WO2023216028A1 - 聚合物及其制备、电解质膜及其制备 - Google Patents

聚合物及其制备、电解质膜及其制备 Download PDF

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WO2023216028A1
WO2023216028A1 PCT/CN2022/091467 CN2022091467W WO2023216028A1 WO 2023216028 A1 WO2023216028 A1 WO 2023216028A1 CN 2022091467 W CN2022091467 W CN 2022091467W WO 2023216028 A1 WO2023216028 A1 WO 2023216028A1
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monomer
polymer
electrolyte membrane
lithium
polymer electrolyte
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PCT/CN2022/091467
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English (en)
French (fr)
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薛文文
刘成勇
何晓宁
张楠楠
胡波兵
黄显
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宁德时代新能源科技股份有限公司
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Priority to CN202280039248.1A priority Critical patent/CN117413400A/zh
Priority to PCT/CN2022/091467 priority patent/WO2023216028A1/zh
Publication of WO2023216028A1 publication Critical patent/WO2023216028A1/zh

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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

Definitions

  • This application relates to a polymer.
  • the present application also relates to an electrolyte membrane including the polymer, a secondary battery including the electrolyte membrane, a battery pack including the secondary battery, a battery module and a power consumption device.
  • lithium-ion batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. As lithium-ion batteries have made great progress, higher requirements have been placed on their electrolytes.
  • This application was made in view of the above problems, and its purpose is to provide a polymer that has good flame retardant properties, is not easily oxidized under high pressure, can improve ion conductivity and lithium ion migration number when used as an electrolyte membrane material, and is suitable for high-voltage battery systems. material and its preparation method; in addition, this application also provides a solid electrolyte membrane containing the polymer with good interface contact with the electrode, high ionic conductivity, good high temperature stability and good mechanical properties and its preparation method . In addition, the present application also provides a secondary battery including the electrolyte membrane.
  • the first aspect of the application provides a polymer, which is polymerized by monomer 1, monomer 2, and monomer 3, wherein the monomer 1 has the structure of formula 1, the monomer 2 has the structure of formula 2, and the monomer 2 has the structure of formula 2.
  • Body 3 has the structure of formula 3,
  • R1 and R3 are each independently selected from hydrogen or C 1-10 alkyl
  • R4 is selected from C 1-10 hydrocarbon groups or C 1-10 hydrocarbon groups containing one or more elements from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus;
  • R2 and R5 are each independently selected from hydrogen, C 1-10 hydrocarbon groups, or one or more elements containing fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • Rf is selected from hydrogen, or an ethoxy chain segment containing one or more elements of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus with a carbon number of less than or equal to 16;
  • x is the number of repeating units of methylene, 0 ⁇ x ⁇ 20;
  • a + is selected from one of the functional groups with nitrogen, sulfur, and phosphorus as the cation center;
  • Q - is one, two or more anions selected from halide, haloborate, halooxaloborate, perhalate, halophosphate, halosulfonimide, optionally Q - It is one, two or more anions selected from chloride ion, tetrafluoroborate, difluoroxaloborate, perchlorate, hexafluorophosphate, and bis(fluorosulfonyl)imide;
  • R6 is selected from hydrogen or C 1-10 alkyl.
  • the polymer provided in this application is formed by the polymerization of three monomers (monomer 1, monomer 2, and monomer 3). It has an ethyl group as the main chain, and its molecular structure contains ionic groups (from monomer 1), amide Functional groups such as (from monomer 1), phosphate ester (from monomer 2) and fluorinated ethoxy (from monomer 3). Each of these functional groups provides a different role to the polymer. It is now believed that, for example, the presence of the ionic group and fluorine element (mainly from monomer 3) is beneficial to improving the oxidation resistance or high-pressure stability of the material (especially high voltages above 5V).
  • the flexible ethoxy side chains in the polymer can drive the migration of lithium ions, and the cation center in the ionic group can interact with the anions in the lithium salt to improve Lithium ion migration number;
  • the synergistic effect of the phosphate ester group from monomer 2 and the fluorine element (mainly from monomer 3) makes the electrolyte containing the polymer exhibit excellent flame retardant properties, which is applied to lithium ion dioxide secondary battery, which can improve the safety of the battery;
  • the amide from monomer 1 makes the polymer molecules have a strong hydrogen bond association force, and the existence of the strong hydrogen bond association force and the phosphate ester (from monomer 2 ) is the center of the cross-linked network, which is beneficial to enhancing the mechanical properties of polymer materials.
  • the polymer has a triblock structure.
  • the tri-block structure of the polymer can block the contact between the ethoxy side chains and reduce the crystallinity of the polymer material.
  • the ionic conductivity can be improved.
  • the fluorine element substitution rate in the Rf group is greater than 29.0%, and the fluorine element substitution rate is a proportion of the number of fluorine atoms, based on the number of hydrogen atoms that can be substituted in the Rf group.
  • the "number of hydrogen atoms that can be substituted" should be understood as the number of sites that can be substituted in the Rf group, that is, it can be related to the carbon atoms present in the group, the possible phosphorus atoms, The maximum number of hydrogen atoms connected to possible nitrogen atoms and possible sulfur atoms. If the hydrogen atoms have been replaced by other elements, such as halogen atoms, the number of hydrogen atoms that can be substituted is calculated as the number of hydrogen atoms and the substituted The sum of the numbers of other atoms.
  • a fluorine element substitution rate of greater than or equal to 29.0% can ensure the flame retardant properties of the polymer and improve the high-voltage stability and high-voltage cycleability of batteries obtained using the polymer.
  • the cation A + is selected from one of the structural formulas (4) to (6):
  • the molar ratio of monomer 1 ranges from 3.7 to 92.6 mol%
  • the molar ratio of monomer 2 ranges from 2.0 to 33.3 mol%
  • the molar ratio of monomer 3 The ratio range is 3.7 to 92.6 mol%, all based on the total number of moles of monomer 1, monomer 2, and monomer 3.
  • the molar ratio of monomer 1 to monomer 2 is in the range of 1:1 to 25:1;
  • the molar ratio of monomer 3 to monomer 2 ranges from 1:1 to 25:1.
  • the thermal conductivity of the polymer is in the range of 0.06 to 0.35 W/m K, and the flame retardant level is 94V-0 or 94V-1.
  • the second aspect of the application provides a method for preparing the polymer described in the first aspect of the application, including the following steps: dissolving the monomer 1, the monomer 2, the monomer 3 and the initiator in a solvent, React in vacuum at 30-100°C for 0.2-24h, optionally 6-24h, and then dry.
  • the polymers are carried out as block copolymers.
  • the drying is performed in a vacuum at 25-140°C for 1-48 hours. The main purpose of drying is to remove the solvent remaining after the reaction.
  • a third aspect of the present application provides a polymer electrolyte membrane, which includes the polymer described in the first aspect of the present application or a polymer prepared by the method described in the second aspect of the present application.
  • the polymer electrolyte membrane further includes a second polymer, the second polymer is dispersed in the polymer to form an interpenetrating network structure, the second polymer is formed from monomer 4, which is The general structure of body 4 is as follows:
  • R7 is selected from hydrogen, or a hydrocarbon group with less than 7 carbon atoms that is unsubstituted or substituted by one or more elements of fluorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • hydrocarbyl groups with less than 7 carbon atoms include, but are not limited to: alkyl groups with less than 7 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl , 2,3-dimethylbutyl, etc.; alkenyl groups with less than 7 carbon atoms, such as ethylene, propylene, butene, butadiene, pentene, pentadiene, hexene, hexadiene, etc.; and Alkynyl groups with less than 7 carbon atoms, such as acetylene, propyne, butyne, pent
  • the hydrocarbon group with less than 7 carbon atoms may be unsubstituted, or may be mono- or poly-substituted by one or more elements selected from fluorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • the second polymer is relative to the foregoing polymer in order to distinguish it from the foregoing polymer.
  • the second polymer described in this application is an oligomer, which has carbonate as the main chain, has a number average molecular weight M n ⁇ 2000 Da, a viscosity of less than 3000 cP, and has certain fluidity.
  • the second polymer may also be referred to as a carbonate polymer.
  • the oligomer serves as a second polymer network and is evenly dispersed in the network of the above-mentioned polymer.
  • the presence of the carbonate main chain in the second polymer network provides guarantee for the high-pressure stability of the formed electrolyte membrane and provides a high-pressure stability for the electrolyte membrane containing all the elements.
  • the electrolyte membrane contributes to the excellent high voltage resistance performance of the secondary battery.
  • the second polymer in the interpenetrating network structure has a certain fluidity and can wet the electrode piece, thereby improving the interface contact between the electrolyte membrane and the positive and negative electrodes. Therefore, in a solid electrolyte membrane including an interpenetrating network of a network formed by a polymer and a network formed by a second polymer, the introduction of a fluid second polymer network not only improves the lubrication between the electrolyte membrane and the electrodes The wet performance improves the interface contact between the electrolyte membrane and the positive and negative electrodes. At the same time, the chain segment movement of carbonate can drive the migration of lithium ions, which also ensures the high ionic conductivity of the electrolyte membrane.
  • the electrolyte membrane containing the above-mentioned interpenetrating network structure described in this application is suitable for high-voltage battery systems, such as 5V high-voltage battery systems.
  • the high-voltage battery body series includes, but is not limited to, LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiCoO 2 , LiMn 2 O 4 , LiNiCoAlO 2 , LiNi 0.5 Mn 1.5 O 4 and other battery systems.
  • the mass ratio of the polymer and the second polymer is 20:1 ⁇ 2:1.
  • the polymer electrolyte membrane further includes a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium bisfluorosulfonyl imide (LiFSI), One or more of lithium trifluoromethanesulfonyl imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium perchlorate (LiClO 4 ), and lithium bisoxalate borate (LiBOB).
  • a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium bisfluorosulfonyl imide (LiFSI), One or more of lithium trifluoromethanesulfonyl imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium perch
  • the type of lithium salt affects the lithium ion migration number of the prepared polymer electrolyte membrane. Different lithium salts have different dissociation degrees between anions and cations due to different structures. Lithium salts with a high degree of dissociation can provide more carriers. The concentration of Li + will affect the relationship between it and the ether oxygen atoms and carbonyl groups in the polymer chain. The "coordination-dissociation" process affects the migration ability of Li + and anions in the battery during the charge and discharge process. Generally, PEO-based electrolytes have a transfer number less than 0.2 due to the multidentate coordination chelation between ether oxygen atoms and Li + and the relatively weak solvent interaction with TFSI – anions.
  • the mass proportion of lithium salt in the polymer electrolyte membrane is in the range of 6.8 to 30.0%, based on the total mass of the polymer electrolyte membrane.
  • the fluorine element content in the polymer electrolyte membrane ranges from 12.5 to 46.0%, based on the total weight of the polymer electrolyte membrane.
  • the substitution of fluorine element in the Rf group of the polymer can optimally maintain a proportion of greater than or equal to 29.0%.
  • the content of fluorine is finally controlled within the above range, which is more conducive to achieving high pressure resistance and flame retardant properties of the electrolyte membrane.
  • a third aspect of the present application provides a method for preparing a polymer electrolyte membrane, including the following steps:
  • monomer 1, monomer 2, and monomer 3 undergo co-block polymerization in the presence of an initiator to form the polymer
  • monomer 4 undergoes a co-block polymerization reaction in the presence of a lithium salt and optionally a catalyst.
  • An ionic copolymerization reaction occurs to form a fluid second polymer.
  • the method for preparing a polymer electrolyte membrane further includes the step of performing anion exchange between the obtained product 1 and a solution of a lithium salt to obtain the product 2.
  • the anions Q- carried by the ionic groups in the formed polymer, such as Cl- which can corrode aluminum foil, can be replaced with the target anion, optionally, with the same anion type as in the lithium salt. anions.
  • the target anion optionally, with the same anion type as in the lithium salt. anions.
  • the method for preparing a polymer electrolyte membrane according to the present application further includes drying the obtained product 2.
  • drying is to remove residual solvent. Drying can be carried out by any means conventionally used in the art, as long as the purpose of removing the solvent is achieved without degrading the electrolyte membrane.
  • a vacuum drying oven can be used for drying.
  • the ratio of the sum of the masses of monomer 1, monomer 2, and monomer 3 to the mass of monomer 4 is 20:1 ⁇ 2:1.
  • the mass ratio of the sum of the masses of monomer 1, monomer 2, monomer 3, and monomer 4 to the lithium salt In the range of 2.3 ⁇ 13.6.
  • the weight ratio of the lithium salt to the initiator is 5:1 to 60:1; if a catalyst is used, the lithium salt The ratio between the weight of the salt and the catalyst and the weight of the initiator is 7:1 to 80:1.
  • the initiator can be used to initiate the block copolymerization of the polymer described in this application, and the lithium salt and the catalyst can be used to initiate the ionic polymerization of the second polymer.
  • the ratio of the two can, in a certain sense, react to the two polymerizations prepared.
  • the polymer described in this application adopts block copolymerization and is prepared by initiator initiation.
  • the second polymer is prepared using ionic polymerization catalyzed by a lithium salt and optionally a catalyst.
  • the monomers of the two polymers are mixed together, they are prepared separately without interfering with each other.
  • each monomer, initiator, and optional catalyst are mixed evenly in the solution before the polymerization reaction is performed, what is obtained after complete polymerization is an interpenetrating network in which the polymer network and the second polymer network are evenly interpenetrated. structure, and the lithium salt is evenly dispersed in it.
  • the present application provides a solid electrolyte membrane prepared by the above method for preparing a solid polymer electrolyte membrane.
  • a fifth aspect of the present application provides a secondary battery, including a positive electrode and a negative electrode, which further includes the polymer electrolyte membrane described in the third aspect of the present application or a polymer electrolyte membrane prepared by the method described in the fourth aspect of the present application.
  • the secondary battery, battery module, battery pack and power consumption device of the present application are described below.
  • the positive electrode includes a positive electrode current collector and a positive electrode film layer
  • the positive electrode film layer includes a positive electrode active material, the above-mentioned second polymer and the above-mentioned lithium salt.
  • the mass proportion of the second polymer in the cathode film layer is 2-15%, and optionally, the mass proportion of the lithium salt in the cathode film layer is 0.5-10%.
  • the second polymer in the positive electrode diaphragm has the following advantages: the internal pores of the positive electrode diaphragm are filled by the fluid second polymer and lithium salt.
  • the fluid second polymer not only wets the inside of the electrode piece, but also At the same time, the movement of its chain segments also provides a channel for the transmission of lithium ions inside the pole piece, thus enhancing the ion transmission inside the positive electrode membrane.
  • the negative electrode includes a negative electrode current collector and a metal sheet formed of lithium metal or lithium alloy.
  • the polymer electrolyte membrane described in this application is suitable for use with lithium metal negative electrodes, lithium alloy negative electrodes, or no negative electrodes with high specific capacity (3860mAh/g) and extremely low potential (-3.04V vs. H 2 /H + ) .
  • the thickness of the negative electrode piece is 9-50 ⁇ m.
  • the lithium alloy includes, but is not limited to, lithium aluminum alloy, lithium magnesium alloy, lithium boron alloy, etc.
