Polymers and methods for preparing them, gel polymer electrolytes, batteries and electrical devices

Abstract

This application discloses a polymer, a method for preparing the same, a gel polymer electrolyte, a battery, and an electrical device. The general formula of the polymer is represented by Formula I. However, m includes 0 and / or 1, n is a positive integer, X1 and X2 each independently include oxygen, sulfur, or an imino group, X3 includes oxygen or sulfur, Y includes oxygen, sulfur, an imino group, -S-C unsubstituted or substituted with any group 1~8 an alkylene group, -NH-C unsubstituted or substituted with any group 1~8 an alkylene group, C unsubstituted or substituted with any group 1~8 an alkylene group, C unsubstituted or substituted with any group 1~8 includes any one of alkyleneoxy groups, and R1, R2, R3, and R4 each independently are hydrogen, fluorine, C unsubstituted or substituted with any group 1~10 an alkyl group, C unsubstituted or substituted with any group 1~10 includes any one of alkoxy groups, and R5 is C unsubstituted or substituted with any group 1~10 an alkyl group, includes any one of Formula (A), and R9 is C unsubstituted or substituted with any group 1~10 includes an alkyl group. 【Chemical Formula 1】 TIFF2026518527000109.tif38170

Description

[Technical Field]

[0001] This application belongs to the field of batteries and specifically relates to polymers and methods for preparing them, gel polymer electrolytes, batteries and electrical devices. [Background technology]

[0002] Lithium-ion batteries are ecological, environmentally friendly, high-energy, and low-carbon, and are not only applied to energy storage systems in hydroelectric, thermal, wind, and solar power plants, but are also widely used in electric vehicles such as electric bicycles, electric motorcycles, and electric cars, as well as in military equipment and aerospace. With the development of modern society, the demand for lithium-ion batteries is increasing more and more. [Overview of the Initiative]

[0003] In light of the technical problems present in the background technology, this application provides a polymer to improve the thermal stability of batteries and reduce the probability of thermal runaway.

[0004] To achieve the above objective, a first aspect of the present invention provides a polymer whose general formula is represented by formula I.

[0005] [ka]

[0006] (wherein m includes 0 and / or 1, n is a positive integer, X1 and X2 each independently include oxygen, sulfur, or an imino group, and X3 includes oxygen or sulfur, Y is oxygen, sulfur, imino group, unsubstituted or any group -SC 1~8 Alkylene group, unsubstituted or any group-substituted -NH-C 1~8 alkylene group, unsubstituted or any substituted C 1~8 alkylene group, unsubstituted or any substituted C 1~8It contains one of the alkylene oxy groups, and R1, R2, R3, and R4 are each independently substituted with hydrogen, fluorine, unsubstituted or any group. 1~10 C is an alkyl group, unsubstituted, or substituted with any group. 1~10 It contains one of the alkoxy groups, and R5 is unsubstituted or substituted with any group. 1~10 alkyl group, [ka] It includes one of the following, and R9 is an unsubstituted or substituted C 1~10 (It contains an alkyl group, and any of the above groups includes at least one of a halogen, alkyl group, alkoxy group, ester group, or carbonyl group.)

[0007] Compared to the prior art, the polymer according to the first embodiment of the present application can have the following beneficial effects. The polymer has flame retardant properties, and when used in a battery (for example, a polymerizable monomer containing a double bond-containing cyclic phosphate ester compound can be introduced into an electrolyte and polymerized under the action of an initiator to obtain a polymer network), the polymer undergoes ring-opening polymerization in the event of abuse such as high temperature or overcharging of the battery, causing the electrolyte to gel, increasing the internal resistance of the battery, and reducing the probability of thermal runaway of the battery. Furthermore, the desired effects can be further satisfied by substituents on the polymer, for example, by halogen substitution, the flame retardant effect can be improved or side reactions of the battery can be reduced. In short, introducing the polymer into a battery is advantageous in improving the thermal stability of the battery and reducing the probability of battery ignition and thermal runaway.

[0008] A second aspect of the present application provides a method for preparing a polymer according to the first aspect of the present application, comprising self-polymerizing a double-bond-containing cyclic phosphate ester compound and / or copolymerizing a double-bond-containing cyclic phosphate ester compound with a second polymerizable compound. Compared to the prior art, this method not only allows for the production of polymers having a cyclic phosphate ester structure, but also allows for the selection of specific types or structures of polymerizable monomers and / or second polymerizable compounds according to actual needs to satisfy different additional needs. When used in the field of batteries, it can improve the thermal stability of batteries and reduce the probability of battery ignition and thermal runaway.

[0009] A third aspect of the present application provides a gel polymer electrolyte comprising a polymer matrix and an electrolyte, wherein the polymer matrix comprises a polymer according to the first aspect of the present application or a polymer obtained by the method according to the second aspect of the present application.

[0010] A fourth aspect of this application provides a battery comprising a gel polymer electrolyte according to the third aspect of this application, and / or a polymer obtained by the method according to the second aspect of this application, and / or a polymer according to the first aspect of this application.

[0011] A fifth aspect of the present application is provided, which includes an electrical device including a battery according to the fourth aspect of the present application.

[0012] The additional aspects and advantages of this application are partially described below, partially evident from the following description, or understood through the practice of this application. [Brief explanation of the drawing]

[0013] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments linked to the following drawings.

[0014] [Figure 1] This is a schematic diagram of the structure of a battery according to one embodiment of the present invention. [Figure 2]This is a schematic diagram of the structure of a battery module according to one embodiment of the present invention. [Figure 3] This is a schematic diagram of the structure of a battery pack according to one embodiment of the present invention. [Figure 4] This is an exploded view of a battery pack according to one embodiment of the present invention. [Figure 5] This is a schematic diagram of one embodiment of an electrical device using a battery as a power source according to one embodiment of the present invention. [Explanation of symbols]

[0015] 1…Secondary battery 2…Battery module 3…Battery pack 4…Upper cabinet 5...Lower cabinet [Modes for carrying out the invention]

[0016] The present application will be further described below, along with specific embodiments. It should be understood that these specific embodiments are merely illustrative of the present application and not intended to limit its scope.

[0017] As used herein, “Examples” means that certain features, structures, or properties described with reference to the Examples are included in at least one Example of this Application. The term, as it appears in various parts of this Specification, does not necessarily refer to the same Example, nor does it mean that any of the Examples are exclusive, independent, or alternative to the others. Those skilled in the art will understand, either explicitly or implicitly, that the Examples described herein can be combined with other Examples.

[0018] The “range” disclosed herein is limited in the form of a lower limit and / or upper limit, and a given range is limited by selecting one lower limit and / or one upper limit, the selected lower limit and / or upper limit defining the boundary of a special range. The range thus limited may or may not include endpoints and may be in any combination; that is, any lower limit may be combined with any upper limit to form an unspecified range, any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single numerical value itself may be combined with any other point or single numerical value as a lower limit or upper limit, or combined with other lower limits or upper limits to form an unspecified range.

[0019] Unless otherwise stated, all embodiments and preferred embodiments of the present application may be combined to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present application.

[0020] Unless otherwise stated, all technical features and selectable technical features of this application can be combined to form new technical solutions, and such technical solutions should be considered to be included in the disclosures of this application.

[0021] Unless otherwise stated, all steps of the present invention may be performed sequentially or randomly, but it is preferable to perform them sequentially. For example, if the method includes steps S1 and S2, the method may include steps S1 and S2 performed sequentially, or steps S2 and S1 performed sequentially. For example, the method mentioned above may further include step S3, and step S3 may be added to the method in any order, for example, the method may include steps S1, S2 and S3, or steps S1, S3 and S2, or steps S3, S1 and S2, and so on.

[0022] Unless otherwise stated, the terms "include" and "include" as used in this application refer to open or closed terms. For example, the terms "include" and "include" may include or include other components not listed, or they may include or include only the listed components. In this application, the terms "multiple" and "multiple types" refer to two or more types.

[0023] Unless otherwise stated, the term "and / or" in this application is used solely to describe the relationship between related objects, indicating that three types of relationships are possible. For example, A and / or B can refer to three situations: A existing alone, A and B existing simultaneously, and B existing alone. Furthermore, the letter " / " in this specification generally indicates that the related objects before and after it are in an "or" relationship.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. Terms used in this specification are solely for the purpose of describing specific embodiments and are not intended to limit this application. The terms “includes” and “have,” and any variations thereof, in the description of this specification, claims, and drawings are intended to cover non-exclusive “inclusion.” Unless otherwise stated, terms used in this application have the common meanings generally understood by those skilled in the art. Unless otherwise stated, the numerical values ​​of each parameter mentioned herein may be measured by various measurement methods commonly used in the art (for example, by testing according to the methods given in the embodiments of this application).

[0025] At present, with the promotion of the theme of being ecological and environmentally friendly, the application of lithium-ion batteries has penetrated deeply into various fields of life, including automobiles, electronic devices, energy storage devices, etc. However, as its application progresses, more and more potential problems are attracting attention. Lithium-ion batteries accumulate internal heat due to causes such as overcurrent, internal short circuit due to internal dendrites, or overcharging. When the heat accumulates to a certain extent, the electrolyte, the positive electrode, and other internal materials undergo a heat dissipation chain reaction, and finally thermal runaway occurs.

[0026] In the present application, by using a polymer having a structure represented by Formula I in a battery, in the case of abuse such as high temperature or overcharging of the battery, ring-opening polymerization occurs to gel the electrolyte, and the characteristics of the polymer that increase the internal resistance of the battery are utilized to reduce the probability of thermal runaway of the battery, improve the thermal stability of the battery, and by providing a substituent to the polymer, the desired effect can be further satisfied. For example, the flame retardant effect can be improved by using halogen substitution, or the side reactions of the battery can be reduced, etc.

[0027] In view of this, as a first aspect of the present application, a polymer having a general formula represented by Formula I is provided.

[0028] [Chemical formula]

[0029] (However, m includes 0 and / or 1, n is a positive integer, X1 and X2 each independently include oxygen, sulfur or an imino group (-NH-), X3 includes oxygen or sulfur, and Y is oxygen, sulfur, an imino group, -S-C unsubstituted or substituted with any group 1~8 an alkylene group, -NH-C unsubstituted or substituted with any group 1~8 an alkylene group, C unsubstituted or substituted with any group 1~8 an alkylene group, C unsubstituted or substituted with any group 1~8 an alkyleneoxy group (i.e., -O-C 1~8It contains one of the alkylene groups, and R1, R2, R3, and R4 are each independently substituted with hydrogen, fluorine, unsubstituted or any group. 1~10 C is an alkyl group, unsubstituted, or substituted with any group. 1~10 It contains one of the alkoxy groups, and R5 is unsubstituted or substituted with any group. 1~10 alkyl group, [ka] It includes one of the following, and R9 is an unsubstituted or substituted C 1~10 (It contains an alkyl group, and any of the above groups includes at least one of a halogen, alkyl group, alkoxy group, ester group, or carbonyl group.)

