CN121237997A - Solid electrolyte, preparation method thereof, lithium ion battery and electric device - Google Patents
Solid electrolyte, preparation method thereof, lithium ion battery and electric deviceInfo
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- CN121237997A CN121237997A CN202511729907.6A CN202511729907A CN121237997A CN 121237997 A CN121237997 A CN 121237997A CN 202511729907 A CN202511729907 A CN 202511729907A CN 121237997 A CN121237997 A CN 121237997A
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Abstract
本申请提供一种固态电解质、其制备方法、锂离子电池和涉电设备。本申请中的固态电解质的制备原料包括如式（1）所示结构的多官能度单体，其在电解液中原位固化形成固态电解质时，多官能度单体的官能度较高，多官能度单体在聚合反应过程中能够形成高度交联的聚合物网络结构，这种结构赋予了聚合物优异的力学性能，如高强度和高模量，使其在承受外部应力时能够保持较好的结构稳定性，也使得聚合物结构耐高电压性能提升，固态电解质不易发生分解或破裂失效，抑制电解质材料在充放电过程中的结构损坏，维持电解质材料的电化学稳定性，从而延长了电池的使用寿命和安全性，保持电池的充放电性能。This application provides a solid electrolyte, its preparation method, a lithium-ion battery, and an electrical device. The raw materials for preparing the solid electrolyte in this application include multifunctional monomers with the structure shown in formula (1). When these monomers are solidified in situ in the electrolyte to form a solid electrolyte, the multifunctional monomers have high functionality. During the polymerization reaction, the multifunctional monomers can form a highly cross-linked polymer network structure. This structure endows the polymer with excellent mechanical properties, such as high strength and high modulus, enabling it to maintain good structural stability when subjected to external stress. It also improves the high voltage resistance of the polymer structure. The solid electrolyte is less prone to decomposition or cracking failure, inhibits structural damage to the electrolyte material during charging and discharging, maintains the electrochemical stability of the electrolyte material, thereby extending the battery's service life and safety, and maintaining the battery's charging and discharging performance.
Description
The application relates to a divisional application, the original application number is 202510907925.2, the application date is 2025, 7 and 2, and the title of the application is a polyfunctional monomer, a preparation method thereof, a solid electrolyte, a lithium ion battery and an electric device.
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a solid electrolyte, a preparation method thereof, a lithium ion battery and electric equipment.
Background
Solid-state batteries, which are one of the leading battery technologies, have recently received attention for their advantages such as high energy density, high safety, and the like. The solid-state battery uses the solid electrolyte to replace the liquid electrolyte in the traditional lithium ion battery, so that the risk of thermal runaway and combustion of the battery can be greatly reduced. The energy density of the solid-state battery is in direct proportion to the working voltage, so that the energy density of the battery can be directly improved by improving the high-voltage resistance of the battery, and the method has important significance for application fields such as electric automobiles, aerospace and the like which need high-energy-density batteries.
However, in the related art, the solid electrolyte is easily decomposed under high voltage conditions, degrading the overall performance of the battery, and further improvement is desired.
Disclosure of Invention
The embodiment of the application provides a solid electrolyte, a preparation method thereof, a lithium ion battery and an electric device, and aims to solve the technical problems.
In a first aspect, embodiments of the present application provide a solid state electrolyte formed from curing a polyfunctional monomer in an electrolyte solution;
The polyfunctional monomer has a structure as shown in formula (1):
Formula (1).
In some embodiments, the solid state electrolyte has a conductivity of 4mS/cm to 10mS/cm.
In some embodiments, the polyfunctional monomer is derived from the reaction of 1, 4-dimethylene cyclohexane diisocyanate and a trifunctional acrylate compound.
In some embodiments, the electrolyte comprises the electrolyte comprising a solvent, a lithium salt, and/or an additive;
the mass percentage of the solvent in the electrolyte is 79% -89%;
The mass percentage of the lithium salt in the electrolyte is 10% -20%;
The mass percentage of the additive in the electrolyte is 1% -5%.
The second aspect of the present application provides a method for producing the solid electrolyte, the method comprising:
providing a pre-polymerization solution, wherein the pre-polymerization solution comprises an electrolyte and a polyfunctional monomer;
enabling the polyfunctional monomer in the prepolymer to undergo an in-situ curing reaction to obtain the solid electrolyte;
wherein the polyfunctional monomer is a polyfunctional monomer with a structure shown in formula (1).