  • the polymer electrolyte membrane has a thickness of 10 to 1000 ⁇ m.
  • a sixth aspect of the present application provides a battery module, which includes the secondary battery described in the fifth aspect of the present application.
  • a seventh aspect of the present application provides a battery pack, which includes the battery module described in the sixth aspect of the present application.
  • An eighth aspect of the present application provides an electrical device, which includes a secondary battery selected from the fifth aspect of the present application, a battery module described in the sixth aspect of the present application, or a battery described in the seventh aspect of the present application. At least one of the packages.
  • Figure 1 is a schematic diagram of the interpenetrating network structure of the polymer and the second polymer of the present application, in which the dots represent the lithium salt, and the two different random lines represent the polymer and the second polymer respectively.
  • Figure 2 is a graph showing the charge and discharge curves of the battery core (that is, the battery obtained after matching the positive and negative electrodes) when the solid electrolyte membrane prepared in Example 1 was tested for high-voltage cycle performance.
  • FIG. 3 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 4 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 3 .
  • FIG. 5 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 6 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 7 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 6 .
  • FIG. 8 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-6.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • the parameter is an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • " ⁇ " and "-" have the same meaning when expressing a range.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • Solid-state batteries can be divided into four categories: polymers, sulfides, oxides, and chlorides according to the solid-state electrolyte chemical system.
  • polymer solid-state electrolytes represented by polyethylene oxide (PEO) systems have good interfacial wetting and excellent processing properties.
  • PEO polyethylene oxide
  • the advantages of performance, light weight and low density, and low cost have led to commercial application in the 1990s.
  • the vast majority of such polymer electrolytes have a low voltage window (such as PEO ⁇ 3.9V) and are difficult to match the high-voltage cathode, which greatly limits the improvement of battery energy density.
  • the flammable characteristics of the polymer cannot meet the requirements of the next generation.
  • First-generation batteries have high safety requirements.
  • the electrolyte membrane is prepared using modified aluminum-based polymers.
  • the electrolyte membrane is prepared by mixing a modified aluminum-based polymer, a branched polymer, and an electrolyte evenly, adding a photoinitiator, and performing cross-linking under stirring conditions.
  • the secondary battery with this electrolyte membrane has high conductivity and can achieve stable cycling at 4.2V.
  • the polymer since the polymer has a cross-linked structure, it can provide high mechanical strength to the solid electrolyte membrane and reduce the generation of dendrites, thereby improving the safety of lithium metal secondary batteries.
  • the modified aluminum-based polymer film uses polyester as the main structure and is not resistant to high pressure.
  • the modified aluminum-based polymer film contains inorganic components. , and is a cross-linked structure.
  • the mechanical properties are improved, this will affect the interface contact between the solid electrolyte membrane prepared by it and the positive and negative electrodes; in addition, the solid electrolyte membrane only focuses on high-pressure resistance characteristics and has no impact on the material itself. Safety properties such as flame retardancy are not covered.
  • this application provides a new polymer, which itself has good flame retardant properties and can form an interpenetrating network structure with other polymers.
  • Using a polymer with this structure as an electrolyte membrane can Provides better mechanical strength, and the secondary battery prepared using the electrolyte membrane has better safety performance, better high-voltage stability and better high-voltage cycle performance, and can achieve a better relationship between the electrolyte membrane and the positive and negative electrodes. Nice interface touch.
  • the first aspect of the application provides a polymer, which is polymerized by monomer 1, monomer 2, and monomer 3, wherein the monomer 1 has the structure of formula 1, the monomer 2 has the structure of formula 2, and the monomer 2 has the structure of formula 2.
  • Body 3 has the structure of formula 3,
  • R1 and R3 are each independently selected from hydrogen or C 1-10 alkyl
  • R4 is selected from C 1-10 hydrocarbon groups or C 1-10 hydrocarbon groups containing one or more elements from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus;
  • R2 and R5 are each independently selected from hydrogen, C 1-10 hydrocarbon groups, or one or more elements containing fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • Rf is selected from hydrogen, or an ethoxy chain segment containing one or more elements of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus with a carbon number of less than or equal to 16;
  • x is the number of repeating units of methylene, 0 ⁇ x ⁇ 20;
  • a + is selected from one of the functional groups with nitrogen, sulfur, and phosphorus as the cation center;
  • Q - is one, two or more anions selected from halide, haloborate, halooxaloborate, perhalate, halophosphate, halosulfonimide, optionally Q - It is one, two or more anions selected from chloride ion, tetrafluoroborate, difluoroxaloborate, perchlorate, hexafluorophosphate, and bis(fluorosulfonyl)imide;
  • R6 is selected from hydrogen or C 1-10 alkyl.
  • C 1-10 alkyl is a straight-chain or branched alkyl group containing 1-10 carbons, which includes, but is not limited to, for example, methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 2,2- Dimethylbutyl, 2,3-dimethylbutyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 2, 3-dimethylpentyl, 2,4-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, 2-methylheptyl, 3-methylheptyl , 4-methylheptyl
  • the C 1-10 hydrocarbon group may include the above-mentioned C 1-10 alkyl group, C 6-10 aromatic group, linear or branched C 2-10 alkenyl group, linear or branched C 2-10 alkyne Ji, et al.
  • the C 6-10 aryl group may be, for example, phenyl, naphthyl, C 1-4 alkyl substituted phenyl.
  • the C 2-10 alkenyl group may be, for example, vinyl, propenyl, allyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, and the like.
  • the C 2-10 alkynyl group may be, for example, ethynyl, propynyl, butynyl, butadiynyl, pentynyl, pentadiynyl, hexynyl, and the like.
  • R4 group of monomer 2 is "a C 1-10 hydrocarbon group containing one or more elements of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus" Can be linear or branched, mono- or poly-substituted, saturated or unsaturated.
  • Constants from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus means containing these elements in a substituted form, such as but not limited to fluorine, chlorine, bromine, iodine , these elements can also be contained in other forms, such as as groups or components of the main structure of the structural formula, such as but not limited to nitrogen, oxygen, sulfur, silicon, boron, and phosphorus, as long as it can be chemically realized.
  • the R4 group may be phenyl, vinyl, propenyl, allyl, pyridyl, pyrimidinyl, etc.
  • C 2-10 alkenyl can be, for example, vinyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, etc.;
  • C 2-10 alkynyl It may be, for example, ethynyl, propynyl, butynyl, butadiynyl, pentynyl, pentadiynyl, hexynyl, etc.
  • Constants from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus means containing these elements in a substituted form, such as but not limited to fluorine, chlorine, bromine, iodine , these elements can also be contained in other forms, such as as groups or components of the main structure of the structural formula, such as but not limited to nitrogen, oxygen, sulfur, silicon, boron, and phosphorus, as long as it can be chemically realized.
  • R2, R5 may be hydrogen, vinyl, propenyl, allyl, etc.
  • the number of carbon atoms of one or more elements containing fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus is less than or equal to "16 ethoxy segment” means it has 1 to 8 ethoxy segments and contains one or more of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus element.
  • Constants from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus means containing these elements in a substituted form, such as but not limited to fluorine, chlorine, bromine, iodine , these elements can also be contained in other forms, such as as groups or components of the main structure of the structural formula, such as but not limited to nitrogen, oxygen, sulfur, silicon, boron, and phosphorus, as long as it can be chemically realized.
  • the chain segment of 1 to 8 ethoxy groups may also be substituted by a branched or linear C 1-10 alkyl group or a haloalkyl group.
  • an ethoxy chain segment containing one or more elements of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus with a carbon number of less than or equal to 16 can be an ethoxy chain segment with a ring.
  • the ethoxy segment connected to the triphosphazene may also be an ethoxy segment substituted by one or more elements selected from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron and phosphorus.
  • the "functional group with nitrogen, sulfur, or phosphorus as the cation center" in the definition of A + means that the functional group contains nitrogen, sulfur, or phosphorus, and the nitrogen, sulfur, or phosphorus is the cation center.
  • a + is a functional group of a nitrogen-containing cation, more optionally, it is selected from the group consisting of ammonium cation, imidazolium cation and pyridinium cation, most optionally, A + is -N(R') 2 + - , wherein each R' is independently selected from hydrogen or C 1-10 alkyl.
  • Q - is defined as one, two or more anions selected from halide, haloborate, halooxaloborate, perhalate, halophosphate, and halosulfonimide,
  • the number of anions depends on the number of cations in A + , for example, in the case of A + group with two positive charges, Q- can be two singly charged anions.
  • the number of ions in A + and Q - is not specifically limited, as long as it can be chemically realized.
  • the halide ion may be fluoride ion, chloride ion, bromide ion, or iodide ion.
  • the halogenation can be fluoro, chlorine, bromo, iodo, optionally fluoro, and the halogenation can be mono-substituted, disubstituted or poly-substituted.
  • the perhalate radical may be perfluorate radical, perchlorate radical, perbromate radical, or periodate radical.
  • the polymer provided in this application is formed by the polymerization of three monomers (monomer 1, monomer 2, and monomer 3). It has an ethyl group as the main chain, and its molecular structure contains ionic groups (from monomer 1), amide Functional groups such as (from monomer 1), phosphate ester (from monomer 2) and fluorinated ethoxy (from monomer 3). Each of these functional groups provides a different role to the polymer. It is now believed that, for example, the presence of the ionic group and fluorine element (mainly from monomer 3) is beneficial to improving the oxidation resistance or high-pressure stability of the material (especially high voltages above 5V).
  • the flexible ethoxy side chains in the polymer can drive the migration of lithium ions, and the cation center in the ionic group can interact with the anions in the lithium salt to improve Lithium ion migration number;
  • the synergistic effect of the phosphate ester group from monomer 2 and the fluorine element (mainly from monomer 3) makes the electrolyte containing the polymer exhibit excellent flame retardant properties, which is applied to lithium ion dioxide secondary battery, which can improve the safety of the battery;
  • the amide from monomer 1 makes the polymer molecules have a strong hydrogen bond association force, and the existence of the strong hydrogen bond association force and the phosphate ester (from monomer 2 ) is the center of the cross-linked network, which is beneficial to enhancing the mechanical properties of polymer materials.
  • the polymers described herein may be random triblock polymers.
  • the polymers described herein have the following structural formula:
  • R1, R2, R3, R4, Rf, E, A + , Q - , x are as defined above, and
  • n, m, p are the number of repeating units, where 0 ⁇ n ⁇ 5000, 0 ⁇ m ⁇ 1000, 0 ⁇ p ⁇ 5000, and
  • the ratio of n to m n:m is in the range of 1:1 to 25:1, and the ratio of p to m p:m is in the range of 1:1 to 25:1.
  • the tildes represent the cross-linking sites of one polymer molecule of Formula 4 to another polymer molecule of Formula 4.
  • the polymer has a triblock structure.
  • the tri-block structure of the polymer can block the contact between the ethoxy side chains and reduce the crystallinity of the polymer material.
  • the ionic conductivity can be improved.
  • the fluorine element substitution rate in the Rf group is greater than 29.0%, and the fluorine element substitution rate is a proportion of the number of fluorine atoms, based on the number of hydrogen atoms that can be substituted in the Rf group.
  • the "number of hydrogen atoms that can be substituted" should be understood as the number of sites that can be substituted in the Rf group, that is, it can be related to the carbon atoms present in the group, the possible phosphorus atoms, The maximum number of hydrogen atoms connected to possible nitrogen atoms and possible sulfur atoms. If the hydrogen atoms have been replaced by other elements, such as halogen atoms, the number of hydrogen atoms that can be substituted is calculated as the number of hydrogen atoms and the substituted The sum of the numbers of other atoms.
  • a fluorine element substitution rate of greater than or equal to 29.0% can ensure the flame retardant properties of the polymer and improve the high-voltage stability and high-voltage cycleability of batteries obtained using the polymer.
  • the cation A + is selected from one of the structural formulas (4) to (6):
  • the molar ratio of monomer 1 ranges from 3.7 to 92.6 mol%
  • the molar ratio of monomer 2 ranges from 2.0 to 33.3 mol%
  • the molar ratio of monomer 3 The ratio range is 3.7 to 92.6 mol%, all based on the total number of moles of monomer 1, monomer 2, and monomer 3.
  • the molar ratio of monomer 1 to monomer 2 is in the range of 1:1 to 25:1;
  • the molar ratio of monomer 3 to monomer 2 is in the range of 1:1 to 25:1.
  • the thermal conductivity of the polymer is in the range of 0.06 to 0.35 W/m K, and the flame retardant level is 94V-0 or 94V-1.
  • the thermal conductivity of the polymer and electrolyte membrane can be determined according to GB T 10294-2008.
  • the flame retardant level of the polymer and electrolyte membrane can be determined according to the UL94 vertical burning test of ASTM D3801.
  • the second aspect of the application provides a method for preparing the polymer described in the first aspect of the application, including the following steps: dissolving the monomer 1, the monomer 2, the monomer 3 and the initiator in a solvent, React in vacuum at 30-100°C for 0.2-24h, optionally 6-24h, and then dry.
  • the polymers are carried out as block copolymers.
  • the drying is performed in a vacuum at 25-140°C for 1-48 hours. The main purpose of drying is to remove the solvent remaining after the reaction.
  • a third aspect of the present application provides a polymer electrolyte membrane, which includes the polymer described in the first aspect of the present application or a polymer prepared by the method described in the second aspect of the present application.
  • the polymer electrolyte membrane further includes a second polymer.
  • the second polymer is dispersed in the polymer to form an interpenetrating network structure.
  • the second polymer is formed from monomer 4.
  • the general structure of body 4 is as follows:
  • R7 is selected from hydrogen, or a hydrocarbon group with less than 7 carbon atoms that is unsubstituted or substituted by one or more elements of fluorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • hydrocarbyl groups with less than 7 carbon atoms include, but are not limited to: alkyl groups with less than 7 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl , 2,3-dimethylbutyl, etc.; alkenyl groups with less than 7 carbon atoms, such as ethylene, propylene, butene, butadiene, pentene, pentadiene, hexene, hexadiene, etc.; and Alkynyl groups with less than 7 carbon atoms, such as acetylene, propyne, butyne, pent
  • the hydrocarbon group with less than 7 carbon atoms may be unsubstituted, or may be mono- or poly-substituted by one or more elements selected from fluorine, bromine, iodine, nitrogen, oxygen, sulfur, silicon, boron, and phosphorus.
  • the second polymer is relative to the foregoing polymer in order to distinguish it from the foregoing polymer.
  • the polymers described in this application can form an interpenetrating network structure with other polymers, optionally polymers with fluidity, to obtain polymers with higher mechanical strength.
  • the above-mentioned second polymer is uniformly dispersed in the polymer to form an interpenetrating network structure. See Figure 1 for a schematic diagram of the interpenetrating network between the polymer and the second polymer.
  • the interpenetrating network structure is a special blend, which can also be called an interpenetrating polymer network (IPN for short).
  • IPN interpenetrating polymer network
  • a solid electrolyte membrane including an interpenetrating network structure formed by a polymer network and a second polymer network
  • the high-pressure stability of the electrolyte membrane can be effectively improved, and the The electrolyte membrane exhibits a wide electrochemical window and is therefore suitable for high-voltage battery systems.