[0030] Unless otherwise specified, in this application, "*" represents a link between identical or different atoms or terminal parts of a chemical formula. It should be understood that the elements or groups at positions X1, X2, and X3 may be identical or different. The selectable range for the term "halogen" is fluorine, chlorine, bromine, and iodine. The term "C 1~8 The term "alkyl group" should be understood to represent a linear or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and the term "C 1~8 The "alkoxy group" is -OC 1~8 It should be understood as an alkyl group, and it represents the bonding of an alkyl group to the rest of the molecule via an oxygen atom. Term "C 1~8 The term "alkylene group" should be understood to represent a straight-chain or branched-chain saturated divalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and the term "C 1~8 The alkylene oxy group is -OC 1~8 It should be understood as an alkylene group. Correspondingly, the term "C 1~10 The term "alkyl group" should be understood to represent a linear or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and the term "C 1~10 The "alkoxy group" is -OC 1~10It should be understood as an alkyl group. The term "C" 3~10 The term "alkyl group" should be understood to represent a straight-chain or branched saturated monovalent hydrocarbon group having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.

[0031] In the term "unsubstituted or substituted with any group," "substituted with any group" means that at least one hydrogen atom bonded to a carbon atom is replaced with any group other than hydrogen, for example, fluorine. 1~10 Let's take "alkyl group" as an example. 1~10 It should be understood that the alkyl group does not need to be substituted, and may be substituted with one or more substituents (e.g., one, two, three, or four) at any position, and if it has two or more substituents, the substituents may be the same or different, and may be at the same position or different positions. In the phrase "substituted with any group" as described in this application, the any group includes, but is not limited to, at least one of halogens, alkyl groups, alkoxy groups, ester groups, and carbonyl groups, and the alkyl or alkoxy group included in the any group may be linear or cyclic, for example, the any group may include one or more of halogens, linear alkyl groups, cyclic alkyl groups, linear alkoxy groups, and cyclic alkoxy groups. Furthermore, it should be understood that when one or more of "R1", "R2", "R3", "R4", "R5", and "R9" are substituted with "any group", the substituents located on "R1", "R2", "R3", "R4", "R5", and "R9" may be the same or different, and at the same time, the number and substitution positions of substituents located on "R1", "R2", "R3", "R4", "R5", and "R9" are independent of each other.

[0032] The polymer according to the first aspect of the present application can have good stability even if the polymer has a five-membered ring or a six-membered ring structure, as long as m is 0 or 1. The polymer having the structure of formula I is a cyclic structure identical or similar to a cyclic phosphate ester (for example, in which the oxygen in the cyclic phosphate ester is replaced by a group such as sulfur or an (imino)amino group). [ka] The polymer possesses good flame retardancy, can improve the thermal stability of batteries, and in the event of abuse such as high temperature or battery overcharging, ring-opening polymerization occurs, causing the electrolyte to gel, increasing the internal resistance of the battery, and reducing the probability of thermal runaway. Furthermore, the desired effects can be further satisfied by substituents on the polymer; for example, it is possible to improve the flame retardant effect or reduce side reactions of the battery by using halogen substitution. In short, introducing this polymer into a battery is advantageous in improving the thermal stability of the battery and reducing the probability of battery ignition and thermal runaway. Here, the structure of the polymer is identified by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), for example, 1 H, 13 C, 19 F, 31 This can be done by conventional methods such as P analysis, mass spectrometry (MS), elemental analysis, gel permeation chromatography (GPC), and laser Raman spectroscopy (LR).

[0033] In the general formula represented by formula I, n represents the number of repeating units in the general formula represented by formula I, and the range of values ​​for n can be selected based on a reasonable polymer molecular weight. The polymer according to the first aspect of the present application may contain multiple compounds that satisfy the general formula represented by formula I, or it may contain only a single compound that satisfies the general formula represented by formula I. If the polymer contains only a single compound that satisfies the general formula represented by formula I, the value of n in formula I may be greater than 1, for example, 5 or more or 10 or more.

[0034] The polymer according to the first aspect of this application may be a single compound or may contain multiple compounds that satisfy the general formula represented by formula I.

[0035] Furthermore, in order to further improve the performance of the polymer according to the first aspect of the present application while satisfying the above conditions, the type of substituent, the selectable range, the average molecular weight, the type of polymerizable monomer, and specific selections can be further controlled, and the performance of the polymer includes, but is not limited to, flame retardancy, electrolyte retention, and improved thermal stability of the battery. In other words, in order to satisfy the above conditions, it is preferable to satisfy one or more of the following conditions.

[0036] In some embodiments of the present application, the "halogen" includes fluorine. That is, in formula I, Y is oxygen, sulfur, an imino group, an unsubstituted or fluorine-substituted -NH-C 1~8 Alkylene group, unsubstituted or fluorine-substituted C 1~8 Alkylene group, unsubstituted or fluorine-substituted C 1~8 It may contain any one of the alkylene oxy groups, and R1, R2, R3, and R4 are each independently hydrogen, fluorine, unsubstituted or fluorine-substituted C 1~10 C111, an alkyl group, unsubstituted or fluorine-substituted C11 1~10 It may contain any one of the alkoxy groups, and R5 is an unsubstituted or fluorine-substituted C 1~10 alkyl group, [ka] It may contain any one of the following. A polymer having the structural formula represented by formula I, after a fluorine-containing substituent (e.g., fluorine-substituted or fluoroalkyl group) is attached, exhibits better oxidation resistance and stability, reducing the heat dissipation value and spontaneous ignition rate of the battery. This not only reduces the probability of battery ignition and thermal runaway, but is also more advantageous in improving the flame retardancy and thermal stability of the battery, further blunts the negative electrode, reduces side reactions between the negative electrode and the electrolyte, and improves the electrolyte's liquid retention.

[0037] In some embodiments of the present application, X1 and X2 may each independently contain oxygen or sulfur, and Y is oxygen, unsubstituted or fluorinated C 1~8 Alkylene group, unsubstituted or fluorine-substituted C 1~8 It may contain any one of the alkylene oxy groups, and R1, R2, R3, and R4 are each independently hydrogen, fluorine, unsubstituted or fluorine-substituted C 1~10 C111, an alkyl group, unsubstituted or fluorine-substituted C11 1~10 It contains one of the alkoxy groups, and R5 is an unsubstituted or fluorine-substituted C 1~10 alkyl group, [ka] It may contain any one of the following, and R9 is an unsubstituted or fluorine-substituted C 1~10 It may contain alkyl groups. Preferably, X1 and X2 may each independently contain oxygen, X3 may contain oxygen, and Y may be oxygen, unsubstituted or fluorinated C 1~8 Alkylene group, unsubstituted or fluorine-substituted C 1~8 The battery may contain any one of the alkylene oxy groups. By selecting X1, X2, X3, Y, R1, R2, R3, R4, R5, and R9 within a predetermined range, the probability of battery ignition and thermal runaway can be further reduced.

[0038] In some embodiments of this application, the average molecular weight of the polymer may be 20,000 to 60,000, for example, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, or any of the above values. The method for measuring the average molecular weight of the polymer includes, but is not limited to, gel permeation chromatography (GPC). The polymer can be used in the electrolyte to improve the thermal stability of the battery. If the average molecular weight is too low, it is difficult to form a network polymer, affecting the improvement effect on the thermal stability of the battery. If the average molecular weight is too high, it is difficult to dissolve in the electrolyte. By keeping the average molecular weight of the polymer within a predetermined range, the dispersibility in the electrolyte can be improved, which is advantageous for uniform film formation on the surfaces of the positive and negative electrodes, improving the compatibility between the electrolyte and the positive and negative electrodes. Furthermore, when ring-opening polymerization occurs, it is advantageous for promoting gelation of the electrolyte, improving the thermal stability of the battery and reducing the probability of battery ignition and thermal runaway.

[0039] In some embodiments of the present application, in the polymer represented by formula I, R1, R2, R3, and R4 are each independently unsubstituted or fluorine-substituted C 1~10 C111, an alkyl group, unsubstituted or fluorine-substituted C11 1~10 It may contain any one of the alkoxy groups, preferably R1, R2, R3, and R4 are each independently substituted with fluorine. 1~10 Alkyl alkyl groups, fluorine-substituted C 1~10It may contain any one of the alkoxy groups. Substitution with a (fluoro)alkyl group or (fluoro)alkoxy group having 1 to 10 carbon atoms is more advantageous than direct substitution with hydrogen or fluorine in order to increase the molecular weight of the polymer and form a network polymer, which can further improve the thermal stability of the battery. Furthermore, after substitution with a fluoroalkyl (oxy) group chain, the strong electronegativity of the fluorine atom significantly improves the oxidation resistance of the polymer, improving the flame retardant effect and the thermal stability of the battery, as well as reducing side reactions between the electrolyte and the negative electrode. As a result, by selecting R1, R2, R3, and R4 within a predetermined range, the probability of battery ignition and thermal runaway can be further reduced.

[0040] In some embodiments of the present application, the polymerizable monomer of the general formula polymer represented by formula I may include double bond-containing cyclic phosphate ester compounds, and the polymerizable monomer contains a cyclic phosphate ester or a cyclic structure similar to a cyclic phosphate ester structure (the cyclic phosphate ester or a cyclic structure similar to a cyclic phosphate ester structure is [ka] By providing the double bond-containing cyclic phosphate ester compounds (including), it is advantageous to improve the thermal stability of the battery. Here, the double bond-containing cyclic phosphate ester compounds can self-polymerize under an initiator or high voltage, or grant copolymerize with other polymerizable compounds to form a network polymer. When used in a battery, it has a film-forming effect on the surface of the positive and negative electrode pieces of the battery, improving the correspondence between the electrolyte and the positive and negative electrode pieces, suppressing side reactions between the electrode pieces and the electrolyte, and reducing the consumption of the electrolyte. Furthermore, by self-polymerizing or copolymerizing with other polymerizable compounds to form a network polymer, the molecular weight of the polymer can be further increased, improving the thermal stability of the battery. Note that the "cyclic phosphate ester compounds" described in this application refer to compounds having a cyclic phosphate ester, any group (e.g., fluorine, (imino)amino group, sulfur, (alkylene oxy)alkoxy group, (alkylene)alkyl group, -NH-C 1~8 Compounds having a cyclic phosphate ester substituted with at least one of the following (such as an alkylene group), and cyclic structures similar to cyclic phosphate esters (e.g., any oxygen in the cyclic phosphate ester is sulfur, (imino)amino group, (alkylene)alkyl group, (alkylene oxy)alkoxy group, -NH-C 1~8 Alkylene group, -SC 1~8 The compound may include, but is not limited to, compounds having at least one of the alkylene groups (which are substituted), and only if the double bond-containing cyclic phosphate ester compound can self-polymerize or copolymerize with other polymerizable compounds to obtain a polymer of the general formula represented by formula I. For example, the "cyclic phosphate ester compound" is, [ka] It may include.

