester solvents;

[0022] Preferably, the solvent includes at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, methyl propionate, methyl acetate, and ethyl acetate.

[0023] Preferably, the conductive electrolyte is a conductive salt capable of providing active cations, and the active cations are adjusted according to the different battery systems used in the gel electrolyte, for example including at least one of lithium ions, sodium ions, and potassium ions.

[0024] As an alternative, if the gel electrolyte is used in a lithium-ion battery, its conductive salt is a conductive lithium salt. Similarly, if the gel electrolyte is used in a sodium-ion battery, its conductive salt is a conductive sodium salt. If the gel electrolyte is used in a potassium-ion battery, its conductive salt is a conductive potassium salt.

[0025] Preferably, the conductive electrolyte includes at least one of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium bis(oxalate)borate, lithium difluorooxalateborate, and lithium difluorobis(oxalate)phosphate.

[0026] Preferably, the concentration of the conductive electrolyte in the base electrolyte is 0.5~5M, and more preferably 1~3M.

[0027] In this invention, the crosslinking agent is selected from any one or more of polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated trimethylolpropoxide, pentaerythritol tetraacrylate, ethyl 2,2,2-trifluoroacrylate, trifluoroethyl methacrylate, pentafluorophenyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, perfluorobutyl acrylate, and N,N′-methylenediacrylamide.

[0028] The initiator is a free radical initiator, preferably one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and azobismethylvalerate.

[0029] In this invention, the concentration of the composite monomer in the mixed solution is 2-30 wt.%; the concentration of the initiator is 0.01-0.1 wt.%; and the concentration of the crosslinking agent is 0.5-3 wt.%. Further, the concentration of the composite monomer is 5-10 wt.%; the concentration of the initiator is 0.01-0.03 wt.%; and the concentration of the crosslinking agent is 0.5-1.5 wt.%.

[0030] The mixed solution further comprises additives, including at least one of vinylene carbonate and fluorovinyl carbonate. Further, the content of the additives in the mixed solution may be less than 1 wt.%, and more particularly, it may be 0.05~0.5 wt.%.

[0031] In this invention, the other components in the mixed solution can be the basic electrolyte, and the content of the components therein is 100%.

[0032] In this invention, the polymerization temperature can be 35~85℃.

[0033] Preferably, the polymerization process includes a first polymerization process and a second polymerization process; wherein the temperature of the first polymerization process is 40~50℃; and the temperature of the second polymerization process is 60~80℃.

[0034] Preferably, the combined monomers, in conjunction with the two-stage gradient polymerization process, can further optimize the polymerization behavior and structure, and further enhance the high-rate, high-temperature long-cycle performance of the electrolyte.

[0035] Preferably, the total polymerization time is 2-36 hours; more preferably 6-20 hours.

[0036] Preferably, when a two-stage polymerization process is used, the time for the first polymerization stage is 1 to 5 hours, and the time for the second polymerization stage is 5 to 15 hours.

[0037] The present invention also provides a gel electrolyte prepared by the preparation method described above.

[0038] In this invention, the co-polymerization of the composite monomers can construct a gel network with excellent interfacial bonding ability, active ions and electronic conduction network based on different polymerization behaviors, thereby endowing the assembled battery with electrochemical performance.

[0039] The present invention also provides the application of the gel electrolyte obtained by the preparation method described above, for use in the preparation of solid batteries;

[0040] Preferably, it is placed between the positive and negative electrodes for the fabrication of a solid-state battery;

[0041] Furthermore, the gel electrolyte can be composited on the surface of the positive electrode near the negative electrode, the surface of the separator, and the surface of the negative electrode near the positive electrode.

[0042] The present invention also provides a modified electrode, comprising an electrode and a gel electrolyte of the present invention composite thereon on its surface; the electrode is a positive electrode and / or a negative electrode.

[0043] In this invention, the mixed solution described herein can be composited on the surface of the electrode, followed by polymerization to form the gel electrolyte on the surface of the electrode.

[0044] The present invention also provides a modified membrane, comprising a base membrane and the gel electrolyte of the present invention composited on the surface.

[0045] In this invention, the mixed solution described herein can be composited on the surface of the diaphragm, followed by polymerization to form the gel electrolyte on the surface of the diaphragm.

[0046] The present invention also provides a solid battery comprising a positive electrode, a barrier layer and a negative electrode sequentially laminated together, wherein the barrier layer comprises the gel electrolyte described in the present invention;

[0047] Preferably, the positive and / or negative electrode is the modified electrode; and / or, the barrier layer is the modified membrane.