  • the polymer electrolyte membrane exhibit excellent flame retardant properties and improves the safety of lithium metal batteries; in addition, the flexible ethoxy chain segments in the polymer network can drive the migration of lithium ions to nitrogen and phosphorus.
  • the ionic group with sulfur as the cation center can limit its movement by interacting with the anions in the lithium salt, thereby increasing the lithium ion migration number; the hydrogen bond association force of the competition between the amide molecules in the polymer network and the phosphate ester as the center
  • the construction of a cross-linked network is conducive to enhancing the mechanical properties of the material; at the same time, the tri-block structure of the polymer can also form contacts with the ethoxy side chain base, reduce the crystallinity of the material, and improve the ionic conductivity of the electrolyte membrane.
  • the second polymer described in this application is an oligomer, which has carbonate as the main chain, has a number average molecular weight M n ⁇ 2000 Da, a viscosity of less than 3000 cP, and has certain fluidity.
  • the second polymer may also be referred to as a carbonate polymer.
  • This oligomer is uniformly dispersed in the polymer network as the second polymer network, that is, in the above-mentioned random triblock polymer, the presence of the carbonate backbone in the second polymer network is the high pressure of the formed electrolyte membrane. The stability is guaranteed and contributes to the excellent high voltage resistance performance of the secondary battery containing the electrolyte membrane.
  • the second polymer in the interpenetrating network structure has a certain fluidity and can wet the electrode piece, thereby improving the interface contact between the electrolyte membrane and the positive and negative electrodes. Therefore, in a solid electrolyte membrane including an interpenetrating network of a network formed by a polymer and a network formed by a second polymer, the introduction of a fluid second polymer network not only improves the lubrication between the electrolyte membrane and the electrodes The wet performance improves the interface contact between the electrolyte membrane and the positive and negative electrodes. At the same time, the chain segment movement of carbonate can drive the migration of lithium ions, which also ensures the high ionic conductivity of the electrolyte membrane.
  • the electrolyte membrane containing the above-mentioned interpenetrating network structure described in this application is suitable for high-voltage battery systems, such as 5V high-voltage battery systems.
  • the high-voltage battery body series includes, but is not limited to, LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiCoO 2 , LiMn 2 O 4 , LiNiCoAlO 2 , LiNi 0.5 Mn 1.5 O 4 and other battery systems.
  • the mass ratio of the polymer and the second polymer is 20:1 ⁇ 2:1.
  • the polymer electrolyte membrane further includes a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium bisfluorosulfonyl imide (LiFSI), One or more of lithium trifluoromethanesulfonyl imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium perchlorate (LiClO 4 ), and lithium bisoxalate borate (LiBOB).
  • a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium bisfluorosulfonyl imide (LiFSI), One or more of lithium trifluoromethanesulfonyl imide (LiTFSI), lithium difluorooxalate borate (LiDFOB), lithium perch
  • the type of lithium salt affects the lithium ion migration number of the prepared polymer electrolyte membrane. Different lithium salts have different dissociation degrees between anions and cations due to different structures. Lithium salts with a high degree of dissociation can provide more carriers. The concentration of Li + will affect the relationship between it and the ether oxygen atoms and carbonyl groups in the polymer chain. The "coordination-dissociation" process affects the migration ability of Li + and anions in the battery during the charge and discharge process. Generally, PEO-based electrolytes have a transfer number less than 0.2 due to the multidentate coordination chelation between ether oxygen atoms and Li + and the relatively weak solvent interaction with TFSI – anions.
  • the mass proportion of lithium salt in the polymer electrolyte membrane is in the range of 6.8 to 30.0%, based on the total mass of the polymer electrolyte membrane.
  • the mass ratio of the interpenetrating network structure to the lithium salt can also be expressed as the mass ratio of the sum of the masses of the polymer and the second polymer to the lithium salt, or
  • the mass ratio of the total mass of the monomers 1 to 4 to the lithium salt is 2.3 to 13.6.
  • the fluorine element content in the polymer electrolyte membrane ranges from 12.5 to 46.0%, based on the total weight of the polymer electrolyte membrane.
  • the substitution of fluorine element in the Rf group of the polymer can optimally maintain a proportion of greater than or equal to 29.0%.
  • the content of fluorine is finally controlled within the above range, which is more conducive to achieving high pressure resistance and flame retardant properties of the electrolyte membrane.
  • a third aspect of the present application provides a method for preparing a polymer electrolyte membrane, including the following steps:
  • the initiator is used to initiate the block copolymerization reaction between monomer 1, monomer 2, and monomer 3 to form the polymer described in this application.
  • the initiator includes, but is not limited to, azo or peroxy molecules, such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(iso Butylnitrile), 2,2'-Azobis(methylbutyric acid nitrile), 1,1'-Azobis(cyanocyclohexane), dibenzoyl peroxide, dodecanoyl peroxide, Di-tert-butyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate.
  • azo or peroxy molecules such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(iso Butylnitrile), 2,2'-Azobis(methylbutyric acid nitrile), 1,1
  • the mass of the initiator does not exceed 5% of the total mass of the two polymer monomers and the lithium salt (ie, the sum of the masses of monomer 1, monomer 2, monomer 3, monomer 4 and lithium salt) %.
  • the lithium salt is as described above.
  • the lithium salt can be used to catalyze the ionic polymerization of monomer 4 to form a fluid second polymer.
  • Catalysts that can be used include, but are not limited to, stannous isooctate, aluminum trifluoromethanesulfonate, aluminum trichloride, trimethylsilyl triflate, boron trifluoride ether, triethylamine, 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • the catalyst catalyzes the polymerization of the second polymer. In this application, the second polymer is obtained through ionic polymerization.
  • the monomer 1, monomer 2, monomer 3 and monomer 4 are dissolved in a solvent. , through stirring or other means to obtain a uniform solution.
  • the uniform solution is poured into a tool commonly used in this field (such as a polytetrafluoroethylene mold), heated to 30 to 100°C and reacted under vacuum for 0.2 to 24 hours.
  • a tool commonly used in this field such as a polytetrafluoroethylene mold
  • the reaction Carry out in a vacuum oven.
  • the method for preparing a polymer electrolyte membrane further includes the step of performing anion exchange between the obtained product 1 and a solution of a lithium salt to obtain the product 2.
  • anions there are Q - anions in monomer 1.
  • Some anions such as chloride ions
  • the anions Q- carried by the ionic groups in the formed polymer, such as Cl- which can corrode aluminum foil, can be replaced with the target anion, optionally, with the same anion type as in the lithium salt. anions. In this way, on the one hand, the occurrence of some side reactions can be prevented, and on the other hand, the binding ability between anions, the polymer and lithium ions can be adjusted.
  • the concentration of anions in the lithium salt solution used for anion exchange needs to be much higher than the concentration of Q - in the polymer.
  • the concentration of Q- can be determined by conventional technical means in the art.
  • silver nitrate can be used for titration. The titration is carried out in a neutral solution, using potassium chromate as an indicator, by consuming silver nitrate. The volume of the solution can be used to calculate the chloride ion concentration.
  • the lithium salt solution is a separately prepared solution, and the lithium salt in the lithium salt solution is the same as or different from the lithium salt in the electrolyte membrane. It is more advantageous when they are the same.
  • anion exchange is performed for 1 to 20 hours. This time is not limiting and can be adjusted depending on the actual situation.
  • the solvent in the lithium salt solution used may be, for example, but not limited to, acetone, acetonitrile, ethylene glycol dimethyl ether, dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate.
  • the method for preparing a polymer electrolyte membrane according to the present application further includes drying the obtained product 2.
  • drying is to remove residual solvent. Drying can be carried out by any means conventionally used in the art, as long as the purpose of removing the solvent is achieved without degrading the electrolyte membrane.
  • a vacuum drying oven can be used for drying.
  • the drying temperature does not exceed 140°C and the drying time at 140°C does not exceed 1 hour.
  • the heat shrinkage temperature of the electrolyte membrane is about 140°C to 160°C.
  • the ratio of the sum of the masses of monomer 1, monomer 2, and monomer 3 to the mass of monomer 4 is 20:1 ⁇ 2:1.
  • the mass ratio of the sum of the masses of monomer 1, monomer 2, monomer 3, and monomer 4 to the lithium salt In the range of 2.3 ⁇ 13.6.
  • the weight ratio of the lithium salt to the initiator is 5:1 to 60:1; if a catalyst is used, the lithium salt The ratio between the weight of the salt and the catalyst and the weight of the initiator is 7:1 to 80:1.
  • the initiator can be used to initiate the block copolymerization of the polymer described in this application, and the lithium salt and the catalyst can be used to initiate the ionic polymerization of the second polymer.
  • the ratio of the two can, in a certain sense, react to the two polymerizations prepared.
  • the solvent used in the preparation of the polymer and the electrolyte membrane of the present application, can be acetonitrile or other solvents commonly used in this field, such as acetone, 1,4-dioxane, N-methylpyrrolidone, Dimethyl sulfoxide, methyl ethyl carbonate, dimethyl carbonate, ethylene carbonate, ethylene glycol dimethyl ether, etc.
  • the polymer described in this application adopts block copolymerization and is prepared by initiator initiation.
  • the second polymer is prepared using ionic polymerization catalyzed by a lithium salt and optionally a catalyst.
  • the monomers of the two polymers are mixed together, they are prepared separately without interfering with each other.
  • each monomer, initiator, and optional catalyst are mixed evenly in the solution before the polymerization reaction is performed, what is obtained after complete polymerization is an interpenetrating network in which the polymer network and the second polymer network are evenly interpenetrated. structure, and the lithium salt is evenly dispersed in it.
  • the present application provides a solid electrolyte membrane prepared by the above method for preparing a solid polymer electrolyte membrane.
  • a fifth aspect of the present application provides a secondary battery, including a positive electrode and a negative electrode, which further includes the polymer electrolyte membrane described in the third aspect of the present application or a polymer electrolyte membrane prepared by the method described in the fourth aspect of the present application.
  • the secondary battery, battery module, battery pack and power consumption device of the present application are described below.
  • the secondary battery described in this application includes a positive electrode sheet, a negative electrode sheet and the polymer electrolyte membrane described in this application.
  • active ions are inserted and detached back and forth between the positive and negative electrodes.
  • the polymer electrolyte membrane plays a role in conducting ions between the positive electrode piece and the negative electrode piece.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes the positive electrode active material of the first aspect of the present application.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon.
  • At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the positive active material includes lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 , LiMn 2 O 4 , etc.), lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 or LiNi 0.6 Co 0.2 Mn 0.2 O 2 ), etc.
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the positive electrode includes a positive electrode current collector and a positive electrode film layer
  • the positive electrode film layer includes a positive electrode active material, the above-mentioned second polymer and the above-mentioned lithium salt.
  • the mass proportion of the second polymer in the cathode film layer is 2-15%, and optionally, the mass proportion of the lithium salt in the cathode film layer is 0.5-10%.
  • the lithium salt in the positive electrode film layer may be of the same type as the lithium salt in the electrolyte, or may be different.
  • the foregoing description of the lithium salt in the electrolyte membrane also applies to the lithium salt in the positive electrode membrane layer.
  • the positive electrode sheet can be prepared by dispersing the positive active material, the conductive agent (for example, Super-p), the above-mentioned monomer 4 used to prepare the second polymer, and any other components.
  • a solvent such as N-methylpyrrolidone, NMP for short
  • the positive electrode slurry is obtained.
  • the drying can be performed in an oven at 30 to 100°C.
  • the positive active material accounts for 80% to 95%
  • the conductive agent accounts for 1 to 5%
  • the monomer 4 accounts for 2 to 15%
  • the The proportion of lithium salt is 0.5 to 10%, based on the total weight of the positive electrode active material, conductive agent, monomer 4 and any other components.
  • the lithium salt in the positive electrode membrane, the lithium salt in the electrolyte membrane, and the lithium salt in the optional anion exchange operation are the same type of lithium salt.
  • the second polymer in the positive electrode diaphragm has the following advantages: the internal pores of the positive electrode diaphragm are filled by the fluid second polymer and lithium salt.
  • the fluid second polymer not only wets the inside of the electrode piece, but also At the same time, the movement of its chain segments also provides a channel for the transmission of lithium ions inside the pole piece, thus enhancing the ion transmission inside the positive electrode membrane.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, where the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode in the secondary battery, includes a negative electrode current collector and a metal sheet formed of lithium metal or lithium alloy.
  • the negative electrode current collector can be copper foil, but is not limited to continuous copper foil, and can also be copper wire braided copper mesh, copper foam or three-dimensional nanoporous copper.
  • the polymer electrolyte membrane described in this application is suitable for use with lithium metal negative electrodes, lithium alloy negative electrodes, or no negative electrodes with high specific capacity (3860mAh/g) and extremely low potential (-3.04V vs. H 2 /H + ) .
  • the thickness of the negative electrode piece is 9-50 ⁇ m.
  • the lithium alloy includes, but is not limited to, lithium aluminum alloy, lithium magnesium alloy, lithium boron alloy, etc. It should be understood that the lithium alloy described in this application is not limited to lithium aluminum alloy, lithium magnesium alloy or lithium boron alloy, and other lithium alloys that can achieve the above purpose are also possible.
  • the negative electrode sheet is commercially available, or can be directly coated on the current collector by cold pressing lithium metal and/or lithium alloy.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the secondary battery uses the solid polymer electrolyte membrane described in this application, which can conduct lithium ions well and has high safety performance.
  • the polymer electrolyte membrane has a thickness of 10 to 1000 ⁇ m.
  • the positive electrode sheet, the solid polymer electrolyte membrane, and the negative electrode sheet are stacked in sequence to assemble a battery.
  • the secondary battery may include an outer package for packaging the positive electrode tab, the negative electrode tab, and the electrolyte.
  • the positive electrode sheet, the solid polymer electrolyte membrane, and the negative electrode sheet can be laminated to form a laminated structure cell or a winding process to form a wound structure cell, and the cell is packaged in an outer package.
  • the number of cells in the secondary battery can be one or several, and can be adjusted according to needs.
  • the present application provides an electrode assembly.
  • the positive electrode piece, the solid electrolyte membrane, and the negative electrode piece can be made into an electrode assembly through a lamination process or a winding process.
  • the outer packaging can be used to package the above-mentioned electrode assembly and solid electrolyte membrane.
  • the outer packaging of the secondary battery may be a soft bag, such as a pouch-type soft bag.
  • the soft bag may be made of plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the present application provides a method for preparing a secondary battery, wherein the polymer electrolyte membrane described in the present application or the polymer electrolyte membrane prepared according to the method described in the present application is used.
  • the preparation of the secondary battery may also include the step of assembling the negative electrode sheet, the positive electrode sheet and the electrolyte of the present application to form a secondary battery.
  • the positive electrode sheet, the polymer electrolyte membrane, and the negative electrode sheet can be stacked in order and cold-pressed to assemble a full battery.
  • FIG. 3 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • a sixth aspect of the present application provides a battery module, which includes the secondary battery described in the fifth aspect of the present application.
  • a seventh aspect of the present application provides a battery pack, which includes the battery module described in the sixth aspect of the present application.