[0041] In some embodiments of the present application, the polymerizable monomer of the polymer represented by formula I may consist solely of double-bond-containing cyclic phosphate ester compounds, where the double-bond-containing cyclic phosphate ester compounds may be of the same type or may include multiple different double-bond-containing cyclic phosphate ester compounds. When used in a battery, the polymerizable monomer may be polymerized before being introduced into the electrolyte, or it may be added directly to the electrolyte and self-polymerized by adding an initiator or under high pressure. By using only double-bond-containing cyclic phosphate ester compounds as polymerizable monomers, the polymer can have an even better flame retardant effect, and the thermal stability of the battery can be significantly improved.

[0042] In some embodiments of this application, the polymerizable monomer of the polymer represented by formula I is [ka] It may also include. For example, the polymerizable monomer of the polymer represented by formula I is [ka] The polymer may include, but is not limited to, one or more of the following. In the actual operation, polymerizable monomers satisfying the general formula may be self-polymerized to obtain a polymer represented by formula I, or polymerizable monomers satisfying the general formula may be copolymerized with other polymerizable compounds to obtain a polymer represented by formula I.

[0043] In some embodiments of the present application, the polymer represented by formula I may contain at least one of the 276 compounds represented by structural formulas I-1 to I-276. Any of the 276 compounds represented by structural formulas I-1 to I-276 may be used individually in the battery, or any combination of multiple compounds may be used in the battery. The 276 compounds represented by structural formulas I-1 to I-276 have a 5-membered or 6-membered ring structure of cyclic phosphate esters, possess good stability, and the oxidation resistance and de-oxidizing effect on the negative electrode can be further improved by fluorine substituents. By using these compounds in a battery, the thermal stability of the battery can be improved, and the probability of battery ignition and thermal runaway can be reduced.

[0044] The structures of the 276 compounds represented by structural formulas I-1 to I-276 are as follows:

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] In some embodiments of the present application, the polymerizable monomer of the polymer represented by formula I may also include a second polymerizable compound other than the double-bond-containing cyclic phosphate ester compound, the second polymerizable compound being a polymerizable compound different from the double-bond-containing cyclic phosphate ester compound, in which case the general formula of the polymer may be represented by formula II.

[0058] [ka]

[0059] However, a and b are independent positive integers, and 0.5 ≤ a / b ≤ 4. For example, the value of a / b may be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4, or it may be within a range of any of the above values. R6 is an unsubstituted or substituted C3-10 alkyl group, or an unsubstituted or substituted C group. 3~10C is an epoxy group, unsubstituted, or substituted with any of the aforementioned groups. 3~10 C is an allyl group, unsubstituted, or substituted with any of the aforementioned groups. 3~10 (methyl)acryloyl group, unsubstituted or substituted with any of the above groups C 3~10 It is one of the acrylates. Both the polymer represented by formula II and the polymer represented by formula I have a cyclic phosphate ester structure, and ring-opening polymerization occurs under abusive conditions such as high temperature or battery overcharging, causing the electrolyte to gel, improving the thermal stability of the battery, and reducing the probability of battery ignition and thermal runaway. Furthermore, the polymer can also possess the properties of a second polymerizable compound. For example, the second polymerizable compound may be a polymerizable monomer of a gel polymer electrolyte. As a result, after copolymerizing a double-bond-containing cyclic phosphate ester compound with a polymerizable monomer of a gel polymer, the resulting polymer can possess both good flame retardancy and the properties of a gel polymer electrolyte. When used in a battery, it is advantageous in reducing the probability of liquid electrolyte leakage and the probability of electrode corrosion and oxidative ignition due to leakage, improving volume expansion during the battery's charge and discharge process, and further improving the battery's thermal stability. Here, in the compound represented by formula II, a is the degree of polymerization of the double bond-containing cyclic phosphate ester compound, and b is the degree of polymerization of the second polymerizable compound. If a is too small compared to b, it is unfavorable for improving the flame retardant performance of the polymer, and if a is too large compared to b, it is unfavorable for the polymer to satisfy the properties of the second polymerizable compound. By controlling the value of a / b within a predetermined range, it is advantageous for the polymer represented by formula II to possess both good flame retardant performance and the properties of the second polymerizable compound.

[0060] In some examples of the present application, the second polymerizable compound may contain at least one of polymerizable monomers, oligomers, and copolymers of gel polymer electrolytes, and the second polymerizable compound within a predetermined range may copolymerize with double-bond-containing cyclic phosphate ester compounds to form a gel phase. Here, the second polymerizable compound is methyl methacrylate, styrene, methyl acrylate, ethyl acrylate, acrylic acid, trimethylsilyl methacrylate, acrolein dimethyl acetal, acrolein diethyl acetal, 2-phenoxyethyl acrylate, tridecafluoro-2-hydroxynonyl ester, trifluoroethyl methacrylate, allyl-1,3-sultone, glycidyl methacrylate, acrylamide, trifluoroethyl acrylate, (acryloxymethyl)dimethylmethoxysilane, cyanoethyl Acrylate, hydroxyethyl acrylate, trialyl trimesinate, hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 1-vinyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-allyl-3-ethylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-allyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,The compound may contain, but is not limited to, at least one of the following: 5-octafluorohexane, pentafluorophenol acrylate, vinylene carbonate, maleic anhydride, cyanoethyl acrylate, butyl acrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, and vinyl ethylene carbonate. Furthermore, the second polymerizable compound may contain vinylene carbonate, maleic anhydride, cyanoethyl acrylate, butyl acrylate, hexafluoroisopropyl methacrylate, etc. Preferably, the polymer is at least one of methacrylate, hexafluorobutyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, and vinyl ethylene carbonate. By selecting a second polymerizable compound within a predetermined range, the polymer can possess both good flame retardant properties and gel polymer electrolyte properties, improving the thermal stability of the battery, reducing the probability of battery ignition and thermal runaway, improving the electrolyte's liquid retention, and mitigating volume expansion that occurs during the charge-discharge process.

[0061] A second aspect of this application provides a method for preparing a polymer according to the first aspect of this application, comprising self-polymerizing a double-bond-containing cyclic phosphate ester compound and / or copolymerizing a double-bond-containing cyclic phosphate ester compound with a second polymerizable compound. Both of these methods can prepare polymers containing a cyclic phosphate ester structure. The features and effects described for the polymer according to the first aspect of this application also apply to the method for preparing the polymer according to the second aspect of this application, and therefore will not be repeated here. In short, compared to the prior art, this method not only allows for the production of polymers having a cyclic phosphate ester structure, but also allows for the selection of specific types or structures of polymerizable monomers and / or second polymerizable compounds as needed to meet different additional needs, and can be used in the battery field to improve the thermal stability of batteries and reduce the probability of battery ignition and thermal runaway.

[0062] In some embodiments of the present application, before self-polymerizing or copolymerizing the double-bond-containing cyclic phosphate ester compound with a second polymerizable compound, a polymerizable monomer of the double-bond-containing cyclic phosphate ester compound may be prepared first. For example, an intermediate product may be prepared and then subjected to a ring-forming or substitution reaction. For example, [ka]

[0063] In some specific examples of this application, as understood by referring to general reaction formula I, a method for preparing polymerizable monomers of double-bond-containing cyclic phosphate ester compounds is: [ka] By performing a ring-forming reaction, the general formula is [ka] This may include obtaining the compound.

[0064] In some specific examples of this application, as understood by referring to general reaction formula II, a method for preparing polymerizable monomers of double-bond-containing cyclic phosphate ester compounds is: [ka] By performing a substitution reaction, the general formula becomes [ka] This may include obtaining the compound. [ka] This may be a single compound, [ka] It may also be obtained by mixing multiple types of compounds that satisfy the requirements.

[0065] However, m includes 0 and / or 1, X1' and X2' each independently include a hydroxyl group, a mercapto group, or an amino group, X1 and X2 each independently include oxygen, sulfur, or an imino group, and R1, R2, R3, and R4 each independently include hydrogen, fluorine, an unsubstituted or any group-substituted C 1~10 C is an alkyl group, unsubstituted, or substituted with any group. 1~10 It contains one of the alkoxy groups, and R7 and R8 are each independently unsubstituted or substituted with any group. 2~11 The compound contains an olefin, where Y' contains hydrogen, a hydroxyl group, a mercapto group, or an amino group, Y'' contains oxygen, sulfur, or an imino group, and R9 is an unsubstituted or substituted C with any group. 1~10 It contains an alkyl group, and the aforementioned arbitrary group includes at least one of a halogen, alkyl group, alkoxy group, ester group, or carbonyl group. [ka] These may all be used as polymerizable monomers for double-bond-containing cyclic phosphate ester compounds.

[0066] In some embodiments of the present application, the reaction general formulas I and II [ka] This may contain, but is not limited to, at least one of ethylene glycol, ethanedithiol, 2-mercaptoethanol, mercaptoethylamine, ethanolamine, ethylenediamine, 1,3-propanediol, 1,3-propanedithiol, 3-mercapto-1-propanol, 3-amino-1-propanol, 3-mercapto-1-propamine, and 1,3-propanediamine. [ka] It would be ideal if it could react with another compound to form a 5-membered or 6-membered ring.

[0067] In some embodiments of this application, the compound in the reaction general formula I [ka] and the compound in general reaction formula II [ka] The synthesis method includes, but is not limited to, the methods represented by general reaction formulas III and IV. Herein, as one specific example in general reaction formula III, Br-R7 is used as allyl bromide, P(OEt)3 (triethyl phosphonate) is reacted with allyl bromide, the resulting diethyl allyl phosphate is dissolved in an organic solvent (e.g., acetonitrile), potassium iodide anhydrous is added, protected with argon gas, trimethylchlorosilane (TMSCl) is added dropwise at room temperature and reacted for a certain period of time, then trimethylchlorosilane and solvent are removed, dichloromethane is added, oxalyl chloride is added dropwise at room temperature and reacted for a certain period of time, and then distilled under reduced pressure. [ka] To obtain. [ka]

[0068] In some specific examples of this application, as can be understood by referring to the reaction equations below, the method for preparing polymerizable monomers of double-bond-containing cyclic phosphate ester compounds may include, but is not limited to, the following: [ka] The prepared polymerizable monomers I-12', I-49', I-192', I-84', and I-108' may be used, in order, as polymerizable monomers for polymers I-12, I-49, I-192, I-84, and I-108, respectively.