[0048] The solid-state battery of the present invention can be prepared based on an in-situ method, the steps of which are: inserting a positive electrode and a negative electrode cell into a battery case, injecting the mixed solution, and then encapsulating and performing in-situ polymerization to obtain the battery.

[0049] In addition, the present invention also provides a non-in-situ preparation method, for example, first preparing the solid electrolyte, or pre-preparing the modified electrode and the modified separator, and then assembling the solid battery in the manner of positive electrode, barrier layer and negative electrode.

[0050] The solid-state battery described in this invention can be at least one of solid lithium-ion batteries, solid sodium-ion batteries, and solid potassium-ion batteries.

[0051] In this invention, the solid-state battery, apart from the gel electrolyte described in this invention, may contain other known electrodes, separators, and structures.

[0052] The positive electrode includes a positive current collector and a positive electrode material composited on the surface of the positive current collector; the positive electrode material is obtained by curing a slurry of positive active material, conductive agent, and binder.

[0053] The weight ratio of the positive electrode active material, conductive agent and binder is 7~9.5:0.5~2:1.

[0054] Preferably, the positive electrode active material is at least one of NCA, NCM111, NCM523, NCM622, NCM811, lithium iron phosphate, lithium cobalt oxide, lithium-rich manganese-based, lithium nickel oxide, lithium manganese oxide, lithium vanadium phosphate, lithium fluorophosphate, elemental sulfur, sulfur-containing polymers, and lithium sulfide.

[0055] Preferably, the conductive agent is one or more of Super P, acetylene black, KS-6, CNT, or graphene;

[0056] Preferably, the binder is one or more of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, and sodium carboxymethyl cellulose;

[0057] Preferably, the negative electrode is one of graphite, silicon, silicon-carbon composite, lithium metal, lithium alloy, and lithium titanate.

[0058] Preferably, the diaphragm is one or more of polypropylene, polyethylene, and glass fiber.

[0059] Beneficial effects

[0060] The present invention unexpectedly discovered that the additive of Formula 1 and the monomer of Formula 2 can unexpectedly exhibit better physicochemical compatibility, which helps to optimize the polymerization method, improve structural integrity, and improve the grafting method. In this way, it can unexpectedly further synergistically improve the overall oxidation stability of the material, reduce the interfacial reactivity of the electrolyte under high temperature conditions, and improve the cycling, fast charging, and high temperature stability of the gel electrolyte. Attached Figure Description

[0061] Figure 1 These are flame retardant test photos of the flame retardant phosphate gel electrolyte obtained in Example 1;

[0062] Figure 2 This is a cycle performance diagram of the lithium battery obtained in Example 1; Detailed Implementation

[0063] Example 1

[0064] This embodiment provides a method for preparing a flame-retardant in-situ polymerized gel electrolyte battery. The structure of the flame-retardant in-situ polymerized gel electrolyte battery includes a positive electrode, a negative electrode, a separator, and a gel electrolyte. The battery preparation process is as follows:

[0065] 1) First, mix the slurry. The positive electrode slurry ratio is lithium iron phosphate: Super P: PVDF = 80:10:10, all in wt%. Coat the positive electrode slurry onto aluminum foil, dry it, and cut it into 12mm diameter electrode sheets. Lithium foil is used for the negative electrode.

[0066] 2) The liquid electrolyte used in the electrolyte precursor reaction solution is a commercial electrolyte, which is 1 mol / L lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate and dimethyl carbonate (the volume ratio of fluoroethylene carbonate and dimethyl carbonate is 1:1). The composite monomer (including monomer 1 (Formula 1A) with a weight ratio of 4:1) is added. ) and monomer 2 (Formula 2A, Add PETEA (crosslinking agent), vinylene carbonate (VC) additive, and AIBN initiator to the liquid electrolyte and stir until homogeneous to obtain the electrolyte precursor reaction solution.

[0067] In the electrolyte precursor reaction solution, the content of the composite monomer is 5 wt.%; the content of the initiator is 0.01 wt.%; the concentration of the crosslinking agent is 1 wt.%; the content of the additive is 0.1 wt.%; and the balance is liquid electrolyte.

[0068] 3) The above-mentioned positive electrode, glass fiber separator, and negative electrode are assembled into the battery case, and then the electrolyte precursor reaction solution is injected during the battery assembly process.

