CN114665151A - Polymer electrolyte, preparation method thereof and application thereof in solid-state battery - Google Patents

Polymer electrolyte, preparation method thereof and application thereof in solid-state battery Download PDF

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CN114665151A
CN114665151A CN202210392080.4A CN202210392080A CN114665151A CN 114665151 A CN114665151 A CN 114665151A CN 202210392080 A CN202210392080 A CN 202210392080A CN 114665151 A CN114665151 A CN 114665151A
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polymer electrolyte
electrolyte
cyclopentene
active hydrogen
monomer
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CN114665151B (en
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刘帅
李久铭
杨琪
俞会根
张晓维
尤猛
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Beijing Weilan New Energy Technology Co ltd
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Beijing WeLion New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
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    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
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Abstract

The invention provides a polymer electrolyte, a preparation method thereof and application thereof in a solid-state battery. The monomer of the polymer electrolyte comprises a cyclopentene structure monomer and an active hydrogen structure monomer, the main chain of the polymer comprises a cyclopentene structure and an active hydrogen group, and the polymer electrolyte is obtained by in-situ polymerization and solidification of the cyclopentene structure monomer, the active hydrogen structure monomer, an initiator, a cross-linking agent and electrolyte. The polymer electrolyte has excellent thermal stability, and can generate a chemically integrated interface with an electrode in a battery curing stage to improve the interface performance. The in-situ polymerization curing method is adopted to prepare the in-situ curing electrolyte, so that the interface compatibility of the solid-state battery is improved, the manufacturing cost of the solid-state battery is reduced, and the performance of the solid-state battery is improved.

Description

Polymer electrolyte, preparation method thereof and application thereof in solid-state battery
Technical Field
The invention relates to the field of solid polymer electrolytes, in particular to a polymer electrolyte and application thereof in a solid battery.
Technical Field
The improvement of energy density is crucial to the development of next-generation rechargeable batteries for various devices. However, the high-energy density battery is prone to thermal runaway, which causes potential safety hazards. Because the liquid electrolyte contains a large amount of flammable and easily-leaked organic carbonate micromolecular solvents, the liquid electrolyte has great potential safety hazard, and at present, the method for improving the safety of the battery is a better method for replacing the traditional flammable liquid electrolyte with the solid electrolyte with higher thermal stability.
However, since the high energy density battery usually uses metallic lithium and pre-lithiated silicon as the negative electrode material, the non-uniform metallic lithium and lithium compound are often distributed on the surface of the negative electrode, the metallic bond energy between lithium atoms in the metallic lithium is low, and lithium atoms in the metallic lithium are more likely to migrate to the surface to form a low dimensional structure, such as lithium dendrite. The growth of lithium dendrites can puncture the conventional polymer electrolyte to the positive electrode to initiate internal short circuits, further initiating thermal runaway.
Therefore, it is necessary to improve the solid polymer electrolyte, to improve the oxidation resistance, thermal stability and toughness of the solid polymer electrolyte, and to improve the interface performance between the electrolyte and the negative electrode, so as to solve the problems of uneven pre-lithium negative electrode, lithium precipitation from the battery cell, thermal runaway and the like of the lithium metal battery.
Disclosure of Invention
In order to solve the problems, the invention provides a polymer electrolyte, a preparation method thereof and application in a solid-state battery. One of the aspects of the present invention is to provide a polymer electrolyte, which is a polymer electrolyte introduced with a cyclopentene structure and active hydrogen groups, the cyclopentene structure and the active hydrogen groups being located on a main chain of the polymer.
Furthermore, the raw materials of the polymer electrolyte comprise cyclopentene structural monomers, active hydrogen structural monomers, an initiator, a cross-linking agent and electrolyte.
Furthermore, the mass ratio of the cyclopentene structural monomer, the active hydrogen structural monomer, the cross-linking agent, the initiator and the electrolyte is (0.01-30): (0.01-20): (0.01-10): (0.0001-1): (40-85).
Further, the raw materials are solidified after in-situ polymerization to obtain the polymer electrolyte.
The polymer electrolyte generated by in-situ polymerization is integrated with an electrode and has no obvious interface, so that the battery has better electrical property. The polymerization process is double bond addition polymerization, and the cyclopentene structure in the polymer electrolyte can effectively improve the heat resistance of the polymer electrolyte and avoid the influence of overhigh carbon ring content on the ionic conductivity.