  • An eighth aspect of the present application provides an electrical device, which includes a secondary battery selected from the fifth aspect of the present application, a battery module described in the sixth aspect of the present application, or a battery described in the seventh aspect of the present application. At least one of the packages.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 5 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Figure 8 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • the device is usually required to be thin and light, and a secondary battery can be used as a power source.
  • N,N,N-trimethyl-3-(2-methylallylamido)-1-propylammonium chloride, triallyl phosphate, perfluoropolyether acrylate (PFPE- MAA-1000) and fluoroethylene carbonate were purchased from Aladdin Reagent, Monomer-Polymer&Dajac Labs, Suzhou Cangmu, and Aladdin Reagent respectively.
  • the second polymer uses fluoroethylene carbonate for ionic polymerization.
  • the process is as follows:
  • the second polymer has a number average molecular weight of 2,000.
  • the molecular weight testing method is as follows:
  • NMP N-methylpyrrolidone
  • GPC gel permeation chromatography
  • LiCoO 2 lithium cobalt oxide
  • NMP N-methylpyrrolidone
  • LiDFOB lithium cobalt oxide
  • stannous isooctate mass concentrations of 12.5% and 2.1% respectively
  • Negative electrode piece Lithium metal (purchased from Shenzhen Kejing Zhida Technology Co., Ltd., specification is 30 ⁇ m thick) is cold-pressed and coated on the copper foil to obtain the negative electrode piece.
  • the above-mentioned positive electrode sheet containing the second polymer, the polymer solid electrolyte membrane, and the lithium metal or lithium alloy negative electrode sheet are stacked in order, cold-pressed and assembled into a full battery, and subsequent charge, discharge, and cycle tests are performed.
  • LiFSI lithium bisfluorosulfonyl imide
  • Electrolyte membrane size 100mm ⁇ 100mm ⁇ 15 ⁇ m
  • the polymer prepared in I-1, the second polymer prepared in I-2 and the electrolyte membrane prepared in I-3 into 30mm ⁇ 30mm square samples, in each case three parallel samples per set , and weigh the mass of each sample. Then, the sample was soaked in 1M LiFSI ethyl methyl carbonate (EMC) solution for 12 hours for swelling. After swelling, use filter paper to gently absorb the excess solvent attached to the surface of the swollen sample, and then measure the mass of the swollen sample.
  • the swelling parameter is the mass increase of the sample after swelling as a percentage of the mass of the original sample.
  • Polyethylene oxide (PEO) was used as a comparison to examine the flame retardant properties of the polymer.
  • the thermal conductivity of the polymer prepared in I-1, the electrolyte membrane prepared in I-3, the comparative polymer PEO in I-5, and the comparative electrolyte membrane prepared using PEO was measured according to GB T 10294-2008.
  • the flame retardant properties of the polymer prepared in I-1, the electrolyte membrane prepared in I-3, the comparative polymer PEO in I-5, and the comparative electrolyte membrane prepared using PEO were determined according to the UL94 vertical combustion test of ASTM D3801.
  • Examples 1-9 were used to examine the effects of monomer 1 and monomer 2 on the mechanical properties of the electrolyte membrane and on the high-voltage stability and high-voltage cycle performance of the battery.
  • the specific operations are as follows:
  • Example 1 Preparation of full cell according to I-3 and I-4.
  • Example 2-9 Preparation is similar to Example 1, the only difference is that the molar proportion of monomers 1 to 3 is changed (based on the total molar amount of monomers 1 to 3), the specific monomer usage amount and molar ratio are in The following table.
  • the performance of the electrolyte membrane and full battery prepared in Examples 1-9 was tested.
  • the test method is as follows:
  • the electrolyte membranes in Examples 1-9 were cut into rectangular electrolyte membrane samples with a size of 150 mm ⁇ 20 mm and a thickness of 15 ⁇ m.
  • the above-mentioned samples were measured from Stretch in the relaxed state until failure, record the tensile strength and length L when the maximum tensile stress breaks, and calculate the elongation at break according to (LL 0 )/L 0 ⁇ 100%.
  • the full battery in the embodiment was subjected to a constant current charge and discharge test at a charge and discharge rate of 0.5C to 0.5C in a voltage range of 2.8 to 4.3V, and each full battery was tested to cycle when 80% of the power remains during the high voltage upper limit charging process.
  • the number of turns (cls) record the value of the number of turns. The more turns, the better the high-pressure cycle stability.
  • the molar ratio of monomer 2 is low, such as Example 8 and Example 6, the tensile strength of the electrolyte membrane obtained is significantly lower.
  • the molar ratio of monomer 2 is too low, such as Example 8, high-pressure cycle Performance drops significantly.
  • the molar ratio of monomer 2 is high, such as in Examples 7 and 9, the elongation of the electrolyte obtained is poor.
  • the electrolyte membrane is prepared by using the same. The high-voltage stability of the battery is poor and the high-voltage cycle performance is significantly reduced. Therefore, for monomer 2, the molar ratio is preferably 2.0 to 33.3%, preferably 5% to 25%.
  • the molar ratio of monomer 1 and the molar ratio of monomer 2 have a greater impact on the mechanical strength (tensile strength and elongation) of the corresponding electrolyte membrane, and have a greater impact on the high-voltage stability of the corresponding battery. properties and high-pressure cycle performance also have a significant impact.
  • Examples 1 and 10 to 11 examine the effects of the cation species and lithium salt species in monomer 1 on the lithium ion migration number.
  • Example 1 As described above, a full cell was prepared according to I-3 and I-4.
  • Example 10 The electrolyte membrane and full battery were prepared similarly to Example 1, except that in the preparation of the electrolyte membrane in I-3, monomer 1 used the monomer in the following table instead of using N,N,N-trimethyl. -3-(2-Methylallylamido)-1-propylammonium chloride, the lithium salt uses LiBOB instead of LiFSI.
  • Example 11 Preparation of electrolyte membrane and full battery similar to Example 1, except that in the preparation of the electrolyte membrane in I-3, monomer 1 uses the monomer in the following table instead of using N,N,N-trimethyl. -3-(2-Methylallylamido)-1-propylammonium chloride, the lithium salt uses LiBF 4 instead of using LiFSI.
  • Comparative Example 1 The electrolyte membrane and full battery were prepared similarly to Example 1, except that in the preparation of the electrolyte membrane in I-3, monomer 1 used the monomer in the following table instead of using N,N,N-trimethyl. Base-3-(2-methylallylamido)-1-propylammonium chloride.
  • the lithium ion migration number of the electrolyte membrane prepared in each embodiment and comparative example was tested.
  • the test method is as follows:
  • R 0 el and R s el are the interface impedances between the electrode and the polymer electrolyte membrane before and after polarization respectively.
  • the interface impedance can be obtained by electrochemical impedance spectroscopy (EIS, also called AC impedance spectroscopy): to the battery system Applying a small amplitude sine wave voltage signal with frequency w1, the system produces a sine wave AC response with frequency w2.
  • the ratio of the applied voltage to the generated current is the impedance of the system.