[0069] 4) Let the battery stand still and soak at 25°C for 12 hours.

[0070] After being soaked, the battery was placed in a high-temperature environment for a gel reaction at 70°C for 12 hours to obtain a gel electrolyte battery.

[0071] 5) Perform an ignition test on the electrolyte. Ignite the prepared flame-retardant phosphate-based gel electrolyte using a high-temperature flamethrower for 5 seconds and observe whether the electrolyte is flammable. The combustion experiment of the flame-retardant phosphate-based gel electrolyte prepared in this case is shown in [link to relevant documentation]. Figure 1 It reaches the non-flammable level.

[0072] 6) Charge-discharge cycle tests were performed on the Blue Electric Test Charge-Discharge Tester under the following conditions: 5C rate (1C = 170mAh / g) charge-discharge cycle, electrochemical window set to 3-4.0V, and test temperature at 60℃. Cyclic stability is shown in [reference needed]. Figure 2 The test results are listed in Table 1.

[0073] Example 2

[0074] Compared with Example 1, the only difference is that in step 2, monomer 1 is replaced with an equal weight of formula 1B ( Other operations and parameters are the same as in Example 1, and the test results are shown in Table 1.

[0075] Example 3

[0076] Compared with Example 1, the only difference is that in step 2, monomer 2 is replaced with an equal weight of formula 2B ( Other operations and parameters are the same as in Example 1, and the test results are shown in Table 1.

[0077] Example 4

[0078] Compared with Example 1, the only difference is that in step 2, the lithium salt in the liquid electrolyte is lithium hexafluorophosphate with a concentration of 1.5M; in the electrolyte precursor reaction solution, the weight ratio of monomer 1 to monomer 2 in the composite monomer is 3:2, and the content of the composite monomer is 10 wt.%; the content of the initiator (azodimethylvalerate) is 0.015 wt.%; the concentration of the crosslinking agent (triethylene glycol dimethacrylate) is 0.8 wt.%; the content of the additive is 0 wt.%; and the balance is liquid electrolyte.

[0079] Example 5

[0080] Compared to Example 1, the only difference is that in step 4, the conditions of the gelation reaction are changed. The experimental group is characterized by:

[0081] Group A: The gelation reaction was a single-stage gelation process at a temperature of 45°C; the gelation reaction time was 16 hours; other operations and parameters were the same as in Example 1.

[0082] Group B: The gelation reaction is a two-stage gradient temperature-controlled reaction. The steps are as follows: the gelation reaction includes a first gelation process at a temperature of 45°C and a second gelation process at a temperature of 70°C; the first gelation process takes 4 hours; the second gelation process takes 8 hours; other operations and parameters are the same as in Example 1.

[0083] Group C: The gelation reaction is a two-stage gradient temperature-controlled reaction. The steps are as follows: the gelation reaction includes a first gelation process at a temperature of 50°C and a second gelation process at a temperature of 65°C; the first gelation process takes 2 hours; the second gelation process takes 12 hours; other operations and parameters are the same as in Example 1.

[0084] Comparative Example 1

[0085] Compared with Example 1, the only difference is that in step 2, the composite monomer contains only monomer 1, and the total amount of monomer is the same as that of the composite monomer in Example 1. Other operations and parameters are the same as those in Example 1. The test results are shown in Table 1.

[0086] Comparative Example 2

[0087] Compared with Example 1, the only difference is that in step 2, the composite monomer contains only Formula 2, and the total amount of monomer is the same as that of the composite monomer in Example 1. Other operations and parameters are the same as in Example 1. The test results are shown in Table 1.

[0088] Comparative Example 3

[0089] Compared with Example 1, the only difference is that in step 2, comparative formula a ( The monomer 1 in the composite monomer was replaced in equal amounts, and other operations and parameters were the same as in Example 1. The test results are shown in Table 1.

[0090] Comparative Example 4

[0091] Compared with Example 1, the only difference is that in step 2, comparative formula b is used. The monomer 2 in the composite monomer was replaced with an equal amount, and other operations and parameters were the same as in Example 1. The test results are shown in Table 1.

[0092] The test results for each case are shown in Table 1;

[0093]

[0094] As shown in Table 1, and as demonstrated in Examples 1 and 1-4, the combination of Formulas 1 and 2 can achieve synergy, which helps to optimize the polymerization method, improve structural integrity, and improve the grafting method. This can unexpectedly further synergistically improve the overall oxidation stability of the material, reduce the interfacial reactivity of the electrolyte under high temperature conditions, and improve the cycling, fast charging, and high temperature stability of the gel electrolyte.