[0069] As one specific example, a method for preparing polymerizable monomer I-12' may include the following: (a) [ka] The synthesis is as follows: Triethyl phosphonate (19.5 g, 117 mmol) and allyl bromide (17.3 g, 143 mmol) are heated at 70°C for 24 hours, and impurities are removed by distillation to obtain a colorless liquid (19.5 g, yield: 93.56%) which is then used in the next step. Diethyl allyl phosphate (25.0 g, 150 mmol), which is the colorless liquid, is taken and dissolved in acetonitrile (100 mL), and potassium iodide anhydrous (42.0 g, 300 mmol) is added and the mixture is protected with argon gas. Trimethylchlorosilane (68.0 g, 600 mmol) is added dropwise at room temperature, and after the addition is complete, the reaction system is allowed to react at 40°C for 2 hours. Remove excess trimethylchlorosilane and acetonitrile by vacuum distillation, add 100 mL of dichloromethane, and add oxalyl chloride (51.0 g, 600 mmol) and (0.5 mL) DMF dropwise at room temperature. After addition is complete, stir at room temperature for 16 hours. Obtain a colorless liquid by vacuum distillation and the product. [ka] (14.3 g, yield: 60%) is obtained. (b) Ring formation reaction: Specifically, 3,3,3-trifluoro-1,2-propanediol (10.52 g, 80.9 mmol) and triethylamine (22.5 mL, 161.8 mmol) are dissolved in anhydrous tetrahydrofuran (100 mL), protected with argon gas, and stirred at room temperature for 5 minutes. Cool to -20°C, [ka] (12.86 g, 80.9 mmol) is added dropwise, and the mixture is stirred at room temperature for 3 hours. After the reaction is complete, water (50 mL) is added to quench the mixture, and the mixture is extracted with ethyl acetate (100 mL x 2 times). The mixture is then washed with 0.1 M hydrochloric acid (100 mL x 2 times) and saturated saline solution (50 mL x 2 times). The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to remove the organic solvent and obtain a colorless liquid (10.89 g, 62.34%), which is the polymerizable monomer I-12'.

[0070] For the obtained target product 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(CDCl3,400MHz),δ(ppm):5.70(m,1H),5.01(m,2H),4.74(m,2H),4.12(m,1H),3.68(m,2H); 13 C NMR(CDCl3,100MHz),δ(ppm):132.7,115.9,114.5,100.4,64.9,28.8; 19 F NMR(CDCl3,376MHz),δ(ppm):-78.9; 31 P NMR(CDCl3,160MHz),δ(ppm):44.2;HRMS(ESI + )m / z [M] + calcd.for C6H8F3O3P:216.0163.found:216.0169.

[0071] As one specific example, the synthesis method for polymer I-12 includes the following: 1.5 g of polymerizable monomer I-12' and 32 mg of AIBN (azobisisobutyronitrile) are placed in a 25 mL neck flask, the reaction system is solidified in liquid nitrogen, then vacuumed with an oil pump and maintained for 10 mins, then dissolved, and argon gas is introduced. This process is repeated four times, and finally the mixture is stirred in an oil bath at 70°C for 22 hours. After the reaction is complete, it is added to 20 mL of n-hexane and precipitated, and the solid is precipitated and filtered by suction to obtain 1.23 g of solid (yield: 82%). Elemental analysis of the target product is performed: Elements analysis: calcd: C, 33.35; H, 3.75; F, 26.38; O, 22.21; P, 14.33.Found: C, 34.15; H, 3.65; O, 21.28; P, 14.52.M n :36000, PDI:1.8.

[0072] As one specific example, a method for preparing polymerizable monomer I-49' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The ring-forming reaction is carried out, and for the detailed process, refer to the method for preparing polymerizable monomer I-12'. 1 1H NMR, 13 1C NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(CDCl3,400MHz),δ(ppm):5.70(m,1H),5.01(m,2H),2.86(m,4H),2.02(m,2H); 13 C NMR(CDCl3,100MHz),δ(ppm):132.7,115.9,31.7,31.1;31P NMR(CDCl3,160MHz),δ(ppm):43.6;HRMS(ESI + )m / z [M]+ calcd.for C5H9S2OP:179.9832.found:179.9837.

[0073] As one specific example, a method for preparing the polymerizable monomer I-192' may include the following: (a) [ka] The synthesis is as follows: Specifically, 3,3,3-trifluoro-1,2-propanediol (10.52 g, 80.9 mmol) and triethylamine (15.23 g, 150.5 mmol) are dissolved in dichloromethane (80 ml), and trichloride phosphate (11.78 g, 76.8 mmol) is added dropwise at 5°C. After the addition is complete, the reaction is continued for 2 hours. The mixture is filtered to remove triethylamine hydrochloride, the filtrate is dried over anhydrous magnesium sulfate, concentrated under reduced pressure to remove dichloromethane, and recrystallized with toluene. [ka] (b) [ka] By performing a substitution reaction, specifically, [ka] Dissolve (11.15 g, 53.0 mmol) and triethylamine (2.46 mL, 17.7 mmol) in anhydrous dichloromethane (50 mL), protect with argon gas, and stir at room temperature for 5 minutes. Add allyl mercaptan (4.33 g, 58.3 mmol) dropwise, stir at room temperature for 2 hours, and after the reaction is complete, add water (50 mL) to quench, extract with ethyl acetate (100 mL x 2 times), and wash with 0.1 M hydrochloric acid (100 mL x 2 times) and saturated brine (50 mL x 2 times). Dry the organic phase over anhydrous sodium sulfate, filter, concentrate under reduced pressure to remove the organic solvent, and obtain a white solid (8.49 g, yield: 64.58%) to obtain the polymerizable monomer I-192'. 11H NMR, 13 13C NMR, 19 19F NMR, 31 1H NMR, 13C NMR, 19F NMR, 31P NMR and HRMS were used for identification and analysis, and the results are as follows. 1 1H NMR (CDCl3, 400 MHz), δ (ppm): 5.96 (m, 1H), 5.06 (m, 2H), 4.12 (m, 1H), 3.68 (m, 2H), 3.23 (m, 2H); 13 13C NMR (CDCl3, 100 MHz), δ (ppm): 132.7, 115.9, 113.8, 99.2, 63.7, 21.0; 19 19F NMR (CDCl3, 376 MHz), δ (ppm): -76.8; 31 31P NMR (CDCl3, 160 MHz), δ (ppm): 43.2; HRMS (ESI + ) m / z [M] + calcd. for C6H8F3O3PS: 247.9884. found: 247.9879.

[0074] As a specific example, the method for preparing the polymerizable monomer I-84' may include the following. (a)

Chemical formula

Chemical formula

[0075] As a specific example, the method for preparing the polymerizable monomer I-108’ may include the following. (a)

Chemical formula

Chemical formula

[0076] As one specific example, a method for preparing polymerizable monomer I-60' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The polymerizable monomer I-60' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-12' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.70(s,1H),5.03(s,1H),4.97(s,1H),3.62(m,1H),2.82(m,2H),2.0(s,2H); 13 C NMR(DMSO-d6,100MHz),δ(ppm):132.7,120.1,115.9,53.7,31.4,18.2; 19 F NMR(DMSO-d6,376MHz),δ(ppm):-72.8; 31 P NMR((DMSO-d6,160MHz),δ(ppm):46.8;HRMS(ESI + )m / z [M] + calcd.for C6H8F3OPS2:247.9706.found:247.9748.

[0077] As one specific example, a method for preparing the polymerizable monomer I-125' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The polymerizable monomer I-125' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-12' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.70(s,1H),5.03(s,1H),4.97(s,1H),4.74(m,2H),3.85(s,4H); 13 C NMR(DMSO-d6,100MHz),δ(ppm):132.7,115.9,114.4,81.1,28.8; 19 F NMR(DMSO-d6,376MHz),δ(ppm):-89.2; 31 P NMR((DMSO-d6,160MHz),δ(ppm):47.4;HRMS(ESI + )m / z [M] + calcd.for C6H9F2O3P:198.0257.found:198.0271.

[0078] As one specific example, a method for preparing the polymerizable monomer I-137' may include the following: (a) [ka] The synthesis of is [ka] Refer to the synthesis of, [ka] (b) Obtained by reacting. [ka] The polymerizable monomer I-137' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-192' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.89(s,1H),5.23(s,2H),4.70(m,2H),4.35(s,4H); 13 C NMR(DMSO-d6,100MHz),δ(ppm):137.5,115.1,114.4,77.3,69.0; 19 F NMR(DMSO-d6,376MHz),δ(ppm):-87.5; 31 P NMR((DMSO-d6,160MHz),δ(ppm):47.9;HRMS(ESI + )m / z [M] + calcd.for C6H9F2O4P:214.0207.found:214.0241.

[0079] As one specific example, a method for preparing polymerizable monomer I-149' may include the following: (a) [ka] The synthesis of this refers to the synthesis of monomer I-137'. [ka] (b) Obtained by reacting. [ka] The polymerizable monomer I-149' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-192' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.89(s,1H),5.23(s,2H),4.20(m,2H),2.88(s,4H);13C NMR(DMSO-d6,100MHz),δ(ppm):137.5,118.7,115.1,74.2,31.9; 19 F NMR(DMSO-d6,376MHz),δ(ppm):-88.3; 31 P NMR((DMSO-d6,160MHz),δ(ppm):46.5;HRMS(ESI + )m / z [M] + calcd.for C6H9F2O2PS2:245.9750.found:245.9721.

[0080] As one specific example, a method for preparing the polymerizable monomer I-173' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The polymerizable monomer I-173' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-192' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 19 F NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.96(s,1H),5.12(s,1H),5.03(s,1H),3.85(s,4H),3.23(m,2H); 13 C NMR(DMSO-d6,100MHz),δ(ppm):132.7,115.9,113.7,79.9,21.0; 19 F NMR(DMSO-d6,376MHz),δ(ppm):-73.2; 31 P NMR((DMSO-d6,160MHz),δ(ppm):44.8;HRMS(ESI + )m / z [M] + calcd.for C6H9F2O3PS:229.9978.found:229.9986

[0081] As one specific example, a method for preparing the polymerizable monomer I-205' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The polymerizable monomer I-205' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-12' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 31Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.70(s,1H),5.03(s,1H),4.97(s,1H),3.83(m,2H),2.75(m,2H),2.0(s,2H); 13 C NMR(DMSO-d6,100MHz),δ(ppm):132.7,115.9,79.7,29.8,23.5; 31 P NMR((DMSO-d6,160MHz),δ(ppm):43.3;HRMS(ESI + )m / z [M] + calcd.for C5H9O2PS:164.0061.found:164.0037.