Specifically, the cyclopentene structural monomer comprises one or more of cyclopentene, dicyclopentadiene, dicyclopentenyl acrylate, ethylene glycol dicyclopentenyl ether methacrylate and dicyclopentenyl methacrylate.
The active hydrogen structure monomer comprises one or more of acrylamide, 2-acrylamido-2-methyl-1-propane sulfonic acid, 2-hydroxyethyl methacrylate and acrylic acid.
The cross-linking agent is an acrylate monomer containing two or more unsaturated double bonds, and preferably comprises one or more of ethylene glycol dimethacrylate, polyethylene glycol acrylate, 1, 4-butanediol diacrylate, 1,6 hexanediol diacrylate, N methylene bisacrylamide, 4' -isopropylidenediphenol dimethylallyl ester, triallyl isocyanurate, trivinylcyclotrisiloxane, triallyl phosphate, triallyl phosphite, tetraallyloxysilane, ethoxylated trihydroxymethylpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
The initiator is a compound which can be decomposed to generate free radicals under certain conditions, and preferably comprises one or more of azodiisobutyronitrile, azodiisoheptanonitrile, dimethyl azodiisobutyrate, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, stannous octoate, lithium acetate, triethyl phosphorus, triphenyl phosphorus, tri-N-butyl phosphorus, tributyl tin oxide, tetrabutyl titanate, tetrabutyl pickaxelate, trialkyl tin alkoxide, dialkyl tin oxide, N-methyl ethylenediamine, dimethylformamide, triethylene ethylenediamine, methyl diglycolamine, triethylene diamine, lithium bis (fluorosulfonyl) imide, aluminum (trifluoromethyl) sulfonate, magnesium (trifluoromethyl) sulfonate, lithium bis (fluorosulfonyl) imide and tin (trifluoromethyl) sulfonate.
The second invention of the invention is to provide a preparation method of the polymer electrolyte.
Further, the preparation method of the polymer electrolyte comprises the steps of uniformly mixing a cyclopentene structural monomer, an active hydrogen structural monomer, a cross-linking agent, an initiator and an electrolyte, infiltrating, heating, and curing after in-situ polymerization to obtain the in-situ cured electrolyte.
Furthermore, the mass ratio of the cyclopentene structural monomer, the active hydrogen structural monomer, the cross-linking agent, the initiator and the electrolyte is (0.01-30): (0.01-20): (0.01-30): (0.0001-1): (30-85).
Further, the soaking time is 5-48 h, the heating temperature is 25-90 ℃, and the heating time is 1-120 h.
The third invention of the invention provides a solid-state battery, which comprises a positive electrode, a negative electrode and the polymer electrolyte.
Compared with the prior art, the invention has the following advantages:
1. the oxidation resistance, the thermal stability and the toughness of the electrolyte are improved, and the thermal runaway risk of the battery is reduced. The polymer electrolyte comprises a polymer, the polymer chain comprises a cyclopentene structure, the cyclopentene structure has excellent thermal stability, and oxidation resistance, thermal stability and toughness of the electrolyte can be improved after the cyclopentene structure is introduced into the polymer main chain.
2. The interface performance, the cycling stability and the safety of the battery are improved. Active metal lithium on the surface of the metallic lithium negative electrode or the pre-lithium negative electrode is eliminated through a chemical reaction mode, so that dendrite cannot be further formed. The polymer chain contains active hydrogen groups, the active hydrogen groups can react with metal lithium or a non-uniform negative electrode of pre-lithium in the early solidification stage of the lithium battery, chemical bonds can be formed between an electrolyte and a negative electrode material to connect the electrolyte and the negative electrode material, the capability of inhibiting dendritic crystals is further improved, the contact property of the electrolyte and an electrode is improved, the interface deterioration caused by the volume expansion of the electrode in the later charging and discharging process is reduced, and the circulation stability is improved. In addition, when the polymer electrolyte is applied to a conventional graphite cathode cell, when the cell is subjected to lithium precipitation, the active hydrogen groups are lithiated to prevent the cell from further growing, and the purpose of improving the safety of the battery can be achieved.
3. As for the preparation method, the in-situ polymerization curing method is adopted to prepare the in-situ cured electrolyte, so that the electrolyte is better contacted with the electrode, the interface compatibility of the solid-state battery is greatly improved, the link of interface modification in the preparation process of the solid-state battery is reduced, the manufacturing cost of the solid-state battery is reduced, and the performance of the solid-state battery is improved.