[0095] As can be seen from Examples 1, 2 and 3, using R2 and R3 as sterically hindered monomers of Formula 1 and / or monomer 2 of Formula 2B can further synergistically optimize polymerization behavior and further enhance the cycling, fast charging and high temperature stability of gel electrolytes.

[0096] Furthermore, as can be seen from Examples 1 and 5, under the synergistic polymerization of Formulas 1 and 2, further combined with a two-stage gradient polymerization method, the cycling, fast charging, and high-temperature stability of the gel electrolyte can be further enhanced.

[0097] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a gel electrolyte, characterized in that, The mixture comprising a base electrolyte, a composite monomer, an initiator, and a crosslinking agent is polymerized to obtain the product; the base electrolyte comprises a solvent and a conductive electrolyte; the composite monomer comprises formula 1 and formula 2. Formula 1; Formula 2; In Formula 1, R1 to R4 are individually H, C1 to C4 alkyl, C1 to C4 alkoxy or halogen; In Formula 2, X is a C1-C4 alkyl or oxanealkyl group; R5-R7 are individually C1-C4 alkyl or alkoxy groups; and R8 is a vinyl or acrylate group.

2. The preparation method according to claim 1, characterized in that, In the composite monomers, the mass ratio of Formula 1 to Formula 2 is 1~5:1; preferably 1.5~4.5:

1.

3. The method for preparing gel electrolyte as described in claim 1, characterized in that, The solvent in the basic electrolyte includes at least one of ether solvents and ester solvents; Preferably, the solvent includes at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, methyl propionate, methyl acetate, and ethyl acetate. Preferably, the conductive electrolyte is a conductive salt capable of providing active cations, wherein the active cations include at least one of lithium ions, sodium ions, and potassium ions; Preferably, the conductive electrolyte includes at least one of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium bis(oxalate)borate, lithium difluorooxalateborate, and lithium difluorobis(oxalate)phosphate. Preferably, the concentration of the conductive electrolyte in the base electrolyte is 0.5~5M, more preferably 1~3M; Preferably, the crosslinking agent is selected from any one or more of polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated trimethylolpropoxide, pentaerythritol tetraacrylate, ethyl 2,2,2-trifluoroacrylate, trifluoroethyl methacrylate, pentafluorophenyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, perfluorobutyl acrylate, and N,N′-methylenediacrylamide. The initiator is a free radical initiator, preferably one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and azobismethylvalerate.

4. The method for preparing gel electrolyte as described in claim 1, characterized in that, In the mixed solution, the concentration of the composite monomer is 2–30 wt.%; the concentration of the initiator is 0.01–1 wt.%; and the concentration of the crosslinking agent is 1–3 wt.%. Preferably, the mixed solution further comprises an additive, which includes at least one of vinylene carbonate and fluoroethylene carbonate.

5. The method for preparing the gel electrolyte according to any one of claims 1 to 4, characterized in that, The polymerization temperature can be 35~85℃; the total polymerization time is 2~36h; Preferably, the polymerization process includes a first polymerization process and a second polymerization process; wherein the temperature of the first polymerization process is 40~50℃; and the temperature of the second polymerization process is 60~80℃. Preferably, the first polymerization stage lasts for 1 to 5 hours; the second polymerization stage lasts for 5 to 15 hours.

6. A gel electrolyte prepared by the preparation method according to any one of claims 1 to 5.

7. The application of a gel electrolyte prepared by the preparation method according to any one of claims 1 to 5, characterized in that, It can be used to prepare solid-state batteries; Preferably, it is placed between the positive and negative electrodes for the fabrication of solid-state batteries.

8. A modified electrode, characterized in that, It includes an electrode and a gel electrolyte of claim 6 composite thereon; the electrode is a positive electrode and / or a negative electrode.

9. A modified diaphragm, characterized in that, Includes a base film and the gel electrolyte of claim 6, which is composited on the surface.

10. A solid-state battery, comprising a positive electrode, a barrier layer, and a negative electrode sequentially laminated together, characterized in that, The barrier layer includes the gel electrolyte as described in claim 6; Preferably, the positive and / or negative electrode is the modified electrode as described in claim 8; and / or, the barrier layer is the modified membrane as described in claim 9.

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