[0082] As one specific example, a method for preparing the polymerizable monomer I-229' may include the following: (a) [ka] The synthesis is as described above. (b) [ka] The polymerizable monomer I-229' is obtained by substitution reaction. [ka] For the obtained target product, refer to the method for preparing polymerizable monomer I-12' for specific and detailed procedures. 1 1H NMR, 13 1C NMR, 31 Identification and analysis were performed using methods such as 1P NMR and HRMS, and the results are as follows. 1 H NMR(DMSO-d6,400MHz),δ(ppm):5.70(s,1H),5.03(s,1H),4.97(s,1H),3.79(m,2H),2.84(m,2H),2.0(m,3H); 13C NMR(DMSO-d6,100MHz),δ(ppm):132.7,115.9,79.6,39.9,29.7; 31 P NMR((DMSO-d6,160MHz),δ(ppm):42.6;HRMS(ESI + )m / z [M] + calcd.for C5H 10 NO2P:147.0449.found:147.0468.

[0083] In some specific examples of the present application, the method for preparing double bond-containing cyclic phosphate ester compounds is further obtained by the reaction general formula I. [ka] The sulfurized reaction and / or the reaction obtained by general formula II [ka] The sulfurization reaction is carried out, for example, using a tetrahydrofuran (THF) solution of Lawesson's reagent (2,4-bis(p-methoxyphenyl)-1,3-dithia-2,4-diphosphacyclobutane-2,4-disulfide) under heating conditions (e.g., constant temperature heating), and the general formula is [ka] Polymerizable monomers and / or general formulas [ka] This includes the ability to obtain polymerizable monomers. This can be understood by referring to the reaction equation below.

[0084] [ka]

[0085] In some embodiments of the present application, the double bond-containing cyclic phosphate ester compound may contain one or more polymerizable monomers, for example, at least one of polymerizable monomers such as I-12' of polymer I-12, I-49' of polymer I-49, I-84' of polymer I-84, I-108' of polymer I-108, and I-192' of polymer I-192.

[0086] In some embodiments of this application, the self-polymerization of double-bond-containing cyclic phosphate ester compounds and / or copolymerization of double-bond-containing cyclic phosphate ester compounds with a second polymerizable compound is carried out under initiator conditions, the initiator may include at least one of azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2'-azabis(2-imidazoline)dihydrochloride, 2,2'-azobisisobutylamidinedihydrochloride, benzoyl peroxide, tert-butylbenzoyl peroxide, and methyl ethyl ketone peroxide. Carrying out the self-polymerization and / or copolymerization reaction under the action of an initiator within a predetermined range is advantageous not only for the formation of network polymers, but also for controlling the polymerization rate and degree of polymerization by adjusting the amount and conditions of the initiator used, and further advantageous for obtaining polymers within a desired molecular weight range. Preferably, the amount of initiator used may be 1 wt% to 10 wt%, based on the total mass of the double-bond-containing cyclic phosphate ester compound and the second polymerizable compound. For example, it may be 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, or any of the above values ​​within a given range. By controlling the amount of initiator used within a predetermined range, the polymerization rate and degree of polymerization can be further improved, which is even more advantageous for obtaining polymers having the desired molecular weight range.

[0087] A third aspect of this application provides a gel polymer electrolyte comprising a polymer matrix containing a polymer according to the first aspect of this application or a polymer prepared by the method according to the second aspect of this application, and an electrolyte. It can be understood that the electrolyte may contain a solvent and a lithium salt, the solvent may be a non-aqueous solvent, and preferably the solvent may contain a main solvent and an auxiliary solvent, where the role of the main solvent includes dissolving the lithium salt to improve the electrochemical stability of the electrolyte, and the role of the auxiliary solvent may include reducing the viscosity of the electrolyte to further improve ionic conductivity, etc. The features and effects described in the polymer according to the first aspect of this application and the method for preparing the polymer according to the second aspect of this application also apply to the gel polymer electrolyte according to the third aspect of this application, so they will not be repeated here. In short, the gel polymer electrolyte can improve the thermal stability of the battery and reduce the probability of ignition and thermal runaway, as well as mitigate volume expansion during the charge-discharge process to some extent and improve volume stability during the cycle process.

[0088] In some embodiments of the present application, the main solvent in the electrolyte may include one or more of ester solvents, ether solvents, sulfone solvents, nitrile solvents, and ionic liquid solvents, but is not limited thereto. Here, the ester solvents may include one or more of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), γ-butyrolactone (BL), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), methyl formate (MF), ethyl formate (EF), methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), ethyl butyrate (EB), etc. and their fluorinated derivatives, but is not limited thereto. The ether solvents may include one or more of dimethyloxymethane (DMM), ethylene glycol dimethyl ether (DME), ethylene glycol diethyl ether (DEE), 1,2-dimethoxypropane (DMP), diethylene glycol dimethyl ether (DGM), tetrahydrofuran (THF), tetrahydropyran (THP), 1,3-dioxolane (DOL), 1,3-dioxane (1,3-DXA), 1,4-dioxane (1,4-DXA), etc. and their fluorinated derivatives, but is not limited thereto. The sulfone solvents may include one or more of dimethyl sulfone, dimethyl sulfoxide, sulfolane, ethyl methyl sulfone, tetramethylene sulfoxide, ethyl methyl sulfoxide, diethyl sulfone, diethyl sulfoxide, methyl phenyl sulfone, methyl phenyl sulfoxide, ethyl phenyl sulfone, ethyl phenyl sulfoxide, vinyl phenyl sulfone, vinyl phenyl sulfoxide, etc. and their fluorinated derivatives, but is not limited thereto. By using the main solvent within the above predetermined range, the dissolution of the lithium salt can be improved, and the electrolyte can be provided with good ion transport performance.

[0089] In some embodiments of the present application, the auxiliary solvent in the electrolyte may be a solvent that cannot dissolve lithium salts but can mix well with the main solvent. Generally, electrolytes with low lithium salt concentrations have low viscosity and high conductivity, but somewhat poor electrochemical stability, while electrolytes with high concentrations have most of the solvent molecules composed of Li + Because it can combine with the main solvent to form a solvent-based outer shell structure, it has high electrochemical stability, but the electrical performance of the electrolyte decreases due to the high viscosity and low ion mobility at high concentrations. The gel polymer electrolyte according to the third aspect of the present invention, using an auxiliary solvent that cannot dissolve the lithium salt but can mix well with the main solvent as a diluent, can not only maintain the properties of a high-concentration electrolyte by adding the diluent to a high-concentration electrolyte to form a locally high-concentration electrolyte, but also obtain the advantages of low viscosity and high ionic conductivity of a low-concentration electrolyte. In other words, the electrolyte can combine the advantages of both low-concentration and high-concentration electrolytes, achieving both high ion mobility and good electrochemical stability, and further improving the dynamic performance of the battery.

[0090] In some embodiments of the present application, the co-solvent in the electrolyte may include one or more of cyclohexane, benzene, toluene, p-xylene, m-xylene, o-xylene, fluorobenzene, p-difluorobenzene, m-difluorobenzene, o-difluorobenzene, trifluorotoluene, trifluoromethoxybenzene, decafluoropentane, perfluoropentanone, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane, bis(2,2,2-trifluoroethyl)ether, 1,1,2,3,3,3-hexafluoropropyl ethyl ether, 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether, ethyl trifluoromethyl ether, difluoromethyl-2,2,3,3,3-pentafluoropropyl ether, heptafluoropropyl-1,2,2,2,2-tetrafluoroethyl ether, difluoromethyl 2,2,3,3-tetrafluoropropyl ether, perfluoroisopropyl methyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, ethyl-1,1,2,2-tetrafluoroethyl ether, ethyl-2,2,2-tetrafluoroethyl ether, bis(1,1,2,2-tetrafluoroethyl)ether, etc., but is not limited thereto. Preferably, the co-solvent in the electrolyte may include one or more of trifluoromethoxybenzene, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane. The co-solvent within a predetermined range has a high electrochemical window, good compatibility, and good ability to promote the formation of a fluorine-rich SEI. By combining with the main solvent, it can not only improve the ionic conductivity and electrochemical stability of the electrolyte, but is also advantageous for reducing the side reaction between the electrolyte and the negative electrode sheet.

[0091] In some embodiments of the present application, the lithium salt in the electrolyte may include one or more of the following: lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluoride phosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoride arsenate (LiAsF6), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTF), lithium difluorophosphate (LiDFP), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium difluoro(dioxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate. However, it is not limited to these. For example, lithium bis(fluorosulfonyl)imide is preferred. The lithium salt can decompose on the negative electrode surface to form an inorganic fluorine-rich SEI component and has excellent dissociation ability, which is advantageous for achieving high ionic conductivity and low viscosity of the electrolyte, and further improves the electrochemical performance of the battery.

[0092] In some embodiments of the present application, the electrolyte may contain an initiator and polymerizable monomers for the polymer matrix, the initiator being used to polymerize the polymerizable monomers for the polymer matrix to form the polymer matrix. Preferably, additives may be added to the electrolyte as needed to achieve the desired effect, for example, additives to suppress the elution of transition metals, and / or additives to promote film formation. Here, the additives to promote film formation may include, but are not limited to, one or more of propane sultone, vinyl sulfate, vinyl sulfite, tris(trimethylsilane) phosphate, tris(trimethylsilane) phosphite, tris(trifluoroethyl) phosphate, tris(trifluoroethyl) phosphite, tris(trimethylsilane) borate, dimethyl maleic anhydride, and 1,4-diisocyanatobutyl. By selecting additives within a predetermined range, further improvements in the stability of the positive and negative electrodes of the battery and extension of the battery life can be achieved.

[0093] In some embodiments of the present application, the mass ratio of the polymer matrix in the gel polymer electrolyte may be 0.5 wt% to 25 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, 25 wt%, or any of the above values. Preferably, the mass ratio of the polymer matrix in the gel polymer electrolyte may be 5 wt% to 25 wt%, and more preferably 5 wt% to 12 wt%. Regarding the polymer composition used in this invention, if the mass ratio of the polymer matrix in the gel polymer electrolyte is too small, it is difficult to achieve good flame retardancy and improve the thermal stability of the battery. If the mass ratio of the polymer matrix is ​​too large, polarization increases, ionic conductivity decreases, and the battery's cycle life is likely to be affected. By controlling the mass ratio of the polymer matrix in the gel polymer electrolyte within a predetermined range, it is possible to simultaneously achieve both the electrochemical performance and thermal stability of the battery, which is advantageous in reducing the probability of battery ignition and thermal runaway, and allows for the acquisition of a battery with a long service life.