Drawings
FIG. 1 is a graph showing the results of the hot box test in experimental group 1;
FIG. 2 is a graph showing the results of the hot box test of comparative example 1;
FIG. 3 is a graph showing the results of the hot box test of comparative example 2;
fig. 4 is a graph showing the results of the hot box test of comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It is to be understood that the description herein is only illustrative of the present invention and is not intended to limit the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention. The reagents and instruments used in the present invention are commercially available, and the characterization means involved can be referred to the description in the prior art, which is not repeated herein.
For a further understanding of the present invention, reference will now be made in detail to the preferred embodiments of the present invention.
Example 1
A polymer electrolyte applied to a battery is a polymer electrolyte introduced with a cyclopentene structure and an active hydrogen group. The polymer electrolyte comprises a polymer and an electrolyte, wherein the cyclopentene structure and the active hydrogen groups are positioned on a main chain of the polymer; the electrolyte includes a salt, which is a lithium salt if the battery is a lithium ion battery. The oxidation resistance and the toughness of electrolyte are improved by introducing a cyclopentene structure into a polymer structure, and an active hydrogen-containing functional group is introduced into the polymer structure, so that the polymer structure can react with metal lithium in a metal lithium battery to form a good interface, and can react with the lithium to form a lithium compound when a lithium anode is not uniform and lithium precipitation occurs in a battery cell, thereby improving the interface stability.
In a further preferred embodiment, the raw materials of the polymer electrolyte comprise a cyclopentene structural monomer, an active hydrogen structural monomer, an initiator, a cross-linking agent and an electrolyte. The mass ratio of the cyclopentene structural monomer, the active hydrogen structural monomer, the cross-linking agent, the initiator and the electrolyte in the raw materials is (0.01-30): (0.01-20): 0.01-10): 0.0001-1): 40-85, such as 0.1:0.1:0.1:0.001:40, 0.5:10:5:0.01:50, 15:20:0.5:0.05:85, 27:13:8:0.6:70, 30:20:10:1:85 and the like.
In a further preferred embodiment, the raw materials are subjected to in-situ polymerization and then cured to obtain the polymer electrolyte.
As a further preferred embodiment, the cyclopentene structural monomer comprises one or more of cyclopentene, dicyclopentene, dicyclopentenyl acrylate, ethylene glycol dicyclopentenyl ether methacrylate, and dicyclopentenyl methacrylate.
As a further preferable embodiment, the active hydrogen structural monomer comprises one or more of acrylamide, 2-acrylamido-2-methyl-1-propane sulfonic acid, 2-hydroxyethyl methacrylate and acrylic acid.
In a further preferred embodiment, the crosslinking agent is a monomer having two or more carbon-carbon double bond groups, and includes one or more of ethylene glycol dimethacrylate, polyethylene glycol acrylate, 1, 4-butanediol diacrylate, 1,6 hexanediol diacrylate, N methylene bisacrylamide, 4' -isopropylidenediphenol dimethylallyl ester, triallyl isocyanurate, trivinylcyclotrisiloxane, triallyl phosphate, triallyl phosphite, tetraallyloxysilane, ethoxylated trihydroxymethylpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
The initiator is a compound which can be decomposed to generate free radicals under certain conditions, and preferably comprises one or more of azodiisobutyronitrile, azodiisoheptanonitrile, dimethyl azodiisobutyrate, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, stannous octoate, lithium acetate, triethyl phosphorus, triphenyl phosphorus, tri-N-butyl phosphorus, tributyl tin oxide, tetrabutyl titanate, tetrabutyl pickaxelate, trialkyl tin alkoxide, dialkyl tin oxide, N-methyl ethylenediamine, dimethylformamide, triethylene ethylenediamine, methyl diglycolamine, triethylene diamine, lithium bis (fluorosulfonyl) imide, aluminum (trifluoromethyl) sulfonate, magnesium (trifluoromethyl) sulfonate, lithium bis (fluorosulfonyl) imide and tin (trifluoromethyl) sulfonate.
Preferably, the initiation is thermal, but other initiation methods can achieve the same effect as the present embodiment.
As a further preferred embodiment, the electrolyte comprises a solvent and a salt.
Preferably, the solvent is one or more of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), Ethylene Carbonate (EC), diethyl carbonate (DEC), Propylene Carbonate (PC), methyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, δ -valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, ethylene glycol dimethyl ether, 1, 3-dioxolane, sulfolane and dimethyl sulfoxide;
the salt is at least one of bis (oxalato) borate (MBOB), difluoro (oxalato) borate (MODFB), bis (fluorosulfonyl) imide salt (MFSI), hexafluorophosphate (MPF6), bis (trifluoromethyl) sulfonyl imide salt (MTFSI), and tetrafluoroborate (MBF4), wherein M is a metal ion including Li+、Na+、Zn2+。
Preferably, the salt is a lithium salt.