In some embodiments, the curing reaction has a curing temperature of 40 ℃ to 80 ℃ and/or a curing time of 12 hours to 72 hours, and/or
The viscosity of the prepolymer solution is 2 Pa.s-8mPa.s at normal temperature, and/or
The prepolymer solution also includes an initiator.
In some embodiments, the polyfunctional monomer is present in the prepolymer at a mass percent of from 1% to 5%, and/or
The mass percentage of the electrolyte in the prepolymer is 94-98.997%, and/or
The electrolyte comprises a solvent, a lithium salt and/or an additive, and/or
The mass percentage of the initiator in the prepolymer liquid is 0.003-0.15 percent, and/or
The initiator comprises at least one of azo initiator and peroxide initiator.
In some embodiments, the solvent comprises at least one of a carbonate solvent and a carboxylate solvent, and/or
The mass percentage of the solvent in the electrolyte is 79% -89%, and/or
The lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium trifluoromethane sulfonyl imide, lithium difluorosulfonyl imide, lithium diacetate borate, lithium tetrafluoroborate, lithium difluorophosphate, and/or
The mass percentage of the lithium salt in the electrolyte is 10-20%, and/or
The additive comprises at least one of propane sultone, vinyl sulfate, 1,3, 6-hexane trinitrile, and/or
The mass percentage of the additive in the electrolyte is 1% -5%.
In a third aspect, embodiments of the present application provide a lithium ion battery comprising a solid electrolyte as described above, or a solid electrolyte prepared by a method as described above.
In a fourth aspect, embodiments of the present application provide an electrical device comprising a solid state electrolyte as described above, or a solid state electrolyte prepared by a method as described above, or a lithium ion battery as described above.
The embodiment of the application has the beneficial effects that:
The polyfunctional monomer has a structure shown in a formula (1), when the polyfunctional monomer is taken as a reactant raw material to be cured in situ in an electrolyte to form a solid electrolyte, in the first aspect, the acrylate groups are reactive functional groups, the number of the acrylate groups is 6, the polyfunctional monomer has higher functionality, the polyfunctional monomer can form a highly crosslinked polymer network structure in the polymerization reaction process, the highly crosslinked polymer network structure is like a tight and closely woven large net, and molecular chains are mutually entangled and fixed through a large number of chemical bonds, so that the movement of the molecular chains is greatly limited. The structure endows the polymer with excellent mechanical properties, such as high strength and high modulus, so that the polymer can keep better structural stability when bearing external stress, the high voltage resistance of the polymer structure is improved, the solid electrolyte is not easy to decompose or crack to fail, the structural damage of the electrolyte material in the charge and discharge process is inhibited, and the electrochemical stability of the electrolyte material is maintained, thereby prolonging the service life and the safety of the battery and keeping the charge and discharge performance of the battery.
In a second aspect, the urethane groups of the backbone chain of the polyfunctional monomer impart a stronger polarity to the monomer molecules, such that the polyfunctional monomer can interact with electrolyte solvent molecules to increase conductivity, and the urethane groups have a stronger chemical bond energy, and can enhance the structural stability of the solid electrolyte by forming hydrogen bonds or the like, such enhanced structural stability helping the solid electrolyte to maintain its morphology and integrity at high pressure, preventing performance degradation due to structural failure.
In a third aspect, the polyfunctional monomer is polymerized to form a crosslinked polymer, the crosslinked polymer and the electrolyte are combined to form a solid electrolyte, the solid electrolyte contains a carbamate group, and a nitrogen atom and a carbonyl oxygen atom in the carbamate group can form a stronger interaction with the conductive ion, and the interaction helps to stabilize the existence form of the conductive ion, reduce migration and aggregation of the conductive ion under high voltage, and further improve the high voltage resistance of the solid electrolyte.
In the fourth aspect, after the polyfunctional monomer is polymerized, two ends of the carbamate group on the backbone chain are bonded with ester group side groups with larger volumes, and nitrogen atoms and carbonyl oxygen atoms in the carbamate group have lone pair electrons, so that the whole carbamate group has negative charges, thereby endowing the carbamate group with stronger polarity, enabling the carbamate group to enhance the electron cloud density of the ester group side groups connected with the carbamate group, pulling down the HOMO energy level (highest occupied molecular orbital energy level) of the crosslinked polymer, enabling the crosslinked polymer to be harder to lose electrons, requiring larger energy and higher voltage from the outside to be oxidized, and therefore, the ester group side groups with larger volumes at the two ends of the carbamate group have the function of protecting umbrella, bring protection effect to the polymer molecular chain, better resist the oxidization property under the external high voltage, reduce the oxidative decomposition or side reaction of the polymer, reduce the oxidative degradation risk of the solid electrolyte under the high voltage environment, and further improve the high voltage resistance performance of the solid electrolyte.