[0094] A fourth aspect of the present application provides a battery comprising a gel polymer electrolyte according to the third aspect of the present application, and / or a polymer obtained by the method according to the second aspect of the present application, and / or a polymer according to the first aspect of the present application. Preferably, the battery may be a secondary battery, for example, a lithium metal secondary battery or a lithium-ion battery.

[0095] In some embodiments of this application, the process of forming the gel polymer electrolyte during battery production includes, but is not limited to, mixing the main solvent, auxiliary solvent, and lithium salt of the gel polymer electrolyte with the polymerizable monomer and initiator of the polymer matrix, injecting the resulting mixture into a cell, packaging it, and curing it. For example, the curing operation may be held at 50°C to 70°C for 8 to 12 hours to polymerize the polymerizable monomer and form the polymer matrix, after which it may be allowed to stand. When characterizing the polymer matrix in a battery, the battery can be disassembled, the obtained gel polymer electrolyte can be vacuum-dried to remove the solvent, washed to remove the lithium salt, dissolved in an appropriate amount of solvent, and finally filtered by precipitation with n-hexane to obtain the polymer matrix. When identifying the structure of the polymer matrix, infrared spectroscopy (IR), nuclear magnetic resonance (NMR), etc., can be used. 1 H, 13 C, 19 F, 31 This can be performed by combining common methods such as P (for example), mass spectrometry (MS), elemental analysis, gel permeation chromatography (GPC), and laser Raman spectroscopy (LR).

[0096] In some embodiments of the present application, the battery may include a positive electrode, a negative electrode, a separator, and the gel polymer electrolyte. During the charging and discharging process of the battery, active ions reciprocate and are inserted into and removed from the positive electrode and the negative electrode. The separator is provided between the positive electrode and the negative electrode and serves to isolate them. The gel polymer electrolyte serves to conduct ions between the positive electrode and the negative electrode.

[0097] [Positive electrode piece] In a battery, the positive electrode typically includes a positive electrode current collector and a positive electrode active material layer provided on the positive electrode current collector, the positive electrode active material layer containing positive electrode active material. The positive electrode current collector can be a conventional metal foil or a composite current collector (a composite current collector may be formed by providing a metal material on a polymer substrate). As an example, an aluminum foil can be used as the positive electrode current collector.

[0098] In this application, the specific type of positive electrode active material is not limited, and active materials known in the art and usable for battery positive electrodes can be used, and those skilled in the art can select them according to their actual needs. For example, the positive electrode active material may include, but is not limited to, lithium transition metal oxides and / or lithium-containing phosphates with an olivine structure. The lithium transition metal oxide may include undoped and / or optionally doped-modified lithium transition metal oxides, uncoated and / or coated-modified lithium transition metal oxides, and the lithium-containing phosphates with an olivine structure may include undoped and / or optionally doped-modified lithium-containing phosphates with an olivine structure, and uncoated and / or coated-modified lithium-containing phosphates with an olivine structure. Positive electrode active materials within a given range can be obtained by preparation and are commercially available.

[0099] In some specific embodiments of the present application, the positive electrode active material may be selected from lithium transition metal oxides, which include lithium cobalt oxide (e.g., LiCoO2), lithium nickel oxide (e.g., LiNiO2), lithium manganese oxide (e.g., LiMnO2, LiMn2O4), lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide (e.g., LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NCM 333 (abbreviated as), LiNi 0.5 Co 0.2 Mn 0.3 O2(NCM 523 (abbreviated as), LiNi 0.5 Co 0.25 Mn 0.25 O2(NCM 211 (abbreviated as), LiNi 0.6 Co 0.2 Mn 0.2 O2(NCM 622 (abbreviated as), LiNi 0.8 Co 0.1 Mn 0.1 O2(NCM 811 (abbreviated as), LiNi 0.96 Co 0.02 Mn0.02 O2(Ni 96 (abbreviated as LiNi) etc., lithium nickel cobalt aluminum oxide (for example, LiNi 0.85 Co 0.15 Al 0.05 It may contain, but is not limited to, one or more of the following: O2, etc., and modified compounds thereof.

[0100] In some specific embodiments of the present application, the positive electrode active material may include, but is not limited to, at least one of the following: lithium iron phosphate (e.g., LiFePO4 (abbreviated as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (e.g., LiMnPO4), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, or a composite material of lithium iron manganese phosphate and carbon.

[0101] In some specific embodiments of the present application, the positive electrode active material layer may optionally contain a binder, a conductive agent, and other selectable auxiliary agents. For example, the conductive agent may include, but is not limited to, one or more of the following: superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, Super P (SP), graphene, and carbon nanofibers. For example, the binder may include, but is not limited to, one or more of the following: styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).

[0102] [Negative electrode piece] In a battery, the negative electrode typically includes a negative electrode current collector and a negative electrode active material layer provided on the negative electrode current collector, the negative electrode active material layer containing the negative electrode active material. The negative electrode current collector can be a general metal foil or a composite current collector (for example, a composite current collector may be formed by providing a metal material on a polymer substrate). As an example, the negative electrode current collector can be a copper foil.

[0103] In some embodiments of the present application, the battery according to the fourth aspect of the present application may be a lithium-ion battery, in which case the specific type of negative electrode active material is not limited, and active materials known in the art and usable for battery negative electrodes can be used, and those skilled in the art can flexibly select according to their actual needs. For example, the negative electrode active material may include, but is not limited to, one or more of artificial graphite, natural graphite, hard carbon, soft carbon, silicon-based materials, and tin-based materials. Preferably, the silicon-based material may include one or more of elemental silicon, silicate compounds (e.g., silicon monoxide), silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. More preferably, the tin-based material may include one or more of elemental tin, stancate compounds, and tin alloys. Negative electrode active materials within a predetermined range can be obtained by preparation and are commercially available.

[0104] In some specific embodiments of the present application, the negative electrode active material may include silicon-based materials, such as composite negative electrode active materials doped with silicon-based materials and carbon materials. Using silicon-based materials in the negative electrode active material layer is advantageous for further improving the energy density of the battery, and preferably the silicon content in the negative electrode active material is 10 wt% or more.

[0105] In some specific embodiments of the present application, the negative electrode active material layer may optionally contain a binder, a conductive agent, and other selectable auxiliary agents. For example, the conductive agent may include, but is not limited to, one or more of the following: superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. For example, the binder may include, but is not limited to, one or more of the following: styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB). For example, other selectable auxiliary agents may include, but are not limited to, thickeners and dispersants (e.g., sodium carboxymethylcellulose CMC-Na) and PTC thermistor materials.

[0106] In some embodiments of the present application, the battery according to the fourth aspect of the present application may be a lithium metal secondary battery, in which case the negative electrode material may include, but is not limited to, pure metallic lithium. For example, the negative electrode material may be an alloy formed of metallic lithium and various other metals or nonmetallic elements, preferably the metallic element may include, but is not limited to, tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga), indium (In), platinum (Pt), etc., and more preferably the nonmetallic element may include, but is not limited to, boron (B), carbon (C), silicon (Si), etc.

[0107] In some embodiments of the present application, the battery according to the fourth aspect of the present application may be a lithium metal battery without a negative electrode, in which case the negative electrode consists only of a metal foil current collector, and there is no lithium metal on its surface, and during the cycle process, only lithium in the positive electrode is used, and lithium metal is deposited and peeled off on the negative electrode side.

[0108] In some embodiments of the present application, the separator in the battery may include, but is not limited to, a polyethylene porous membrane, a polypropylene porous membrane, a polyimide porous membrane, and a porous membrane formed by the composite of multiple types of polymers.

[0109] In some embodiments of the present application, the shape of the battery according to the fourth aspect of the present application is not particularly limited, and those skilled in the art can flexibly select according to actual requirements. For example, it may be cylindrical, square (understand by referring to FIG. 1), or any other arbitrary shape.

[0110] In some embodiments of the present application, the battery may include an outer package for packaging the positive electrode sheet, negative electrode sheet, separator, and electrolyte.

[0111] In some embodiments, the outer package may include a case and a cover plate. Here, the case includes a bottom plate and side plates connected to the bottom plate, and the bottom plate and side plates surround to form a housing cavity. The case has an opening communicating with the housing cavity, and the cover plate can cover the opening to seal the housing cavity.

[0112] In some embodiments, the positive electrode sheet, negative electrode sheet, and separator can form an electrode assembly by a winding process or a lamination process. The electrode assembly is packaged in the housing cavity. A gel polymer electrolyte can be used for the electrolyte, and the electrode assembly is impregnated with the electrolyte solution in the gel polymer electrolyte. The number of electrode assemblies included in the battery may be one or more, and can be adjusted as needed.

[0113] In some embodiments, the outer package of the battery may be a rigid case, and the rigid case may be a metal case or a non-metal case, such as a rigid plastic case, an aluminum case, a steel case, etc.

[0114] In some embodiments, the battery casing may be a soft pack, such as a bag-type soft pack. The material of the soft bag may include plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), or it may be, for example, an aluminum plastic film.

[0115] In some embodiments of the present invention, the battery may be a battery cell 1 (as understood by referring to Figure 1), a battery module 2 (as understood by referring to Figure 2), or a battery pack 3 (as understood by referring to Figure 3), which consists of a battery cell 1.

[0116] In some embodiments, the battery may be a battery module, and the number of battery cells contained in the battery module may be one or more, the specific number of which can be adjusted according to the application and capacity of the battery module. Figure 2 shows a battery module 2 as one example. Referring to Figure 2, in the battery module 2, a plurality of battery cells 1 may be arranged sequentially along the longitudinal direction of the battery module 2. Of course, they may be arranged in any other manner. Furthermore, the plurality of battery cells 1 may be fixed by fastening means. Preferably, the battery module 2 may include a housing having a housing space in which the plurality of battery cells 1 are housed.

[0117] In some embodiments, the battery modules may be assembled as a battery pack, and the number of battery modules included in the battery pack can be adjusted according to the application and capacity of the battery pack. Referring to Figure 3 or 4 (Figures 3 and 4 show a battery pack 3 as one example), the battery pack 3 may include a battery box and a plurality of battery modules 2 provided in the battery box. The battery box may include an upper housing 4 and a lower housing 5, the upper housing 4 being covered by the lower housing 5 and forming a sealed space for housing the battery modules 2. The plurality of battery modules 2 may be arranged in the battery box in any configuration.