  • the complex plane diagram of this value changing with the sine wave frequency ⁇ is: Nyquist diagram, the semicircular part in the high frequency region corresponds to the charge transfer process, and the diameter of the semicircle represents the interface impedance.
  • Examples 12 to 15 The electrolyte membrane and full battery were prepared similarly to Example 1, except that the molar ratio of monomer 3 was not changed (the amounts of monomers 1 and 2 were based on the molar ratio in Example 1 and Table 3 The mass of monomer 3 in monomer 3 is changed accordingly), only the Rf group and E group in monomer 3 are changed. See Table 5 below for details.
  • Example 16 The dosages of monomer 1, monomer 2, and monomer 3 are 0.221g, 0.218g, and 9.836g respectively, and the molar proportions are 9.10%, 9.10%, and 81.80% respectively.
  • Example 17 The amounts of monomer 1, monomer 2, and monomer 3 are 1.985g, 0.218g, and 1.094g respectively, and the molar proportions are 81.80%, 9.10%, and 9.10% respectively.
  • Example 18 The amounts of monomer 1, monomer 2, and monomer 3 are 0.049g, 0.218g, and 10.690g respectively, and the molar proportions are 2.0%, 9.10%, and 88.90% respectively.
  • Example 19 The amounts of monomer 1, monomer 2, and monomer 3 are 2.087g, 0.218g, and 0.589g respectively, and the molar proportions are 86.0%, 9.10%, and 4.90% respectively.
  • electrolyte membranes and full cells prepared in each example were subjected to the following tests:
  • the content of fluorine in the electrolyte membrane was detected by X-ray photoelectron spectroscopy (XPS).
  • the substitution rate of fluorine element is based on the number of hydrogen atoms that can be substituted in the Rf group, that is, the number of fluorine atoms/(the number of all halogen atoms + the number of hydrogen atoms).
  • Examples 24 to 27 Preparation was similar to Example 1, except that the amount of monomers 1 to 3 and the amount of lithium salt added were kept unchanged, and only the amount of monomer 4 was changed.
  • Examples 28 to 31 Preparation was similar to Example 1, except that the amount of monomers 1 to 4 was kept unchanged, and only the amount of added lithium salt was changed.
  • the mass proportion of lithium salt is calculated as the mass of lithium salt/the total mass of (monomers 1 to 4 + initiator + lithium salt + catalyst) ⁇ 100%.

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Abstract

本申请提供一种聚合物，其由单体1、单体2、单体3聚合而成，其中所述单体1具有式1结构，单体2具有式2结构，单体3具有式3结构，其中，R1、R2、R3、R4、R5、Rf、x、A+、Q-、E如说明书中的定义。本申请还提供一种包括由聚合物和碳酸酯聚合物形成的互穿网络结构的聚合物电解质膜。本申请提供的聚合物电解质膜机械强度优异、具有改善的离子电导率和离子迁移率，其制备的电池耐高压且高压循环性能优异。

Description

[根据细则37.2由ISA制定的发明名称]　聚合物及其制备、电解质膜及其制备 技术领域
本申请涉及一种聚合物。此外，本申请还涉及包含所述聚合物的电解质膜、包含所述电解质膜的二次电池、包括所述二次电池的电池包、电池模块和用电装置。
背景技术
近年来，随着锂离子电池的应用范围越来越广泛，锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于锂离子电池取得了极大的发展，因此对其电解质提出了更高的要求。
目前的商业化锂电池绝大多数采用有机液态电解质，其具有离子电导率高(10 -3S/cm)和电极表面润湿性好的优点。但是，有机液态电解质由于其易流动、易挥发、热稳定性差等缺点，极大地限制了锂电池在安全性方面的提升空间。另一方面，现代社会的快速发展对电池的能量密度和循环寿命提出了更高的要求。因而，具有高比容量(例如3860mAh/g)、极低电位(例如-3.04V vs.H 2/H +)的锂金属负极再次引起科研工作者的关注。然而，锂的高反应活性和锂枝晶短路的问题是锂金属发展不可逾越的障碍。固态电解质的出现打破了这个障碍。采用固态电解质替代有机液态电解质不仅可以从根本上解决电池的安全问题，也为进一步开发锂金属电池提供了可能。
采用铝基化聚合物用作金属锂二次电池中的固态聚合物电解质膜是目前比较有效的手段。然而，该固态聚合物电解质膜耐高压性能和安全性能尚有进步的空间。因此，目前仍需提供一种在具有较高机 械强度的同时还具有良好的耐高压特性和优异的阻燃性能的固态电解质膜。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种阻燃性能好、高压下不易氧化、用作电解质膜材料时能够改善离子电导率及锂离子迁移数且适合高压电池体系的聚合物及其制备方法；此外，本申请还提供一种与电极之间界面接触良好、离子电导率较高、高温稳定性好且机械性能好的包含所述聚合物的固态电解质膜及其制备方法。另外，本申请还提供一种包括所述电解质膜的二次电池。
因此，本申请的第一方面提供了聚合物，其由单体1、单体2、单体3聚合而成，其中所述单体1具有式1结构，单体2具有式2结构，单体3具有式3结构，
Figure PCTCN2022091467-appb-000001
其中，
R1、R3各自独立地选自氢或C 1-10烷基；
R4选自C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的C 1-10烃基；
R2、R5各自独立地选自氢、C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于10的含有C＝C或C≡C的烃基；
Rf选自氢、或含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于16的乙氧基链段；
x为亚甲基的重复单元数，0≤x≤20；
A +选自以氮、硫、磷为阳离子中心的官能团中的一种；
Q -为一个、两个或多个选自卤离子、卤代硼酸根、卤代草酸硼酸根、高卤酸根、卤代磷酸根、卤代磺酰亚胺根的阴离子，可选地Q -为一个、两个或多个选自氯离子、四氟硼酸根、二氟草酸硼酸根、高氯酸根、六氟磷酸根、双(氟磺酰)亚胺根的阴离子；
E选自(1)～(3)的结构，
Figure PCTCN2022091467-appb-000002
其中R6选自氢或C 1-10烷基。
本申请提供的聚合物由三种单体(单体1、单体2、单体3)聚合形成，其以乙基为主链，分子结构中含有离子基团(来自单体1)、酰胺(来自单体1)、磷酸酯(来自单体2)和氟化乙氧基(来自单体3)等功能性基团。这些功能性基团各自为所述聚合物提供了不同的作用。现认为，例如，所述离子基团与氟元素(主要来自单体3)的存在有利于提升材料的抗氧化性或高压稳定性(尤其是5V以上的高压)。在将所述聚合物作为电解质膜材料用于二次电池时，聚合物中的柔性乙氧基侧链可以带动锂离子迁移，离子基团中的阳离子中心可与锂盐中的阴离子作用从而提高锂离子迁移数；来自单体2的磷酸酯基团及氟元素(主要来自单体3)的协同效应，使得包含所述聚合物的电解质表现出极好的阻燃特性，其应用于锂二次电池，能够提高电池的安全性；来自单体1的酰胺使得聚合物分子间具有较强的氢键缔合力，所述较强的氢键缔合力的存在以及以磷酸酯(来自单体2)为中心的交联网络的构建有利于增强聚合物材料的机械性能。
可选地，所述聚合物具有三嵌段结构。所述聚合物的三嵌段的结构可以阻隔乙氧基侧链间的接触，降低聚合物材料结晶度，将其用于电解质膜，可以提升离子电导率。
在任意实施方式中，Rf基团中，氟元素取代率大于29.0％，所述氟元素取代率为氟原子的数目占比，基于Rf基团中可被取代的氢原子数目计。
所述“可被取代的氢原子的数目”应理解为在Rf基团中，可被取代的位点的数目，也即，可与该基团中存在的碳原子、可能存在的磷原子、可能存在的氮原子、可能存在的硫原子相连的氢原子的最大数目，如果所述氢原子已经被其他元素取代，例如卤素原子，则可被取代的氢原子数目计为氢原子数目和取代的其他原子数目之和。
氟元素取代率大于或等于29.0％能够确保聚合物的阻燃性能并且改善使用聚合物得到的电池的高压稳定性和高压循环性。
在任意实施方式中，在所述的聚合物中，阳离子A +选自(4)～(6)结构式中的一种：
Figure PCTCN2022091467-appb-000003
在任意实施方式中，在所述的聚合物中，单体1所占摩尔比范围为3.7～92.6摩尔％，单体2所占摩尔比范围为2.0～33.3摩尔％，单体3所占摩尔比范围为3.7～92.6摩尔％，全部基于单体1、单体2、单体3的总摩尔数计，
可选地，单体1与单体2的摩尔比在1:1至25:1范围内；
更可选地，单体3与单体2的摩尔比在1:1至25:1范围内。
在任意实施方式中，所述聚合物的导热系数在0.06～0.35W/m K范围内，阻燃级别为94V-0或94V-1。
本申请第二方面提供制备本申请第一方面所述的聚合物的方法，包括以下步骤：将所述单体1、所述单体2、所述单体3和引发剂溶于溶剂中，在30～100℃下在真空中反应0.2～24h、可选6～24h，然后 干燥。所述聚合物以嵌段共聚的形式进行。可选地，所述干燥在25～140℃下在真空中进行1～48h。干燥的主要目的是去除反应后存留的溶剂。
本申请第三方面提供一种聚合物电解质膜，其包括本申请第一方面所述的聚合物或由本申请第二方面所述的方法制备的聚合物。
在任意实施方式中，所述聚合物电解质膜还包括第二聚合物，所述第二聚合物分散于聚合物中，形成互穿网络结构，所述第二聚合物由单体4形成，单体4的通式结构如下：
Figure PCTCN2022091467-appb-000004
其中，
R7选自氢、或未被取代的或被氟、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素取代的碳原子数小于7的烃基。
如上所述，“碳原子数小于7的烃基”包括，但不限于：碳原子数小于7的烷基，例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、异丙基、异丁基、叔丁基、异戊基、叔戊基、新戊基、2-甲基戊基、3-甲基戊基、2,2-二甲基丁基、2,3-二甲基丁基等；碳原子数小于7的烯基，例如，乙烯、丙烯、丁烯、丁二烯、戊烯、戊二烯、己烯、己二烯等；和碳原子数小于7的炔基，例如，乙炔、丙炔、丁炔、戊炔、己炔等。碳原子数小于7的烃基可以是未取代的，也可以被氟、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素单取代或多取代。
本申请中，第二聚合物是相对于前述聚合物而言的，目的是为了与前述聚合物区分开。
本申请所述的第二聚合物为寡聚物，其以碳酸酯为主链，数均分子量M n<2000Da，粘度小于3000cP，具有一定的流动性。所述第二聚合物也可称为碳酸酯聚合物。该寡聚物作为第二聚合物网络均匀分散于上述聚合物的网络中，第二聚合物网络中碳酸酯主链的存在， 为所形成的电解质膜的高压稳定性提供了保障，为含有所述电解质膜的二次电池的优异的耐高压性能作出了贡献。所述互穿网络结构中的第二聚合物具有一定的流动性，可以起到润湿极片的作用，从而改善电解质膜和正负极之间的界面接触。因此，在包括由聚合物形成的网络和第二聚合物形成的网络的互穿网络的固态电解质膜中，具有流动性的第二聚合物网络的引入，不仅提高了电解质膜与电极间的润湿性能，改善了电解质膜与正负极之间的界面接触，同时由于碳酸酯的链段运动能够带动锂离子的迁移，也保证了该电解质膜较高的离子电导率。
在一些可选实施方式中，本申请所述的含有上述互穿网络结构的电解质膜适合高压电池体系，例如5V的高压电池体系。高压电池体系列包括，但不限于，LiNi 0.8Co 0.1Mn 0.1O 2、LiCoO 2、LiMn 2O 4、LiNiCoAlO 2、LiNi 0.5Mn 1.5O 4等电池体系。
可选地，所述互穿网络结构中，所述聚合物和所述第二聚合物的质量比为20:1～2:1。
在任意实施方式中，所述聚合物电解质膜还包括锂盐，所述锂盐选自六氟磷酸锂(LiPF 6)、四氟硼酸锂(LiBF 4)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、二氟草酸硼酸锂(LiDFOB)、高氯酸锂(LiClO 4)、双乙二酸硼酸锂(LiBOB)中的一种或多种。
锂盐的种类影响所制备的聚合物电解质膜的锂离子迁移数。不同锂盐因结构不同，阴阳离子间的离解度也存在差异，离解度高的锂盐可提供更多的载流子，Li +的浓度会影响它与高分子链中醚氧原子、羰基间的“配位-解离”过程，进而影响充放电过程中Li +及阴离子在电池中的迁移能力。通常PEO基电解质因醚氧原子与Li +间的多齿配位螯合作用，以及与TFSI –阴离子相对弱的溶剂作用使得转移数小于0.2。
在任意实施方式中，所述聚合物电解质膜中锂盐的质量占比在6.8～30.0％范围内，基于聚合物电解质膜总质量计。
在任意实施方式中，所述聚合物电解质膜中氟元素含量占比在12.5～46.0％范围内，基于聚合物电解质膜的总重量计。
为确保使用聚合物制备的电解质膜的耐高压和阻燃的双重特性，在聚合物的Rf基团中，氟元素的取代最佳地可保持占比大于等于29.0％。而在采用聚合物制备的聚合物电解质膜中，最后将氟元素的含量占比控制在上述范围内，这样更有利于实现电解质膜的耐高压和阻燃性能。
本申请的第三方面提供一种制备聚合物电解质膜的方法，包括以下步骤：
使本申请前述的单体1、单体2、单体3和本申请前述的单体4、本申请前述的锂盐、任选地催化剂、引发剂在30～100℃下反应0.2～24h，得到产物1。
现认为，该步骤中，单体1、单体2、单体3在引发剂的存在下发生共嵌段聚反应形成所述聚合物，单体4在锂盐和任选地催化剂的存在下发生离子共聚反应形成流动态的第二聚合物。
在任意实施方式中，在制备聚合物电解质膜的方法中，还包括使所得到产物1与锂盐的溶液进行阴离子交换得到产物2的步骤。
阴离子交换后可将形成的所述聚合物中的离子基团自带的阴离子Q -，如可腐蚀铝箔的Cl -，替换成目标阴离子，可选地，替换成与锂盐中阴离子种类相同的阴离子。这样，一方面可防止一些副反应的发生，另一方面也可调节阴离子与所述聚合物、锂离子间的结合能力。
在任意实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，还包括干燥所得到的产物2。
干燥的目的在于去除残留的溶剂。可采用本领域中常规使用的任何手段进行干燥，只要达到去除溶剂的目的且不会使电解质膜降解即可。可使用真空干燥箱进行干燥。
在任意实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述单体1、单体2、单体3的质量总和与单体4的质量之比为20:1～2:1。