The solvents and salts listed above are only illustrative and do not represent the only embodiments, and other solvents and salts may be selected to achieve the same effect as in this example.
As a further preferred embodiment, in order to further increase the performance of the polymer electrolyte, the electrolyte may further include an additive that does not participate in the in-situ polymerization reaction, although it is also possible that individual substances participate in the process of forming the polymer. The additive may include at least one of fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), trimethyl phosphate (TMP), ethoxypentafluorocyclotriphosphazene (PFPN), and vinyl sulfate (DTD).
In this embodiment, the main chain of the polymer contains a cyclopentene structure and an active hydrogen group, and the cyclopentene structure and the active hydrogen group are introduced into the polymer electrolyte at the same time, so that the thermal safety performance and the electrical performance of the battery can be further improved by combining the cyclopentene structure and the active hydrogen group, the battery can work normally at normal temperature and high temperature, and the voltage can be kept stable, so that the cyclopentene structure and the active hydrogen group have a synergistic effect.
Example 2
A preparation method of a polymer electrolyte comprises the steps of uniformly mixing a cyclopentene structural monomer, an active hydrogen structural monomer, a cross-linking agent, an initiator and an electrolyte, infiltrating, heating, carrying out in-situ polymerization and then curing to obtain an in-situ cured electrolyte. The soaking time is 18-30 h, such as 20h, 22.5h, 25h and the like; the temperature during the infiltration is room temperature, which is usually 10-40 ℃, such as 25 ℃, 30 ℃, 35 ℃ and the like; the heating temperature is 50-100 ℃, such as 50 ℃, 60 ℃, 75 ℃ and the like; the heating time is 1-120 h, preferably 20-30 h, such as 20h, 24h, 30h and the like. The heating process is to cure the polymer electrolyte in situ, and if other initiators are selected, the polymer electrolyte is cured in situ in other ways, which can achieve the same effect as the present embodiment.
The mass ratio of the cyclopentene structural monomer, the active hydrogen structural monomer, the cross-linking agent, the initiator and the electrolyte is (5-30): 5-20): 5-10): 0.001-1): 40-85. Preferably, the mass ratio of the cyclopentene structural monomer, the active hydrogen structural monomer, the cross-linking agent, the initiator and the electrolyte is (5-20): (10-20): 5-10): 0.001-1): 60-85, such as 5:20:10:0.5:70, 10:10:5:1:85, 15:10:7:0.1:60, 25:10:15:0.5:70, 30:20:30:1:85 and the like.
Example 3
A solid state battery comprising a protective sheet and an in situ cured cell comprising the polymer electrolyte of example 1. The in-situ cured battery cell comprises a positive electrode, a negative electrode, a diaphragm and the in-situ cured electrolyte.
Experimental group 1
5g of ethylene glycol dicyclopentenyl ether acrylate, 15g of acrylamide, 10g of polyethylene glycol dimethacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC ═ 1:1:11M LiPF6) are uniformly mixed, injected into a soft package cell assembled by NCM811/Li, soaked for 24 hours at 25 ℃, put into a 60 ℃ oven and heated and cured for 24 hours to prepare the in-situ cured cell.
Experimental group 2
Uniformly mixing 10g of cyclopentene, 10g of dicyclopentene, 15g of 2-hydroxyethyl methacrylate, 3g of polyethylene glycol acrylate, 5g of ethoxylated trihydroxy methyl propane triacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC ═ 1:1:11M LiPF6), injecting into a soft package cell assembled by NCM811/Li, soaking for 30h at 20 ℃, putting into an oven at 80 ℃ and heating for 20h to prepare the in-situ cured cell.
Experimental group 3
30g of dicyclopentenyl acrylate, 20g of acrylic acid, 5g of pentaerythritol triacrylate, 5g of pentaerythritol tetraacrylate, 0.3g of azobisisobutyronitrile and 85g of electrolyte (EC/EMC/DEC ═ 1:1:11M LiPF6) are uniformly mixed, injected into a NCM811/Li assembled soft package cell, soaked for 20 hours at 30 ℃, put into a 50 ℃ oven and heated and cured for 30 hours to prepare the in-situ cured cell.