[0118] Furthermore, the present application further provides an electrical device including a battery according to a fourth aspect of the present application. The battery, for example, a battery cell, a battery module, or a battery pack, may serve as a power source for the electrical device or as an energy storage unit for the electrical device. The electrical device may include, but is not limited to, mobile devices (e.g., mobile phones, laptop computers), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), trains, ships, and satellites, and energy storage systems. As can be understood by referring to Figure 5, the electrical device may be a vehicle as one specific example. The electrical device may select a specific type of battery according to its usage needs, for example, a battery cell, a battery module, or a battery pack.

[0119] As one example, the electrical device may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the requirements for high power output and high energy density of the battery in the electrical device, a battery pack or battery module may be employed.

[0120] Other examples include mobile phones, tablet computers, and laptop computers. These devices are typically required to be lightweight and thin, and can employ cells as their power source.

[0121] Examples of the present application are described below. The examples described below are illustrative and are for illustrative purposes only, and should not be understood as limiting the present application. Unless otherwise specified in the examples, specific techniques or conditions shall be followed in accordance with the techniques or conditions or product specifications described in the literature in the art. Unless otherwise specified by the manufacturer, the reagents or equipment used are all common products available on the market.

[0122] Example 1 (1) Manufacturing of positive electrode pieces Lithium nickel-cobalt manganese oxide (LiNi) is used as the positive electrode active material. 0.8 Co 0.1 Mn 0.1 O2 (NCM811), acetylene black as a conductive agent, and PVDF as a binder were mixed in a mass ratio of 98:1:1. N-methylpyrrolidone (NMP) was added as a solvent, and the mixture was stirred until the reaction system was homogeneous to obtain a positive electrode slurry (solid content of 70 wt%). The positive electrode slurry was added at a concentration of approximately 25 mg / cm³. 2 The positive electrode current collector aluminum foil was uniformly coated with the specified amount on both sides, dried at room temperature, then transferred to an oven to continue drying, and finally cut into 40mm x 50mm rectangles to form positive electrode pieces, with a positive electrode surface capacitance of 3.5mAh / cm². 2 That is the case.

[0123] (2) Manufacturing of negative electrode pieces A 50 μm lithium foil was coated onto a 12 μm copper foil using a roll press, and then cut into a 41 mm x 51 mm rectangle to prepare the negative electrode piece.

[0124] (3) Preparation of gel polymer electrolyte 1.0 g of 1,2-dimethoxyethane (DME) was prepared as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt, forming a 1.5 M electrolyte. Then, 0.9 g of polymerizable monomer I-12' and 16.9 mg of azobisdimethylvaleronitrile were added as initiators. (After injection and packaging, the mixture was cured at 60°C for 12 hours to prepare a gel polymer electrolyte.)

[0125] (4) Manufacturing of separators A 12 μm thick porous polyethylene membrane was used as a separator and cut into 45 mm x 55 mm rectangles.

[0126] (5) Manufacturing of secondary batteries Battery assembly: One cut positive electrode and two cut negative electrodes were matched, the positive and negative electrodes were separated in the middle via the aforementioned separator, and the assembly was wrapped in an aluminum-plastic composite bag to form a laminated dry cell. 0.3 g of the compounded electrolyte was injected, and the aluminum-plastic composite bag was vacuum hot-pressed packaged. After standing at room temperature for at least 6 hours, a cycle test was started. The rated capacity of the laminated battery manufactured by this method is 140 mAh.

[0127] Comparative Example 1 The differences from Example 1 are as follows: The gel polymer electrolyte was replaced with a liquid electrolyte.

[0128] Preparation of electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) was used as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) was used as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide was used as the lithium salt to form an electrolyte at a concentration of 1.5 M.

[0129] Comparative Example 2 The differences from Example 1 are as follows: The type of polymerizable monomer added when preparing the gel polymer electrolyte is different.

[0130] (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in a 1.5 M electrolyte solution, and then 0.9 g of methyl acrylate and 16.9 mg of azobisdimethylvaleronitrile as an initiator were added.

[0131] Comparative Examples 3-5 The differences from Comparative Example 2 are as follows: The type of secondary polymerizable monomer added when preparing the gel polymer electrolyte is different.

[0132] The second polymerizable monomers used in Comparative Examples 3, 4, and 5 were vinylene carbonate, hexafluoroisopropyl methacrylate, and hydroxyethyl methacrylate, respectively, as shown in Table 1.

[0133] Examples 2-5 The differences from Example 1 are as follows: When preparing the gel polymer electrolyte, the types of polymerizable monomers added are different. The polymerizable monomers used in Examples 2, 3, 4, and 5 are I-49', I-192', I-84', and I-108', respectively, as shown in Table 1 for details.

[0134] Example 6 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in an electrolyte solution of 1.5 M concentration, and then 0.45 g of polymerizable monomer I-12', 0.45 g of polymerizable monomer I-108', and 20 mg of azobisdimethylvaleronitrile as an initiator were added.

[0135] Example 7 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in an electrolyte solution of 1.5 M concentration, and then 0.45 g of polymerizable monomer I-84', 0.45 g of polymerizable monomer I-192', and 20 mg of azobisdimethylvaleronitrile as an initiator were added.

[0136] Example 8 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in an electrolyte solution of 1.5 M concentration, and then 0.45 g of polymerizable monomer I-12', 0.45 g of the second polymerizable monomer methyl acrylate, and 20 mg of azobisdimethylvaleronitrile as an initiator were added.

[0137] Examples 9-11 The differences from Example 8 are as follows: The type of secondary polymerizable monomer added when preparing the gel polymer electrolyte is different.

[0138] The second polymerizable monomers used in Examples 9, 10, and 11 were vinylene carbonate, hexafluoroisopropyl methacrylate, and hydroxyethyl methacrylate, respectively, as shown in Table 1.

[0139] Examples 12-18 The differences from Example 1 are as follows: When preparing the gel polymer electrolyte, the type of polymerizable monomer added is different. The polymerizable monomers used in Examples 12 to 18 are polymers I-60', I-125', I-137', I-149', I-173', I-205', and I-229', respectively, and are I-60', I-125', I-137', I-149', I-173', I-205', and I-229'. Details are shown in Table 1.

[0140] Example 19 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in a 1.5 M electrolyte solution, and 0.089 g of polymerizable monomer I-12' and 6.0 mg of azobisdimethylvaleronitrile as the initiator were added.

[0141] Example 20 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were formed in an electrolyte solution of 1.5 M concentration, and 0.445 g of polymerizable monomer I-12' and 6.0 mg of azobisdimethylvaleronitrile as an initiator were added.

[0142] Example 21 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt were prepared in a 1.5 M electrolyte solution, and 1.335 g of polymerizable monomer I-12' and 31.0 mg of azobisdimethylvaleronitrile as an initiator were added.

[0143] Example 22 The differences from Example 1 are as follows: (3) Preparation of gel polymer electrolyte: 1.0 g of 1,2-dimethoxyethane (DME) was prepared as the main solvent, 6.4 g of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as the auxiliary solvent, and 1.5 g of lithium bisfluorosulfonyliimide as the lithium salt was prepared in an electrolyte solution of concentration 1.5. Then, 2.225 g of polymerizable monomer I-12' and 31.0 mg of azobisdimethylvaleronitrile were added as initiators.

[0144] The above-described examples of this application exemplify methods for preparing several gel polymer electrolytes. Other gel polymer electrolytes can be prepared by reference to these exemplary methods. Those skilled in the art can readily obtain specific methods for achieving each synthesis step from relevant scientific literature or standard textbooks in the field. Unless otherwise stated, commercially available or literature-known compounds can be used as raw materials for synthesis. Those skilled in organic synthesis will recognize that the properties and order of the proposed synthesis steps can be modified to optimize the production of the compounds described herein. Furthermore, all raw materials, reagents, etc., not explicitly derived from the preparation process are common commercially available products.

[0145] Performance testing: 1. Characterization of the polymer matrix in the obtained gel polymer electrolyte. After mixing the electrolyte obtained in step (3) with the polymerizable monomer and initiator, it was cured at 60°C for 12 hours, then vacuum dried to remove the solvent, washed to remove the lithium salt, dissolved in an appropriate amount of solvent, and finally filtered by precipitation with n-hexane to obtain the polymer matrix. Infrared spectroscopy (IR), nuclear magnetic resonance (NMR), e.g., 1 H or 13 C or 19 F or 31The obtained polymer matrix was characterized by one or more of the following methods: P), mass spectrometry (MS), elemental analysis, gel permeation chromatography (GPC), and laser Raman spectroscopy (LR).

[0146] 2. Needle-piercing test of secondary batteries Under conditions of 25°C, the cells were charged to 4.3V at 0.2C, then charged to 0.05C at a constant voltage of 4.3V, and a 3mm diameter high-temperature resistant steel needle was inserted through the geometric center of the cell at a speed of 25mm / s. The needle remained inside the cell, and the heat generation state at that time was observed. Five parallel test groups were provided for each example. The highest temperature reached was measured using a thermocouple attached 2cm from the needle insertion point on the surface of each cell, and the average value of the five parallel test groups was measured.

[0147] The polymer matrices obtained in Examples 1-22 were characterized by nuclear magnetic resonance (NMR), for example. 1 1H NMR and 19 Characteristic functional groups in the polymer were identified by 1F NMR and infrared spectroscopy (IR), and the polymer structure was identified by elemental analysis. The results of the characterization showed that the polymer matrices obtained by polymerizing the polymerizable monomers in Examples 1 to 22 under initiator conditions have a structure represented by general formula I or general formula II of this application.

[0148] The secondary batteries obtained in Examples 1-22 and Comparative Examples 1-5 were subjected to needle-stick tests under the same conditions, and the test results are shown in Table 1.

[0149] [Table 1]

[0150] Note: The polymerizable monomers I-12', I-49', I-192', I-84', I-108', I-60', I-125', I-137', I-149', I-173', I-205', and I-229' used in Examples 1-22 were all obtained by the manufacturing methods disclosed herein. Methyl acrylate CAS: 96-33-3, Mycryn, 99% purity. Vinylen carbonate CAS: 872-36-6, Heowns, 99% purity. Hexafluoroisopropyl methacrylate CAS: 3063-94-3, Romyer, 99% purity. Hydroxyethyl methacrylate CAS: 868-77-9, Arabitene Biochemistry, 99% purity.