在任意实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述单体1、单体2、单体3、单体4的质量总和与所述锂盐的质量比在2.3～13.6的范围内。
在任意实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述锂盐与所述引发剂的重量比为5:1～60:1；如果使用催化剂，所述锂盐和催化剂重量之和与引发剂重量之间的比例为7:1～80:1。
引发剂可用于引发本申请所述的聚合物的嵌段共聚反应，锂盐和催化剂可用于引发第二聚合物的离子聚合反应，二者的比例在一定意义上能够反应出所制备的两种聚合物的分布和互穿网络的结构组成。
现认为，本申请所述的聚合物采用嵌段共聚，通过引发剂引发而制备。第二聚合物采用离子聚合通过锂盐和任选地催化剂催化而制备。虽然两种聚合物各自单体混合在一起，但是各自进行各自的制备，不会互相干扰。并且，由于在进行聚合反应之前将各个单体、引发剂、任选地催化剂在溶液中混合均匀，因此，完全聚合后得到的是聚合物网络和第二聚合物网络均匀互穿的互穿网络结构，并且锂盐在其中均匀分散。
可选地，在任意实施方式中，本申请提供由上述制备固态聚合物电解质膜的方法制备的固态电解质膜。
本申请第五方面提供一种二次电池，包括正极、负极，其中，还包括本申请第三方面所述的聚合物电解质膜或由本申请第四方面所述的方法制备的聚合物电解质膜。下文对本申请的二次电池、电池模块、电池包和用电装置进行说明。
在任意实施方式中，所述正极包括正极集流体和正极膜层，所述正极膜层包括正极活性物质、上述第二聚合物和上述锂盐。可选地，所述第二聚合物在正极膜层中的质量占比为2～15％，可选地，所述锂盐在正极膜层中的质量占比为0.5～10％。
在正极膜片中使用第二聚合物具有以下优势：正极膜片内部孔隙由流动态的第二聚合物和锂盐填充，流动态的第二聚合物不仅起到润 湿极片内部的作用，同时其链段的运动还提供了锂离子在极片内部传输的通道，从而增强了正极膜片内部的离子传输。
在任意实施方式中，在所述的二次电池中，所述负极包括负极集流体和由锂金属或锂合金形成的金属片。
本申请所述的聚合物电解质膜适合与具有高比容量(3860mAh/g)、极低电位(-3.04V vs.H 2/H +)的锂金属负极、锂合金负极，或无负极搭配使用。可选地，负极极片厚度为9～50μm。
所述锂合金包括，但不限于，锂铝合金、锂镁合金、锂硼合金等。
在任意实施方式中，在所述的二次电池中，所述聚合物电解质膜的厚度为10～1000μm。
本申请的第六方面提供一种电池模块，其中，包括本申请第五方面所述的二次电池。
本申请的第七方面提供一种电池包，其中，包括本申请第六方面所述的电池模块。
本申请的第八方面提供一种用电装置，其中，包括选自本申请第五方面所述的二次电池、本申请第六方面所述的电池模块或本申请第七方面所述的电池包中的至少一种。
附图说明
图1为本申请所述聚合物和第二聚合物的互穿网络结构示意图，其中圆点代表锂盐，两种不同的无规线条分别代表所述聚合物和所述第二聚合物。
图2为对实施例1中制备的固态电解质膜进行高压循环性能测试时电芯(即匹配正负极之后得到的电池)的充放电曲线图。
图3是本申请一实施方式的二次电池的示意图。
图4是图3所示的本申请一实施方式的二次电池的分解图。
图5是本申请一实施方式的电池模块的示意图。
图6是本申请一实施方式的电池包的示意图。
图7是图6所示的本申请一实施方式的电池包的分解图。
图8是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的聚合物、聚合物电解质膜、锂电池及其制造方法的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-6。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。本文中，在表示一个范围时，“～”和“-”具有相同含义。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A、B、或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
固态电池按照固态电解质化学体系可分为聚合物、硫化物、氧化物、氯化物四类，其中以聚氧化乙烯(PEO)体系为代表的聚合物固态电解质因其良好的界面浸润、优异的加工性能、轻质低密的特点、成本低廉等优势已经在上世纪90年代率先实现了商业化应用。然而，绝大多数这样的聚合物电解质的电压窗口较低(如PEO∽3.9V)，难以匹配高压正极，这大大限制了电池能量密度的提升，同时聚合物的易燃特性，也不能满足下一代电池对高安全性的要求。
目前可耐高压的固态电解质膜的一个实例是采用改性铝基化聚合物来制备。该电解质膜由改性铝基化聚合物、支化聚合物、电解液 混合均匀后，加入光引发剂，在搅拌条件下进行交联制得。具有该电解质膜的二次电池具有较高的电导率，能在4.2V下实现稳定循环。而且，由于该聚合物为交联结构，因此能够为固态电解质膜提供较高的机械强度，并且能够减少枝晶的产生，从而能够提高锂金属二次电池的安全性等。然而，该改性铝基化聚合物膜以聚酯为主体结构，本身不耐高压，铝基化后对高压稳定性的提升有限；其次，该改性铝基化聚合物膜含有无机组分，且为交联结构，虽然机械性能得到提升，但这会影响由其制备的固态电解质膜与正负极之间的界面接触；另外，该固态电解质膜仅侧重耐高压特性，对材料本身的阻燃等安全性能没有涉及。
出乎意料地，本申请提供了一种新的聚合物，其本身具有良好的阻燃性能，且能够与其他聚合物形成互穿网络结构，使用具有该结构的高聚物作为电解质膜，可以提供更好的机械强度，并且使用该电解质膜制备的二次电池具有更好的安全性能、更好的高压稳定性和更好的高压循环性能，且能够实现电解质膜与正负极之间更好的界面接触。
因此，本申请的第一方面提供了聚合物，其由单体1、单体2、单体3聚合而成，其中所述单体1具有式1结构，单体2具有式2结构，单体3具有式3结构，
Figure PCTCN2022091467-appb-000005
其中，
R1、R3各自独立地选自氢或C 1-10烷基；
R4选自C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的C 1-10烃基；
R2、R5各自独立地选自氢、C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于10的含有C＝C或C≡C的烃基；
Rf选自氢、或含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于16的乙氧基链段；
x为亚甲基的重复单元数，0≤x≤20；
A +选自以氮、硫、磷为阳离子中心的官能团中的一种；
Q -为一个、两个或多个选自卤离子、卤代硼酸根、卤代草酸硼酸根、高卤酸根、卤代磷酸根、卤代磺酰亚胺根的阴离子，可选地Q -为一个、两个或多个选自氯离子、四氟硼酸根、二氟草酸硼酸根、高氯酸根、六氟磷酸根、双(氟磺酰)亚胺根的阴离子；
E选自(1)～(3)的结构，
Figure PCTCN2022091467-appb-000006
其中R6选自氢或C 1-10烷基。
本申请中，C 1-10烷基为含1-10个碳的直链或支链烷基，其包括、但不限于，例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、异丙基、异丁基、叔丁基、异戊基、叔戊基、新戊基、2-甲基戊基、3-甲基戊基、2,2-二甲基丁基、2,3-二甲基丁基、2-甲基己基、3-甲基己基、2,2-二甲基戊基、3,3-二甲基戊基、2,3-二甲基戊基、2,4-二甲基戊基、3-乙基戊基、2,2,3-三甲基丁基、2-甲基庚基、3-甲基庚基、4-甲基庚基、2,2-二甲基己烷基、3,3-二甲基己烷基、2,3-二甲基己烷基、2,4-二甲基己烷基、2,5-二甲基己烷基、3,4-二甲基己烷基、3-乙基己烷基、2,2,3-三甲基戊烷基、2,2,4-三甲基戊烷基、2,3,3-三甲基戊烷基、2,3,4-三甲基戊烷基、2-甲基-3-乙基戊烷基、3-甲基-3-乙基戊烷基、2,2,3,3-四甲基丁烷基、壬烷基、癸烷基。
本申请中，C 1-10烃基可包括上述C 1-10烷基、C 6-10芳香基、直链或支链的C 2-10烯基、直链或支链的C 2-10炔基、等。C 6-10芳香基可为例如苯基、萘基、C 1-4烷基取代的苯基。C 2-10烯基可为，例如，乙烯基、丙烯基、烯丙基、丁烯基、丁二烯基、戊烯基、戊二烯基、己烯基等。C 2-10炔基可为，例如，乙炔基、丙炔基、丁炔基、丁二炔基、戊炔基、戊二炔基、己炔基等。
本申请中，单体2的R4基团定义中，“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的C 1-10烃基”可为直链或支链的、单取代或多取代的、饱和的或不饱和的。“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素”表示以取代的形式含有这些元素，例如但不限于氟、氯、溴、碘，也可以以其他的形式含有这些元素，例如将这些元素作为基团或结构式主体结构的组成部分，例如但不限于氮、氧、硫、硅、硼、磷，只要化学上能实现即可。作为实例，R4基团可为苯基、乙烯基、丙烯基、烯丙基、吡啶基、嘧啶基等。
本申请中，单体2的R2、R5基团定义中，“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于10的含有C＝C或C≡C的烃基。”也可表示为含有氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的C 2-10烯基或C 2-10炔基，其可为直链或支链的、单取代或多取代的。如上所述，C 2-10烯基可为，例如，乙烯基、丙烯基、丁烯基、丁二烯基、戊烯基、戊二烯基、己烯基等；C 2-10炔基可为，例如，乙炔基、丙炔基、丁炔基、丁二炔基、戊炔基、戊二炔基、己炔基等。“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素”表示以取代的形式含有这些元素，例如但不限于氟、氯、溴、碘，也可以以其他的形式含有这些元素，例如将这些元素作为基团或结构式主体结构的组成部分，例如但不限于氮、氧、硫、硅、硼、磷，只要化学上能实现即可。作为实例，R2、R5可为氢、乙烯基、丙烯基、烯丙基等。
本申请中，单体3的Rf基团定义中，“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于16的乙氧基链段”表示其具有1～8个乙氧基的链段，并且含有氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素。“含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素”表示以取代的形式含有这些元素，例如但不限于氟、氯、溴、碘，也可以以其他的形式含有这些元素，例如将这些元素作为基团或结构式主体结构的组成部分，例如但不限于氮、氧、硫、硅、硼、磷，只要化学上能实现即可。所述1～8个乙氧基的链段也可被支链的或直链的C 1-10烷基或卤代烷基取代。作为实例，含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于16的乙氧基链段，可以为与环三磷腈相连的乙氧基链段，也可以为被氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素取代的乙氧基链段。
本申请中，A +定义中“以氮、硫、磷为阳离子中心的官能团”表示该官能团含有氮、硫或磷，且所述氮、硫或磷为阳离子中心。可选地，A +为含氮基阳离子的官能团，更可选地，其选自铵阳离子、咪唑鎓阳离子和吡啶鎓阳离子，最可选地，A +为-N(R’) 2 +-、
Figure PCTCN2022091467-appb-000007
其中R’各自独立地选自氢或C 1-10烷基。
本申请中，Q -定义为一个、两个或多个选自卤离子、卤代硼酸根、卤代草酸硼酸根、高卤酸根、卤代磷酸根、卤代磺酰亚胺根的阴离子，阴离子的数量取决于A +中阳离子的数量，例如，在A +基团带两个正电荷的情况下，Q -可以为两个带单电荷的阴离子。A +、Q -中的离子的数量不作具体限定，只要化学上能够实现即可。
本申请中，所述卤离子可为氟离子、氯离子、溴离子、碘离子。所述卤代可为氟代、氯代、溴代、碘代，可选为氟代，所述卤代可为单取代、二取代或多取代。所述高卤酸根可为高氟酸根、高氯酸根、高溴酸根、高碘酸根。
本申请提供的聚合物由三种单体(单体1、单体2、单体3)聚合形成，其以乙基为主链，分子结构中含有离子基团(来自单体1)、酰胺(来自单体1)、磷酸酯(来自单体2)和氟化乙氧基(来自单体3)等功能性基团。这些功能性基团各自为所述聚合物提供了不同的作用。现认为，例如，所述离子基团与氟元素(主要来自单体3)的存在有利于提升材料的抗氧化性或高压稳定性(尤其是5V以上的高压)。在将所述聚合物作为电解质膜材料用于二次电池时，聚合物中的柔性乙氧基侧链可以带动锂离子迁移，离子基团中的阳离子中心可与锂盐中的阴离子作用从而提高锂离子迁移数；来自单体2的磷酸酯基团及氟元素(主要来自单体3)的协同效应，使得包含所述聚合物的电解质表现出极好的阻燃特性，其应用于锂二次电池，能够提高电池的安全性；来自单体1的酰胺使得聚合物分子间具有较强的氢键缔合力，所述较强的氢键缔合力的存在以及以磷酸酯(来自单体2)为中心的交联网络的构建有利于增强聚合物材料的机械性能。
本申请所述聚合物可为无规三嵌段聚合物。在一些实施方式中，本申请所述的聚合物具有以下结构式：
Figure PCTCN2022091467-appb-000008
其中，R1、R2、R3、R4、Rf、E、A +、Q -、x如上所定义，且
n、m、p为重复单元的数量，其中0<n≤5000，0<m≤1000，0<p≤5000，且
n与m的比值n：m在1:1～25:1范围内，p与m的比值p:m在1:1～25:1范围内，
波浪号代表一个式4的聚合物分子与另一个式4的聚合物分子的交联位点。
可选地，所述聚合物具有三嵌段结构。所述聚合物的三嵌段的结构可以阻隔乙氧基侧链间的接触，降低聚合物材料结晶度，将其用于电解质膜，可以提升离子电导率。
在一些实施方式中，Rf基团中，氟元素取代率大于29.0％，所述氟元素取代率为氟原子的数目占比，基于Rf基团中可被取代的氢原子数目计。
所述“可被取代的氢原子的数目”应理解为在Rf基团中，可被取代的位点的数目，也即，可与该基团中存在的碳原子、可能存在的磷原子、可能存在的氮原子、可能存在的硫原子相连的氢原子的最大数目，如果所述氢原子已经被其他元素取代，例如卤素原子，则可被取代的氢原子数目计为氢原子数目和取代的其他原子数目之和。
氟元素取代率大于或等于29.0％能够确保聚合物的阻燃性能并且改善使用聚合物得到的电池的高压稳定性和高压循环性。
在一些实施方式中，在所述的聚合物中，阳离子A +选自(4)～(6)结构式中的一种：
Figure PCTCN2022091467-appb-000009
在一些实施方式中，在所述的聚合物中，单体1所占摩尔比范围为3.7～92.6摩尔％，单体2所占摩尔比范围为2.0～33.3摩尔％，单体3所占摩尔比范围为3.7～92.6摩尔％，全部基于单体1、单体2、单体3的总摩尔数计，
可选地，单体1与单体2的摩尔比在1:1～25:1范围内；
更可选地，单体3与单体2的摩尔比在1:1～25:1范围内。
在一些实施方式中，所述聚合物的导热系数在0.06～0.35W/m K范围内，阻燃级别为94V-0或94V-1。
所述聚合物的及电解质膜的导热系数可根据GB T 10294-2008来测定。
所述聚合物的及电解质膜的阻燃级别可根据ASTM D3801的UL94垂直燃烧试验来判定。
本申请第二方面提供制备本申请第一方面所述的聚合物的方法，包括以下步骤：将所述单体1、所述单体2、所述单体3和引发剂溶于溶剂中，在30～100℃下在真空中反应0.2～24h、可选6～24h，然后干燥。所述聚合物以嵌段共聚的形式进行。可选地，所述干燥在25～140℃下在真空中进行1～48h。干燥的主要目的是去除反应后存留的溶剂。
本申请第三方面提供一种聚合物电解质膜，其包括本申请第一方面所述的聚合物或由本申请第二方面所述的方法制备的聚合物。
在一些实施方式中，所述聚合物电解质膜还包括第二聚合物，所述第二聚合物分散于聚合物中，形成互穿网络结构，所述第二聚合物由单体4形成，单体4的通式结构如下：
Figure PCTCN2022091467-appb-000010
其中，
R7选自氢、或未被取代的或被氟、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素取代的碳原子数小于7的烃基。
如上所述，“碳原子数小于7的烃基”包括，但不限于：碳原子数小于7的烷基，例如，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、异丙基、异丁基、叔丁基、异戊基、叔戊基、新戊基、2-甲基戊基、3-甲基戊基、2,2-二甲基丁基、2,3-二甲基丁基等；碳原子数小于7的烯基，例如，乙烯、丙烯、丁烯、丁二烯、戊烯、戊二烯、己烯、己二烯等；和碳原子数小于7的炔基，例如，乙炔、丙炔、丁 炔、戊炔、己炔等。碳原子数小于7的烃基可以是未取代的，也可以被氟、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素单取代或多取代。
本申请中，第二聚合物是相对于前述聚合物而言的，目的是为了与前述聚合物区分开。
本申请所述的聚合物可以与其他聚合物、可选地具有流动性的聚合物形成互穿网络结构，得到具有更高机械强度的高聚物。可选地，将上述第二聚合物均匀分散于所述聚合物中形成互穿网络结构。所述聚合物与第二聚合物的互穿网络示意图参见图1。
所述互穿网络结构是一种特殊的共混物，也可称为互穿网络高聚物(interpenetrating polymer network，简称IPN)。