Experimental group 4
15g of ethylene glycol dicyclopentenyl ether methacrylate, 10g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 5g of dipentaerythritol pentaacrylate, 0.3g of azobisisobutyronitrile and 85g of electrolyte (EC/EMC/DEC is 1:1:11M LiPF6) are uniformly mixed, injected into a soft package cell assembled by NCM811/Li, soaked for 20 hours at 30 ℃, put into a 50 ℃ oven and heated and cured for 30 hours to prepare the in-situ cured cell.
Experimental group 5
5g of dicyclopentenyl methacrylate, 5g of acrylamide, 5g of dipentaerythritol hexaacrylate, 0.3g of azobisisobutyronitrile and 40g of electrolyte (EC/EMC/DEC: 1:11M LiPF6) are uniformly mixed, injected into a soft package battery cell assembled by NCM811/Li, soaked for 20 hours at 25 ℃, and then placed into a 60 ℃ oven for heating and curing for 20 hours to prepare the in-situ cured battery cell.
Comparative example 1
20g of ethylene glycol dicyclopentenyl ether acrylate, 10g of polyethylene glycol dimethacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC is 1:1:11M LiPF6) are uniformly mixed, injected into a soft package battery cell assembled by NCM811/Li, soaked for 24 hours at 25 ℃, put into a 60 ℃ oven and heated and cured for 24 hours to prepare the in-situ cured battery cell. The comparative example provides a polymer electrolyte that does not contain active hydrogen groups.
Comparative example 2
20g of acrylamide, 10g of polyethylene glycol dimethacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC is 1:1:11M LiPF6) are uniformly mixed, injected into a soft package battery cell assembled by NCM811/Li, soaked for 24 hours at 25 ℃, put into a 60 ℃ oven and heated and cured for 24 hours to prepare an in-situ cured battery cell. The polymer electrolyte provided by this comparative example does not contain a cyclopentene structure.
Comparative example 3
5g of ethylene carbonate, 15g of acrylamide, 10g of polyethylene glycol dimethacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC ═ 1:1:11M LiPF6) are uniformly mixed, injected into a soft package cell assembled by NCM811/Li, soaked for 24 hours at 25 ℃, put into a 60 ℃ oven and heated and cured for 24 hours to prepare the in-situ cured cell. This comparative example is substantially the same as experimental group 1 except that the ethylene glycol dicyclopentenyl ether acrylate was changed to ethylene carbonate.
Comparative example 4
5g of ethylene glycol dicyclopentenyl ether acrylate, 15g N, N dimethylacrylamide, 10g of polyethylene glycol dimethacrylate, 0.3g of azobisisobutyronitrile and 70g of electrolyte (EC/EMC/DEC ═ 1:1:11M LiPF6) are uniformly mixed, injected into a soft package cell assembled by NCM811/Li, soaked for 24 hours at 25 ℃, then placed into a 60 ℃ oven for heating and curing for 24 hours, and the in-situ cured cell is prepared. This comparative example is substantially the same as experimental group 1 except that the monomer acrylamide in experimental group 1 was changed to N, N dimethylacrylamide, i.e., the active hydrogen was substituted with a methyl group.
Performance comparison experiment:
0.3C charge-discharge cycle tests were performed on the cells assembled in examples 1-5 and comparative examples 1-4, and the test results are shown in Table 1; 4 electric cores assembled in the experimental group 1 and the comparative examples 1-3 are subjected to a hot box test, and the temperature of the hot box is uniformly increased to 200 ℃ along with time. And recording the temperature and the voltage of the battery cell at each moment, wherein the test results are shown in the figures 1, 2, 3 and 4.
TABLE 1 comparison of test results at Normal temperature
Figure BDA0003596049230000071
Figure BDA0003596049230000081
From cycle tests, the battery cells provided by each experimental group have high capacity, good cycle retention rate at normal temperature and good thermal stability, the voltage does not fluctuate greatly along with the temperature, and the voltage is basically kept in a relatively constant range, as shown in fig. 1, and the overall effect is good.
As can be seen from comparative example 1, when the active hydrogen groups are absent in the polymer electrolyte, the initial capacity and capacity retention rate of the cell are both significantly reduced, and the thermal stability is poor, and although the thermal runaway phenomenon does not occur in the cell, the voltage fluctuates greatly with the temperature increase, and the electrical property is poor, as shown in fig. 2.