[0151] Results and conclusions As can be seen from Examples 1-22 and Comparative Examples 1-5, the use of polymers having a cyclic phosphate ester structure in the electrolyte is advantageous in improving the thermal stability of the battery and reducing the probability of battery ignition and thermal runaway. Furthermore, as can be seen from Examples 1-5 and Examples 12-18, in cyclic phosphate ester polymers, when X1 and X2 are oxygen rather than sulfur or imino groups, it is advantageous in improving the thermal stability of the battery; when Y is an alkyl group or alkoxy group rather than sulfur or imino groups, it is advantageous in improving the thermal stability of the battery; and as can be seen from Examples 2 and 12, when the cyclic phosphate ester polymer is substituted with fluorine rather than when there is no fluorine-substituted structure, it is advantageous in improving the thermal stability of the battery. Moreover, as can be seen from Examples 1 and Examples 19-22, the thermal stability of the battery also improved as the polymer matrix content in the gel polymer electrolyte increased.

[0152] Finally, it should be noted that the above embodiments are merely illustrative of the technical concepts of the present application and do not limit them. Although the present application has been described in detail with reference to the above embodiments, those skilled in the art will understand that it is still possible to modify the technical concepts described in the above embodiments or to make equivalent substitutions for some or all of the technical features therein, and that such modifications or substitutions do not deviate the essence of the corresponding technical concepts from the scope of the technical concepts of the embodiments of the present application, and that they should all be included within the scope of the claims and specification of the present application. In particular, the technical features described in each embodiment can be combined in any way, provided that there is no structural contradiction. The present application is not limited to the specific embodiments disclosed herein, but includes all technical concepts included in the claims.

Claims

1. A polymer whose general formula is represented by formula I. 【Chemistry 1】 (where m includes 0 and / or 1, n is a positive integer, X １ , X ２ Each independently contains oxygen, sulfur, or an imino group, X ３ It contains oxygen or sulfur, Y contains any one of oxygen, sulfur, an imino group, -S-C substituted with an unsubstituted or arbitrary group １～８ an alkylene group, -NH-C substituted with an unsubstituted or arbitrary group １～８ an alkylene group, C substituted with an unsubstituted or arbitrary group １～８ an alkylene group, C substituted with an unsubstituted or arbitrary group １～８ including any one of alkyleneoxy groups, R １ , R ２ , R ３ , R ４ are each independently hydrogen, fluorine, C substituted with an unsubstituted or arbitrary group １～１０ an alkyl group, C substituted with an unsubstituted or arbitrary group １～１０ including any one of alkoxy groups, R ５ is C substituted with an unsubstituted or arbitrary group １～１０ an alkyl group 【Chemistry 2】 It includes any one of the following, R ９ C is either unsubstituted or substituted with any group. １～１０ (The alkyl group is included, and the arbitrary group includes at least one of the following: halogen, alkyl group, alkoxy group, ester group, and carbonyl group.)

2. The polymer according to claim 1, wherein the halogen contains fluorine.

3. X １ , X ２ Each independently contains either oxygen or sulfur, and Y is oxygen, unsubstituted, or fluorine-substituted C １～８ Alkylene group, unsubstituted or fluorine-substituted C １～８ It contains any one of the alkylene oxy groups, R １ , R ２ , R ３ , R ４ These are, independently, hydrogen, fluorine, unsubstituted or fluorine-substituted C １～１０ C11 is an alkyl group, unsubstituted, or fluorine-substituted C11. １～１０ It contains any one of the alkoxy groups, R ５ C is either unsubstituted or fluorine-substituted. １～１０ alkyl group, 【Transformation 3】 It includes any one of the following, R ９ C is either unsubstituted or fluorine-substituted. １～１０ The polymer according to claim 2, comprising an alkyl group.

4. X １ , X ２ Each contains oxygen independently, X ３ C contains oxygen, and Y is oxygen, unsubstituted, or fluorine-substituted. １～８ Alkylene group, unsubstituted or fluorine-substituted C １～８ The polymer according to claim 3, comprising any one of the alkylene oxy groups.

5. The polymer according to any one of claims 1 to 4, wherein the average molecular weight is 20,000 to 60,000.

6. R １ , R ２ , R ３ , R ４ Each of these is independently unsubstituted or fluorine-substituted C １～１０ C11 is an alkyl group, unsubstituted, or fluorine-substituted C11. １～１０ A polymer according to any one of claims 1 to 5, comprising any one of the alkoxy groups.

7. The polymer according to any one of claims 1 to 6, wherein the polymerizable monomer of the polymer comprises a double bond-containing cyclic phosphate ester compound.

8. The polymer according to any one of claims 1 to 7, wherein the polymerizable monomer is a double-bond-containing cyclic phosphate ester compound.

9. The polymerizable monomer comprises the polymer according to any one of claims 1 to 8. 【Chemistry 4】

10. The polymer according to any one of claims 1 to 9, wherein the polymer comprises at least one of the following compounds. 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】

11. The polymer according to claim 7 or 9, wherein the polymerizable monomer of the polymer further comprises a second polymerizable compound, and the general formula of the polymer is represented by formula II. 【Chemistry 16】 (However, a and b are independent positive integers, and 0.5 ≤ a / b ≤ 4, R ６ C is either unsubstituted or substituted with any of the aforementioned groups. ３～１０ C is an alkyl group, unsubstituted, or substituted with any of the aforementioned groups. ３～１０ C is an epoxy group, unsubstituted, or substituted with any of the aforementioned groups. ３～１０ C is an allyl group, unsubstituted, or substituted with any of the aforementioned groups. ３～１０ (methyl)acryloyl group, unsubstituted or substituted with any of the above groups C ３～１０ It is one of the following acrylates.

12. The polymer according to claim 11, wherein the second polymerizable compound comprises at least one of polymerizable monomers, oligomers, and copolymers of gel polymer electrolytes.

13. The second polymerizable compound is methyl methacrylate, styrene, methyl acrylate, ethyl acrylate, acrylic acid, trimethylsilyl methacrylate, acrolein dimethyl acetal, acrolein diethyl acetal, 2-phenoxyethyl acrylate, tridecafluoro-2-hydroxynonyl ester, trifluoroethyl methacrylate, allyl-1,3-sultone, glycidyl methacrylate, acrylamide, trifluoroethyl acrylate, (acryloxymethyl)dimethylmethoxysilane, cyanoethyl acrylate, hydroxyethyl acrylate, trialyl trimesinate, hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 1-vinyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-allyl-3-ethylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-allyl-1-methylpyrrolidinium bis The polymer according to claim 11 or 12, comprising at least one of (trifluoromethanesulfonyl)imide, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, pentafluorophenol acrylate, vinylene carbonate, maleic anhydride, cyanoethyl acrylate, butyl acrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, and vinylethylene carbonate, preferably at least one of vinylene carbonate, maleic anhydride, cyanoethyl acrylate, butyl acrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyethyl methacrylate, and vinylethylene carbonate.

14. A method for preparing a polymer according to any one of claims 1 to 13, Autopolymerization of double-bond-containing cyclic phosphate ester compounds, and / or, A method for preparing a polymer, comprising copolymerizing a double-bond-containing cyclic phosphate ester compound with a second polymerizable compound.

15. The method for preparing the double bond-containing cyclic phosphate ester compound is as follows: 【Chemistry 17】 By performing a ring-forming reaction, the general formula is [Chemistry 18] To obtain the compound, and / or, 【Chemistry 19】 By performing a substitution reaction, the general formula becomes 【Chemistry 20】 A method for preparing a polymer according to claim 14, comprising obtaining a compound. (where m is 0 or 1, X １ ', X ２ Each of the following independently contains a hydroxyl group, a mercapto group, or an amino group, X １ , X ２ Each independently contains oxygen, sulfur, or an imino group. R １ , R ２ , R ３ , R ４ Each of these is independently a C atom substituted with hydrogen, fluorine, an unsubstituted or arbitrary group. １～１０ C is an alkyl group, unsubstituted, or substituted with any group. １～１０ It contains any one of the alkoxy groups, R ７ , R ８ Each of these is an unsubstituted or substituted C ２～１１ It contains an olefin, Y' contains hydrogen, a hydroxyl group, a mercapto group or an amino group, Y'' contains oxygen, sulfur or an imino group, R ９ C is either unsubstituted or substituted with any group. １～１０ (It includes an alkyl group, and the aforementioned optional group includes at least one of a halogen, an alkyl group, or an alkoxy group.)

16. The aforementioned 【Chemistry 21】 A method for preparing a polymer according to claim 15, wherein the polymer comprises at least one of ethylene glycol, ethanedithiol, 2-mercaptoethanol, mercaptoethylamine, ethanolamine, ethylenediamine, 1,3-propanediol, 1,3-propanedithiol, 3-mercapto-1-propanol, 3-amino-1-propanol, 3-mercapto-1-propamine, and 1,3-propanediamine.

17. The method for preparing the double bond-containing cyclic phosphate ester compound further includes: 【Chemistry 22】 By subjecting it to a sulfidation reaction, the general formula is 【Chemistry 23】 To obtain the compound, and / or, 【Chemistry 24】 By subjecting it to a sulfidation reaction, the general formula is 【Chemistry 25】 A method for preparing a polymer according to claim 15 or 16, comprising obtaining a compound of the above.

18. The method for preparing a polymer according to any one of claims 14 to 17, wherein the double bond-containing cyclic phosphate ester compound comprises at least one polymerizable monomer from polymer I-12, polymer I-49, polymer I-84, polymer I-108, and polymer I-192.

19. A method for preparing a polymer according to any one of claims 14 to 18, wherein the self-polymerization and / or copolymerization is carried out under initiator conditions, the initiator comprising at least one of azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2'-azabis(2-imidazoline) dihydrochloride, 2,2'-azobisisobutylamidine dihydrochloride, benzoyl peroxide, tert-butylbenzoyl peroxide, and methyl ethyl ketone peroxide.

20. A gel polymer electrolyte comprising a polymer matrix and an electrolyte, The polymer matrix comprises a polymer according to any one of claims 1 to 13 or a polymer obtained by a method for preparing a polymer according to any one of claims 14 to 19, wherein the polymer matrix is ​​a gel polymer electrolyte.

21. The gel polymer electrolyte according to claim 20, wherein the mass ratio of the polymer matrix is ​​0.5 wt% to 25 wt%, preferably 5 wt% to 15 wt%, and more preferably 5 wt% to 12 wt%.

22. A battery comprising a gel polymer electrolyte according to claim 20 or 21, and / or a polymer prepared by the polymer preparation method according to any one of claims 13 to 18, and / or a polymer according to any one of claims 1 to 12.

23. An electrical device comprising the battery described in claim 22.

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