在包括由聚合物网络和第二聚合物网络形成的互穿网络结构的固态电解质膜中，由于聚合物网络中离子基团和氟元素的存在，可有效提升电解质膜的高压稳定系，并且使得该电解质膜表现出较宽的电化学窗口，因而适合高压电池体系，例如，能够在NCM811/Li电池中展现出很好的循环稳定性；此外，由于聚合物网络中磷酸酯基团及氟元素的协同效应，使得该聚合物电解质膜表现出极好的阻燃特性，提高了锂金属电池的安全性；另外，聚合物网络中柔性乙氧基链段可带动锂离子迁移，以氮、磷、硫为阳离子中心的离子基团可通过与锂盐中的阴离子作用，限制其运动，进而提高锂离子迁移数；聚合物网络中的酰胺分子间较量的氢键缔合力以及以磷酸酯为中心的交联网络的构建有利于增强材料的机械性能；同时，聚合物的三嵌段的结构还可以组个乙氧基侧链碱的接触，降低材料的结晶度，提升电解质膜的离子电导率。
应理解，前述对聚合物的描述，也适用于互穿网络或电解质膜中的聚合物。
本申请所述的第二聚合物为寡聚物，其以碳酸酯为主链，数均分子量M n<2000Da，粘度小于3000cP，具有一定的流动性。所述第二聚合物也可称为碳酸酯聚合物。该寡聚物作为第二聚合物网络均匀 分散于聚合物网络中，即上述无规三嵌段聚合物中，第二聚合物网络中碳酸酯主链的存在，为所形成的电解质膜的高压稳定性提供了保障，为含有所述电解质膜的二次电池的优异的耐高压性能作出了贡献。所述互穿网络结构中的第二聚合物具有一定的流动性，可以起到润湿极片的作用，从而改善电解质膜和正负极之间的界面接触。因此，在包括由聚合物形成的网络和第二聚合物形成的网络的互穿网络的固态电解质膜中，具有流动性的第二聚合物网络的引入，不仅提高了电解质膜与电极间的润湿性能，改善了电解质膜与正负极之间的界面接触，同时由于碳酸酯的链段运动能够带动锂离子的迁移，也保证了该电解质膜较高的离子电导率。
在一些可选实施方式中，本申请所述的含有上述互穿网络结构的电解质膜适合高压电池体系，例如5V的高压电池体系。高压电池体系列包括，但不限于，LiNi 0.8Co 0.1Mn 0.1O 2、LiCoO 2、LiMn 2O 4、LiNiCoAlO 2、LiNi 0.5Mn 1.5O 4等电池体系。
可选地，所述互穿网络结构中，所述聚合物和所述第二聚合物的质量比为20:1～2:1。
在一些实施方式中，所述聚合物电解质膜还包括锂盐，所述锂盐选自六氟磷酸锂(LiPF 6)、四氟硼酸锂(LiBF 4)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、二氟草酸硼酸锂(LiDFOB)、高氯酸锂(LiClO 4)、双乙二酸硼酸锂(LiBOB)中的一种或多种。
锂盐的种类影响所制备的聚合物电解质膜的锂离子迁移数。不同锂盐因结构不同，阴阳离子间的离解度也存在差异，离解度高的锂盐可提供更多的载流子，Li +的浓度会影响它与高分子链中醚氧原子、羰基间的“配位-解离”过程，进而影响充放电过程中Li +及阴离子在电池中的迁移能力。通常PEO基电解质因醚氧原子与Li +间的多齿配位螯合作用，以及与TFSI –阴离子相对弱的溶剂作用使得转移数小于0.2。
在一些实施方式中，所述聚合物电解质膜中锂盐的质量占比在6.8～30.0％范围内，基于聚合物电解质膜总质量计。
可选地，所述聚合物电解质膜中，所述互穿网络结构与锂盐的质量比，也可表示为所述聚合物和所述第二聚合物的质量总和与锂盐的质量比或者单体1～4的质量总和与锂盐的质量比，即，为2.3～13.6。
在一些实施方式中，所述聚合物电解质膜中氟元素含量占比在12.5～46.0％范围内，基于聚合物电解质膜的总重量计。
为确保使用聚合物制备的电解质膜的耐高压和阻燃的双重特性，在聚合物的Rf基团中，氟元素的取代最佳地可保持占比大于等于29.0％。而在采用聚合物制备的聚合物电解质膜中，最后将氟元素的含量占比控制在上述范围内，这样更有利于实现电解质膜的耐高压和阻燃性能。
本申请的第三方面提供一种制备聚合物电解质膜的方法，包括以下步骤：
使本申请前述的单体1、单体2、单体3和本申请前述的单体4、本申请前述的锂盐、任选地催化剂、引发剂在30～100℃下反应0.2～24h，得到产物1。现认为，该步骤中，单体1、单体2、单体3在引发剂的存在下发生共嵌段聚反应形成所述聚合物，单体4在锂盐和任选地催化剂的存在下发生离子共聚反应形成流动态的第二聚合物。
引发剂用于引发单体1、单体2、单体3之间的嵌段共聚反应以形成本申请所述的聚合物。所述引发剂包括，但不限于，偶氮类或过氧类分子，如2,2’-偶氮双(2,4-二甲基戊腈)、2,2’-偶氮双(异丁基腈)、2,2’-偶氮双(甲基丁酸腈)、1,1’-偶氮双(氰基环己烷)、过氧化二苯甲酰、过氧化十二酰、过氧化二叔丁基、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯。
可选地，所述引发剂的质量不超过两种聚合物单体和锂盐总质量(即，单体1、单体2、单体3、单体4和锂盐质量之和)的5％。
所述锂盐如前文所述。锂盐可用于催化单体4的离子聚合反应以形成流动态的第二聚合物。
在一些情况下，仅使用锂盐催化单体4的离子聚合反应是不够的，还需使用催化剂。可使用的催化剂包括，但不限于，异辛酸亚锡、三 氟甲基磺酸铝、三氯化铝、三氟甲磺酸三甲基硅酯、三氟化硼乙醚、三乙胺、1,8-二氮杂二环[5.4.0]十一碳-7-烯。所述催化剂催化第二聚合物的聚合。本申请中，所述第二聚合物通过离子聚合的形式获得。
可选地，在制备聚合物电解质膜的方法中，使所述的单体1、单体2、单体3和所述的单体4、所述的锂盐、催化剂、引发剂溶于溶剂中，通过搅拌或其他手段，得到均匀溶液。
可选地，将所述均匀溶液倒入本领域中常规使用的工具(例如聚四氟乙烯模具)中，加热至30～100℃并在真空下反应0.2～24h，可选地，所述反应在真空烘箱中进行。
在一些实施方式中，在制备聚合物电解质膜的方法中，还包括使所得到产物1与锂盐的溶液进行阴离子交换得到产物2的步骤。
如前所述，单体1中存在Q -阴离子，有些阴离子(例如氯离子)可能对电芯体系不利，例如可能会产生腐蚀作用，因此，需要进行阴离子交换。阴离子交换后可将形成的所述聚合物中的离子基团自带的阴离子Q -，如可腐蚀铝箔的Cl -，替换成目标阴离子，可选地，替换成与锂盐中阴离子种类相同的阴离子。这样，一方面可防止一些副反应的发生，另一方面也可调节阴离子与所述聚合物、锂离子间的结合能力。
一般而言，用于进行阴离子交换的锂盐溶液中阴离子的浓度需要远高于所述聚合物中Q -的浓度。Q -的浓度的确定可采用本领域常规技术手段进行，例如，在Cl -的情况下，可用硝酸银进行滴定，滴定在中性溶液中进行，以铬酸钾为指示剂，通过消耗硝酸银溶液的体积即可计算氯离子浓度。
所述锂盐溶液为单独配制的溶液，所述锂盐溶液中的锂盐与电解质膜中的锂盐相同或不同，相同时是更有利的。可选地，阴离子交换进行1～20h，此时间不是限制性的，可视实际情况而进行调整。
在阴离子交换中，所使用的锂盐溶液中的溶剂可为，例如，但不限于，丙酮、乙腈、乙二醇二甲醚、碳酸二甲酯、碳酸甲乙酯、碳酸乙烯酯。
在一些实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，还包括干燥所得到的产物2。
干燥的目的在于去除残留的溶剂。可采用本领域中常规使用的任何手段进行干燥，只要达到去除溶剂的目的且不会使电解质膜降解即可。可使用真空干燥箱进行干燥。
可选地，所述干燥的温度不超过140℃且在140℃下的干燥时间不超过1h。
可选地，所述电解质膜的热收缩温度在140～160℃左右。
在一些实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述单体1、单体2、单体3的质量总和与单体4的质量之比为20:1～2:1。
在一些实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述单体1、单体2、单体3、单体4的质量总和与所述锂盐的质量比在2.3～13.6的范围内。
在一些实施方式中，在根据本申请所述的制备聚合物电解质膜的方法中，所述锂盐与所述引发剂的重量比为5:1～60:1；如果使用催化剂，所述锂盐和催化剂重量之和与引发剂重量之间的比例为7:1～80:1。
引发剂可用于引发本申请所述的聚合物的嵌段共聚反应，锂盐和催化剂可用于引发第二聚合物的离子聚合反应，二者的比例在一定意义上能够反应出所制备的两种聚合物的分布和互穿网络的结构组成。
根据本申请，在本申请聚合物和电解质膜的制备中，所使用的溶剂可为乙腈或本领域常规使用的其他溶剂，如丙酮、1,4-二氧六环、N-甲基吡咯烷酮、二甲基亚砜、碳酸甲乙酯、碳酸二甲酯、碳酸乙烯酯、乙二醇二甲醚等。
现认为，本申请所述的聚合物采用嵌段共聚，通过引发剂引发而制备。第二聚合物采用离子聚合通过锂盐和任选地催化剂催化而制备。虽然两种聚合物各自单体混合在一起，但是各自进行各自的制备，不会互相干扰。并且，由于在进行聚合反应之前将各个单体、引发剂、任选地催化剂在溶液中混合均匀，因此，完全聚合后得到的是聚合物 网络和第二聚合物网络均匀互穿的互穿网络结构，并且锂盐在其中均匀分散。
应理解，此处电解质膜的制备中关于溶剂、引发剂等方法参数条件的描述也适用于前述聚合物的制备方法。
可选地，在一些实施方式中，本申请提供由上述制备固态聚合物电解质膜的方法制备的固态电解质膜。
本申请第五方面提供一种二次电池，包括正极、负极，其中，还包括本申请第三方面所述的聚合物电解质膜或由本申请第四方面所述的方法制备的聚合物电解质膜。下文对本申请的二次电池、电池模块、电池包和用电装置进行说明。
二次电池
本申请所述二次电池包括正极极片、负极极片和本申请所述的聚合物电解质膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。聚合物电解质膜在正极极片和负极极片之间起到传导离子的作用。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括本申请第一方面的正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
可选地，正极活性材料包括锂钴氧化物(LiCoO 2)、锂锰氧化物(LiMnO 2、LiMn 2O 4等)、锂镍钴锰氧化物(LiNi 0.8Co 0.1Mn 0.1O 2或LiNi 0.6Co 0.2Mn 0.2O 2)等。
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，所述正极包括正极集流体和正极膜层，所述正极膜层包括正极活性物质、上述第二聚合物和上述锂盐。可选地，所述第二聚合物在正极膜层中的质量占比为2～15％，可选地，所述锂盐在正极膜层中的质量占比为0.5～10％。
正极膜层中的锂盐可与电解质中的锂盐种类相同，也可不同。前述针对电解质膜中的锂盐的描述也适合于正极膜层中的锂盐。
在一些可选实施方式中，可通过以下方式制备正极极片，将正极活性物质、导电剂(例如，Super-p)、上述用于制备第二聚合物的单体4以及任意其他组分分散于溶剂(例如N-甲基吡咯烷酮，简称NMP)中，然后加入上述锂盐和任选地催化剂，混合后形成均匀的正极浆料；将正极浆料涂覆在正极集流体上，经干燥等工序后，得到正极极片。可选地，所述干燥可在30～100℃的烘箱中进行。可选地，在该制备中，所述正极活性物质占比为80％～95％，所述导电剂占比为1～5％，所述单体4占比为2～15％，所述锂盐占比为0.5～10％，均基于正极活性物质、导电剂、单体4和任意其他组分的总重量计。
可选地，正极膜片中的锂盐、电解质膜中的锂盐以及任选进行的阴离子交换操作中的锂盐为相同种类的锂盐。
在正极膜片中使用第二聚合物具有以下优势：正极膜片内部孔隙由流动态的第二聚合物和锂盐填充，流动态的第二聚合物不仅起到润湿极片内部的作用，同时其链段的运动还提供了锂离子在极片内部传输的通道，从而增强了正极膜片内部的离子传输。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集 流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，在所述的二次电池中，所述负极包括负极集流体和由锂金属或锂合金形成的金属片。
所述负极集流体可为铜箔，但不限于连续的铜箔，也可以是铜丝编织型铜网、泡沫铜或三维纳米多孔铜。
本申请所述的聚合物电解质膜适合与具有高比容量(3860mAh/g)、极低电位(-3.04V vs.H 2/H +)的锂金属负极、锂合金负极，或无负极搭配使用。可选地，负极极片厚度为9～50μm。
所述锂合金包括，但不限于，锂铝合金、锂镁合金、锂硼合金等。应理解，本申请所述的锂合金不限于锂铝合金、锂镁合金或锂硼合金这三种，其他能够实现上述目的的锂合金也是可以的。
在一些实施例中，负极极片可商购获得，也可通过将锂金属和/或锂合金通过冷压的方式直接覆在集流体上。
[聚合物电解质膜]
电解质在正极极片和负极极片之间起到传导离子的作用。特别地，所述二次电池使用本申请所述的固态聚合物电解质膜，其能够很好地传导锂离子并且具有很高的安全性能。
在一些实施方式中，在所述的二次电池中，所述聚合物电解质膜的厚度为10～1000μm。
将所述正极极片、所述固态聚合物电解质膜、所述负极极片按顺序叠放，组装成电池。
[外包装]
在一些实施方式中，二次电池可以包括外包装，其用于封装正极极片、负极极片和电解质。作为一个示例，正极极片、固态聚合物电解质膜、负极极片可经叠片形成叠片结构电芯或经卷绕工艺形成卷绕 结构电芯，电芯封装在外包装内。二次电池中电芯的数量可以为一个或几个，可以根据需求来调节。
在一个实施方式中，本申请提供一种电极组件。在一些实施方式中，正极极片、固态电解质膜、负极极片可通过叠片工艺或卷绕工艺制成电极组件。所述外包装可用于封装上述电极组件及固态电解质膜。
在一些实施方式中，二次电池的外包装可以是软包，例如袋式软包。软包的材质可以是塑料，如可包括聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)、聚丁二酸丁二醇酯(PBS)等中的一种或几种。在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。
二次电池的制备方法
在一个实施方式中，本申请提供一种二次电池的制备方法，其中，使用本申请所述的聚合物电解质膜或根据本申请所述的方法制备的聚合物电解质膜。
二次电池的制备还可以包括将本申请的负极极片、正极极片和电解质组装形成二次电池的步骤。在一些实施方式中，可将正极极片、聚合物电解质膜、负极极片按顺序叠放，冷压组装成全电池。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图3是作为一个示例的方形结构的二次电池5。
在一些实施方式中，参照图4，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
本申请的第六方面提供一种电池模块，其中，包括本申请第五方面所述的二次电池。
本申请的第七方面提供一种电池包，其中，包括本申请第六方面所述的电池模块。
本申请的第八方面提供一种用电装置，其中，包括选自本申请第五方面所述的二次电池、本申请第六方面所述的电池模块或本申请第七方面所述的电池包中的至少一种。
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图5是作为一个示例的电池模块4。参照图5，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图6和图7是作为一个示例的电池包1。参照图6和图7，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图8是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
下面是用于说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
下面实施例中，N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵、磷酸三烯丙酯、全氟聚醚丙烯酸酯(PFPE-MAA-1000)、氟代碳酸乙烯酯分别采购自阿拉丁试剂、Monomer-Polymer&Dajac Labs、苏州仓慕、阿拉丁试剂。
I.聚合物、第二聚合物、电解质膜、二次电池的制备
I-1.聚合物的制备
在25℃下，在氮气气氛下，将1.103g的N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵、0.218g的磷酸三烯丙酯、5.465g的全氟聚醚丙烯酸酯(PFPE-MAA-1000)和0.063g的偶氮二异丁腈(AIBN)加入20mL乙腈中，通过磁力搅拌混合均匀，加热至65℃，反应10h后，再置于45℃真空烘箱中干燥6h，即可制聚合物。
I-2.第二聚合物的制备
第二聚合物使用氟代碳酸乙烯酯进行离子聚合，过程如下：
在65℃的温度下，将1.4g的氟代碳酸乙烯酯、0.014g的异辛酸亚锡酯和1.871g的双氟磺酰亚胺锂均匀混合，反应10h后，可得具 有流动性的第二聚合物。所述第二聚合物的数均分子量为2000。分子量测试方法如下：
将上述聚合物溶解在N-甲基吡咯烷酮(NMP)中，通过凝胶渗透色谱法(GPC)，使溶解的分子经过含有微孔填料的色谱柱，依据其大小进行分离。当样品被分离并从色谱柱洗脱时，可通过一系列检测器(普适校正及三重检测)进行表征。
I-3聚合物电解质膜的制备
在25℃下，将1.103g的N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵(单体1)、0.218g的磷酸三烯丙酯(单体2)、5.465g的全氟聚醚丙烯酸酯(PFPE-MAA-1000)(单体3)、0.063g的偶氮二异丁腈(AIBN)(引发剂)、1.4g的氟代碳酸乙烯酯(单体4)、0.014g的异辛酸亚锡酯(催化剂)和1.871g的双氟磺酰亚胺锂(锂盐)加入20mL乙腈中并混合均匀。将该均匀溶液倒入具有固定深度的聚四氟乙烯模具中，在65℃真空烘箱中保持10h，随后将该电解质膜浸泡在50mL的3M LiFSI的丙酮溶液中进行阴离子交换12h，再经45℃真空烘箱干燥6h，即可制得厚度为15μm的聚合物固态电解质膜。