As can be seen from comparative example 2, when the cyclopentene-containing structure was absent from the polymer electrolyte, the initial capacity of the cell was significantly decreased, although the capacity retention rate was still acceptable, which is second only to the experimental group, but the thermal stability was extremely poor, and the cell thermally runaway at 160 ℃ resulted in explosion, as shown in fig. 3. Correspondingly, when the hydrogen-active group and the cyclopentene-containing structure in the application are contained simultaneously, as shown in an experiment group 1, the battery cell has excellent capacity and capacity retention rate, and the thermal stability is good, and as can be seen from a hot box test experiment, the battery cell temperature of the experiment group 1 uniformly rises along with the temperature of the hot box, the voltage is stable, the thermal runaway phenomenon does not occur when the temperature rises to 200 ℃ from the test end, and the thermal safety is good, as shown in fig. 1, the battery cell has good overall performance and excellent application prospect and significance.
In addition, comparative example 3 has a clear defect at high temperature although the performance is still acceptable at normal temperature, and the cells thereof all suffer thermal runaway at 160 ℃ to cause explosion, as shown in fig. 4. The room-temperature capacity retention rate of comparative example 4 was significantly reduced, and the thermal stability thereof was poor. Therefore, the comparative examples 1 to 4 lack application bases and meanings, which indirectly shows that the cyclopentene structure and the active hydrogen group supplement the performance improvement of the polymer electrolyte, and the combined action of the cyclopentene structure and the active hydrogen group enables the polymer electrolyte provided by the application to well improve and enhance the performance of the cell.
In conclusion, the solid-state battery applied by the in-situ solidified electrolyte provided by the invention has good cycle stability and high thermal safety.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A polymer electrolyte for use in a battery, wherein the polymer electrolyte is a polymer electrolyte into which a cyclopentene structure and active hydrogen groups are introduced, the cyclopentene structure and the active hydrogen groups being present on a main chain of the polymer.
2. The polymer electrolyte according to claim 1, wherein the raw materials of the polymer electrolyte comprise cyclopentene structural monomer, active hydrogen structural monomer, initiator, cross-linking agent, and electrolyte.
3. The polymer electrolyte of claim 2, wherein the mass ratio of the cyclopentene monomer, the active hydrogen monomer, the cross-linking agent, the initiator and the electrolyte is (0.01-30): (0.01-20): 0.01-10): 0.001-1): 40-85.
4. The polymer electrolyte of claim 2, wherein the cyclopentene structural monomer comprises one or more of cyclopentene, dicyclopentadiene, dicyclopentenyl acrylate, ethylene glycol dicyclopentenyl ether methacrylate, and dicyclopentenyl methacrylate.
5. The polymer electrolyte of claim 2, wherein the active hydrogen structural monomer comprises one or more of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-hydroxyethyl methacrylate, acrylic acid.
6. The polymer electrolyte according to claim 2, wherein the cross-linking agent is an acrylate monomer having two or more unsaturated double bonds, and includes one or more of ethylene glycol dimethacrylate, polyethylene glycol acrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, N-methylene bisacrylamide, 4' -isopropylidenediphenol dimethylallyl ester, triallyl isocyanurate, trivinylcyclotrisiloxane, triallyl phosphate, triallyl phosphite, tetraallyloxysilane, ethoxylated trihydroxymethylpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate;
preferably, the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, stannous octoate, lithium acetate, triethyl phosphate, triphenyl phosphate, tri-N-butyl phosphate, tributyl tin oxide, tetrabutyl titanate, tetrabutyl fumarate, trialkylstannate, dialkyltin oxide, N-methylethylenediamine, dimethylformamide, triethylene ethylenediamine, methyl diglycolamine, triethylene diamine, lithium bis-fluorosulfonylimide, aluminum triflate, magnesium triflate, lithium bis-fluorosulfonylimide, and tin triflate.
7. A preparation method of the polymer electrolyte according to any one of claims 1 to 6, wherein the preparation method comprises the steps of uniformly mixing a cyclopentene structural monomer, an active hydrogen structural monomer, a cross-linking agent, an initiator and an electrolyte, infiltrating, heating, carrying out in-situ polymerization and then curing to obtain the in-situ cured electrolyte.
8. The method of claim 7, wherein the mass ratio of the cyclopentene monomer, the active hydrogen monomer, the cross-linking agent, the initiator, and the electrolyte is (0.01-30): (0.01-20): (0.01-30): (0.0001-1): (30-85).
9. The preparation method of the polymer electrolyte according to claim 7, wherein the soaking time is 5-48 h, the heating temperature is 25-90 ℃, and the heating time is 1-120 h.
10. A solid-state battery comprising a positive electrode and a negative electrode and the polymer electrolyte according to any one of claims 1 to 6.
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