制备的电解质膜尺寸：100mm×100mm×15μm
I-4.电池的制备
步骤1：正极极片的制备
将4.5g钴酸锂(LiCoO 2)、0.05g导电剂Super-p和0.275g氟代碳酸乙烯酯加入到2ml N-甲基吡咯烷酮(NMP)中充分混合，然后将1.2ml的二氟草酸硼酸锂(LiDFOB)和异辛酸亚锡的NMP溶液(质量浓度分别为12.5％和2.1％)加入到上述浆料中，快速混合均匀，得到正极浆料，将该浆料涂附在13μm铝箔上并于50–80℃鼓风烘箱中干燥，即可制得正极极片。
步骤2：负极极片的准备
负极极片：将锂金属(购自深圳市科晶智达科技有限公司，规格为30μm厚)冷压覆在铜箔上，得到负极极片。
步骤3：聚合物电解质膜的制备
电解质膜的制备参见I-3。
步骤4：全电池的制备
将上述含第二聚合物的正极极片，聚合物固态电解质膜，锂金属或锂合金负极片，按顺序叠放，冷压组装成全电池，并进行后续充放电及循环测试。
I-5.对比聚合物和对比固态电解质膜
采用购自阿拉丁试剂的平均分子量Mv～1,000,000的PEO作为对比，将其制成电解质膜，制备方法如下：
将2gPEO粉末和0.3g双氟磺酰亚胺锂(LiFSI)溶解在35g乙腈中，搅拌至完全溶解，然后加入0.7g TiO 2粉末(10-20nm)，搅拌30min，并超声分散，将分散好的浆料倒入自制模具中，置于60℃真空烘箱中干燥12h，干燥后即可得PEO电解质膜。
电解质膜尺寸：100mm×100mm×15μm
II.聚合物、电解质膜、电池的性能考察
II-1.溶胀参数
采用以下方法测试I-1中制备的聚合物和I-2中制备的第二聚合物及I-3中制备的聚合物电解质膜的溶胀参数：
将I-1中制备的聚合物、I-2中制备的第二聚合物及I-3中制备的电解质膜分别裁成30mm×30mm的正方形样品，在每种情况下每组三个平行样品，并称量每个样品质量。然后，将样品放入1M LiFSI的碳酸甲乙酯(EMC)溶液中浸泡12h进行溶胀。溶胀后先用滤纸轻轻将溶胀样品表面附着的多余溶剂吸干，然后测出溶胀后样品的质量。溶胀参数为溶胀后样品的质量增量占原样品质量的百分比。
表1：溶胀参数测试结果
考察项目 本申请聚合物 第二聚合物 电解质膜
溶胀参数 29％ 12％ 24％
上表结果表明，电解质膜的溶胀参数在聚合物和第二聚合物之间，可在一定程度上表明电解质膜为聚合物和第二聚合物的共混物。
II-2.阻燃性能
以聚氧化乙烯(PEO)作为对比，考察聚合物的阻燃性能。
I-1中制备的聚合物、I-3中制备的电解质膜、I-5中的对比聚合物PEO及采用PEO制备的对比电解质膜的导热系数根据GB T 10294-2008来测定。
I-1中制备的聚合物、I-3中制备的电解质膜、I-5中的对比聚合物PEO及采用PEO制备的对比电解质膜的阻燃性能根据ASTM D3801的UL94垂直燃烧试验来判定。
性能测试结果如下表所示。
表2：聚合物阻燃性能
测试物质 导热系数(W m -1K -1) 阻燃性能
I-1中制备的聚合物 0.25 UL94 V-0，无滴落
I-5中的对比聚合物PEO 40 1s内燃烧，滴落
I-3中制备的电解质膜 0.31 UL94 V-0，无滴落
I-5中制备的对比电解质膜(PEO) 42 3s内燃烧，滴落
上表结果表明，与对比的PEO和对比的电解质膜相比，本申请提供的聚合物及采用聚合物制备的电解质膜具有极好的阻燃性能。
II-3.单体1、单体2对电解质膜及电池的性能影响
实施例1-9
采用实施例1-9来考察单体1、单体2对电解质膜的机械性能以及对电池的高压稳定性和高压循环性能的影响。具体操作如下：
实施例1：根据I-3和I-4制备全电池。
实施例2-9：类似于实施例1制备，不同之处仅在于改变单体1～3的摩尔占比(基于单体1～3总摩尔量计)，具体单体使用量和摩尔比参加下表。
对实施例1-9中制备的电解质膜和全电池的性能进行测试，测试方法如下：
(1)电解质膜的拉伸强度和伸长率测试
将实施例1-9中的电解质膜裁成尺寸为150mm×20mm、15μm厚的长方形电解质膜试样，采用通用测试机参照标准ASTM D882-10以50mm/min十字头速度将上述试样分别从松弛状态进行拉伸至失 效，记录试样最大拉伸应力断裂时的拉伸强度和长度L，根据(L-L 0)/L 0×100％计算断裂伸长率。
(2)电池的高压稳定性能测试
通过线性扫描伏安法以5.0mV s -1的速度在2～6V范围内对各全电池进行将线性电位扫描，记录电流的变化。将电解质膜夹在不锈钢片和金属锂片之间，组装成扣式电池，其中不锈钢片作为工作电极、金属锂片作为参比电极，通过电化学工作站以1.0mV/s的扫描速率在2～6V范围内对其进行将线性电位扫描，电压从开路设置到6.0V。记录电解质膜发生氧化分解时的起始电压，该电压越高，稳定性越好。
对实施例1的电池进行测试中得到的曲线图参见图2。
(3)电池的高压循环性能测试
以0.5C～0.5C的充放电倍率在2.8～4.3V的电压范围内对实施例中的全电池进行恒流充放电测试，测试各全电池在高电压上限充电过程中电量剩余80％时循环的圈数(cls)，记录该圈数的数值，圈数越多，高压循环稳定性越好。
测试结果参见下表。
Figure PCTCN2022091467-appb-000011
当单体2摩尔比低时，例如实施例8和实施例6，所获得的电解质膜的拉伸强度显著较低，当单体2的摩尔比过低的时候，例如实施例8，高压循环性能显著下降。当单体2的摩尔比高时，例如实施例7和9，所获得的电解质的伸长率较差，当单体2的摩尔比过高时，例如实施例9，采用其电解质膜制得的电池的高压稳定性差且高压循环性能显著下降。因此，对于单体2，优选其摩尔比可为2.0～33.3％，优选可为5％～25％。
综上，可以看出，单体1的摩尔比、单体2的摩尔比对相应得到的电解质膜的机械强度(拉伸强度和伸长率)影响较大，对各自相应得到的电池的高压稳定性和高压循环性能也有明显影响。
II-4.单体1中的阳离子和锂盐对电解质膜的锂离子迁移数的影 响
实施例1、10～11
实施例1、10～11考察单体1中的阳离子种类和锂盐种类对锂离子迁移数的影响。
实施例1：如上所述，根据I-3和I-4制备全电池。
实施例10：类似于实施例1制备电解质膜和全电池，不同之处在于I-3中电解质膜的制备中单体1使用下表中的单体而不是使用N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵，锂盐使用LiBOB而不是使用LiFSI。
实施例11：类似于实施例1制备电解质膜和全电池，不同之处在于I-3中电解质膜的制备中单体1使用下表中的单体而不是使用N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵，锂盐使用LiBF 4而不是使用LiFSI。
对比例1：类似于实施例1制备电解质膜和全电池，不同之处在于I-3中电解质膜的制备中单体1使用下表中的单体而不是使用N,N,N-三甲基-3-(2-甲基烯丙酰氨基)-1-氯化丙铵。
对各实施例和对比例中制备的电解质膜的锂离子迁移数进行测试，测试方法如下：
通过恒电位极化法测定聚合物固态电解质中的锂离子迁移数。锂离子迁移数t +的测试方式如下：
组装Li/聚合物固态电解质/Li对称电池，对所测对称电池施加小而恒定的电势差ΔV(10mV左右)，同时记录电流随时间的变化。初始状态下，电池系统中所有可迁移的离子均对电荷传输有影响，此时电流最大，记录为I 0(初始电流)。随着极化的进行，在电池内部逐渐形成稳定的离子浓度梯度，阴离子迁移被抑制，电池体系的电流由阳离子(即锂离子)贡献，记录此时的电流I s(稳态电流)。通过式1即可计算锂离子迁移数t +，
式1：
Figure PCTCN2022091467-appb-000012
其中R 0 el和R s el分别为极化前后电极与聚合物电解质膜的界面阻抗，界面阻抗可通过电化学阻抗谱(Electrochemical Impedance Spectroscopy，简称EIS，也叫交流阻抗谱)得到：给电池系统施加一个频率w1的小振幅的正弦波电压信号，系统产生一个频率为w2的正弦波交流响应，施加电压与产生电流的比值即为系统的阻抗，该值随正弦波频率ω变化的复数平面图为Nyquist图，高频区的半圆形部分对应电荷转移过程，半圆直径表示界面阻抗。
表4
Figure PCTCN2022091467-appb-000013
上表结果表明，与不含阳离子的对比例1相比，使用含阳离子的单体1有利于提高聚合物固态电解质的锂离子迁移数，且阳离子周围的电荷密度越高，锂盐的解离能力越强，锂离子迁移数越大。
II-5.单体3对电解质膜和电池性能的影响
实施例12～23
考察单体3中Rf种类、氟元素取代率、基团E种类及单体3的用量对电解质膜和电池性能的影响。
实施例12～15：类似于实施例1制备电解质膜和全电池，不同之处在于不改变单体3的摩尔占比(单体1和2的量根据实施例1中的 摩尔比和表3中的单体3的质量作相应改变)，仅改变单体3的中的Rf基团、E基团。具体参见下表5。
实施例16：单体1、单体2、单体3的用量分别为0.221g、0.218g、9.836g，摩尔占比分别为9.10％、9.10％、81.80％。
实施例17：单体1、单体2、单体3的量分别为1.985g、0.218g、1.094g，摩尔占比分别为81.80％、9.10％、9.10％。
实施例18：单体1、单体2、单体3的量分别为0.049g、0.218g、10.690g，摩尔占比分别为2.0％、9.10％、88.90％。
实施例19：单体1、单体2、单体3的量分别为2.087g、0.218g、0.589g，摩尔占比分别为86.0％、9.10％、4.90％。
对各实施例中制备的电解质膜和全电池进行以下测试：
(1)离子电导率的测试：
将电解质膜片裁成
Figure PCTCN2022091467-appb-000014
的圆片，组装不锈钢片Ⅰ电解质膜Ⅰ不锈钢片的R2032纽扣电池，静置12h后，用电化学工作站做交流阻抗谱(EIS)测试，从0.1-10 5Hz进行频率扫描，电压振幅为5mV；图形与横轴交点即为聚合物膜的阻抗R，离子电导率σ可根据公式
σ＝d/RA
计算得到，其中d为电解质膜的厚度，R为阻抗值，A为电解质膜片的面积。
(2)电解质膜中氟元素含量占比测试：
电解质膜中氟元素的含量根据X射线光电子能谱(XPS)检测得到。
(3)Rf基团中氟元素取代率计算：
氟元素取代率基于Rf基团中可被取代的氢原子数目计，即氟原子个数/(所有卤族原子数+氢原子数)。
(4)单体3的摩尔占比计算：单体3的质量/单体3的分子量为单体3的摩尔数，单体3的摩尔数/(单体1的摩尔数+单体2的摩尔数+单体3的摩尔数)即为单体3的摩尔占比。
电解质膜的锂离子迁移数和电池的高压稳定性、高压循环性的测试参见上文。
Figure PCTCN2022091467-appb-000015
Figure PCTCN2022091467-appb-000016
II-6.第二聚合物的单体和锂盐的量对电解质膜、电池的影响
实施例1、20～27
考察制备第二聚合物的单体4对电解质膜、电池的性能影响。
实施例1：如上所述
实施例24～27：类似于实施例1制备，不同之处在于保持单体1～3的量和锂盐的添加量不变，仅改变单体4的量。
实施例28～31：类似于实施例1制备，不同之处在于保持单体1～4的量不变，仅改变添加的锂盐的量。
表格中，锂盐的质量占比计算为锂盐的质量/(单体1～4+引发剂+锂盐+催化剂)的总质量×100％。
拉伸强度、伸长率、高压稳定性和高压循环性能测试参见上文，测试结果参见下表。
Figure PCTCN2022091467-appb-000017

Claims (24)

  1. 一种聚合物，其由单体1、单体2、单体3聚合而成，其中所述单体1具有式1结构，单体2具有式2结构，单体3具有式3结构，
    Figure PCTCN2022091467-appb-100001
    其中，
    R1、R3各自独立地选自氢或C 1-10烷基；
    R4选自C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的C 1-10烃基；
    R2、R5各自独立地选自氢、C 1-10烃基或者含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于10的含有C＝C或C≡C的烃基；
    Rf选自氢、或含氟、氯、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素的碳原子数小于或等于16的乙氧基链段；
    x为亚甲基的重复单元数，0≤x≤20；
    A +选自以氮、硫、磷为阳离子中心的官能团中的一种；
    Q -为一个、两个或多个选自卤离子、卤代硼酸根、卤代草酸硼酸根、高卤酸根、卤代磷酸根、卤代磺酰亚胺根的阴离子，可选地Q -为一个、两个或多个选自氯离子、四氟硼酸根、二氟草酸硼酸根、高氯酸根、六氟磷酸根、双(氟磺酰)亚胺根的阴离子；
    E选自(1)～(3)的结构，
    Figure PCTCN2022091467-appb-100002
    其中R6选自氢或C 1-10烷基。
  2. 根据权利要求1所述的聚合物，其特征在于，Rf基团中，氟元素取代率大于29.0％，所述氟元素取代率为氟元素的数目占比，基于Rf基团中可被取代的氢原子数目计。
  3. 根据权利要求1或2所述的聚合物，其特征在于，阳离子A +选自(4)～(6)结构式中的一种：
    Figure PCTCN2022091467-appb-100003
  4. 根据权利要求1～3中任一项所述的聚合物，其特征在于，单体1所占摩尔比范围为3.7～92.6摩尔％，单体2所占摩尔比范围为2.0～33.3摩尔％，单体3所占摩尔比范围为3.7～92.6摩尔％，全部基于单体1、单体2、单体3的总摩尔数计，
    可选地，单体1与单体2的摩尔比在1:1～25:1范围内；
    更可选地，单体3与单体2的摩尔比在1:1～25:1范围内。
  5. 根据权利要求1～4中任一项所述的聚合物，其特征在于，所述聚合物的导热系数在0.06～0.35W/m K范围内，阻燃级别为94V-0或94V-1。
  6. 制备权利要求1～5中任一项所述的聚合物的方法，包括以下步骤：将所述单体1、所述单体2、所述单体3和引发剂溶于溶剂中，在30～100℃下在真空中保持0.2～24h，然后干燥。
  7. 一种聚合物电解质膜，其包括权利要求1～5中任一项所述的聚合物或由权利要求6所述的方法制备的聚合物。
  8. 根据权利要求7所述的聚合物电解质膜，其特征在于，其还包括第二聚合物，所述第二聚合物分散于所述聚合物中，形成互穿网络结构，所述第二聚合物由单体4形成，单体4的通式结构如下：
    Figure PCTCN2022091467-appb-100004
    其中，
    R7选自氢、或未被取代的或被氟、溴、碘、氮、氧、硫、硅、硼、磷中的一种或多种元素取代的碳原子数小于7的烃基。
  9. 根据权利要求7或8所述的聚合物电解质膜，其特征在于，其还包括锂盐，所述锂盐选自六氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、二氟草酸硼酸锂、高氯酸锂、双乙二酸硼酸锂中的一种或多种。
  10. 根据权利要求7～9中任一项所述的聚合物电解质膜，其特征在于，锂盐的质量占比在6.8～30.0％范围内，基于聚合物电解质膜总质量计。
  11. 根据权利要求8～10中任一项所述的聚合物电解质膜，其特征在于，氟元素含量占比在12.5～46.0％范围内，基于聚合物电解质膜的总重量计。
  12. 制备聚合物电解质膜的方法，包括：
    使权利要求1～11中任一项所述的单体1、单体2、单体3和权利要求8～11中任一项所述的单体4、权利要求9～11中任一项所述的锂盐、任选地催化剂、引发剂在30-100℃下反应0.2-24h，得到产物1。
  13. 根据权利要求12所述的制备聚合物电解质膜的方法，其特征在于，还包括使所得到产物1与锂盐的溶液进行阴离子交换，得到产物2。
  14. 根据权利要求13所述的制备聚合物电解质膜的方法，其特征在于，还包括干燥所得到的产物2。
  15. 根据权利要求12～14中任一项所述的制备聚合物电解质膜的方法，其特征在于，所述单体1、单体2、单体3的质量总和与所述单体4的质量之比为20:1～2:1。
  16. 根据权利要求12～15中任一项所述的制备聚合物电解质膜的方法，其特征在于，所述单体1、单体2、单体3、单体4的质量总和与所述锂盐的质量比在2.3～13.6的范围内。
  17. 根据权利要求12～16中任一项所述的制备聚合物电解质膜的方法，其特征在于，所述锂盐与所述引发剂的重量比为5:1～60:1；如果使用催化剂，所述锂盐和催化剂重量之和与引发剂重量之间的比例为7:1～80:1。
  18. 一种二次电池，包括正极、负极，其特征在于，还包括权利要求7～11所述的聚合物电解质膜或由权利要求12～17所述的方法制备的聚合物电解质膜。
  19. 根据权利要求18所述的二次电池，其特征在于，所述聚合物电解质膜的厚度为10～1000μm。
  20. 根据权利要求18或19所述的二次电池，其特征在于，所述负极包括负极集流体和由锂金属和/或锂合金形成的金属片。
  21. 根据权利要求18～20中任一项所述的二次电池，其特征在于，所述正极包括正极集流体和正极膜层，所述正极膜层包括正极活性物质、权利要求8～11中任一项所述的第二聚合物和权利要求9～16中任一项所述的锂盐。
  22. 一种电池模块，其特征在于，包括权利要求18～21中任一项所述的二次电池。
  23. 一种电池包，其特征在于，包括权利要求22所述的电池模块。
  24. 一种用电装置，其特征在于，包括选自权利要求18～21中任一项所述的二次电池、权利要求22所述的电池模块或权利要求23所述的电池包中的至少一种。
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