Drawings
For a clearer description of the application or of the solutions of the prior art, a brief introduction will be given to the drawings that are needed in the description of the embodiments or of the prior art, it being obvious that the drawings in the description below are some embodiments of the application, from which other drawings can be obtained, without the inventive effort, for a person skilled in the art;
FIG. 1 is an infrared spectrum of a polyfunctional monomer of example 1 of the present application;
FIG. 2 is a graph of electrochemical stability window scan for a solid state electrolyte of example 1 of the present application;
fig. 3 is a high voltage cycling graph of the solid state soft pack full cells of example 1 and comparative example 1 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower directions of the device in actual use or operation, and specifically the directions of the drawings in the drawings, while "inner" and "outer" are used with respect to the outline of the device.
In the related art, the solid electrolyte is easily decomposed under the high voltage condition, and the overall performance of the battery is reduced, which needs to be further improved.
The application provides a polyfunctional monomer which is applied to solid electrolyte, and the polyfunctional monomer has a structure shown as a formula (1):
Formula (1);
Wherein each R 1、R2、R3、R4、R5、R6 is independently selected from an acrylate group or a hydroxyl group, and at most only one of R 1、R2、R3、R4、R5、R6 is a hydroxyl group, R 7 is selected from an alkyl group or a cycloalkyl group.
In this embodiment, the polyfunctional monomer has a structure as shown in formula (1), and when the polyfunctional monomer is used as a reactant raw material to form a solid electrolyte by in-situ curing in an electrolyte, in the first aspect, the acrylate groups are reactive functional groups, the number of the acrylate groups is at least 5, the polyfunctional monomer has higher functionality, the polyfunctional monomer can form a highly crosslinked polymer network structure in the polymerization reaction process, the highly crosslinked polymer network structure is like a tightly woven large network, and the molecular chains are intertwined and fixed through a large number of chemical bonds, so that the movement of the molecular chains is greatly limited. The structure endows the polymer with excellent mechanical properties, such as high strength and high modulus, so that the polymer can keep better structural stability when bearing external stress, the high voltage resistance of the polymer structure is improved, the solid electrolyte is not easy to decompose or crack to fail, the structural damage of the electrolyte material in the charge and discharge process is inhibited, and the electrochemical stability of the electrolyte material is maintained, thereby prolonging the service life and the safety of the battery and keeping the charge and discharge performance of the battery.
In a second aspect, the urethane groups of the backbone chain of the polyfunctional monomer impart a stronger polarity to the monomer molecules, such that the polyfunctional monomer can interact with electrolyte solvent molecules to increase conductivity, and the urethane groups have a stronger chemical bond energy, and can enhance the structural stability of the solid electrolyte by forming hydrogen bonds or the like, such enhanced structural stability helping the solid electrolyte to maintain its morphology and integrity at high pressure, preventing performance degradation due to structural failure.
In a third aspect, the polyfunctional monomer is polymerized to form a crosslinked polymer, the crosslinked polymer and the electrolyte are combined to form a solid electrolyte, the solid electrolyte contains a carbamate group, and a nitrogen atom and a carbonyl oxygen atom in the carbamate group can form a stronger interaction with the conductive ion, and the interaction helps to stabilize the existence form of the conductive ion, reduce migration and aggregation of the conductive ion under high voltage, and further improve the high voltage resistance of the solid electrolyte.
In the fourth aspect, after the polyfunctional monomer is polymerized, two ends of the carbamate group on the backbone chain are bonded with ester group side groups with larger volumes, and nitrogen atoms and carbonyl oxygen atoms in the carbamate group have lone pair electrons, so that the whole carbamate group has negative charges, thereby endowing the carbamate group with stronger polarity, enabling the carbamate group to enhance the electron cloud density of the ester group side groups connected with the carbamate group, pulling down the HOMO energy level (highest occupied molecular orbital energy level) of the crosslinked polymer, enabling the crosslinked polymer to be harder to lose electrons, requiring larger energy and higher voltage from the outside to be oxidized, and therefore, the ester group side groups with larger volumes at the two ends of the carbamate group have the function of protecting umbrella, bring protection effect to the polymer molecular chain, better resist the oxidization property under the external high voltage, reduce the oxidative decomposition or side reaction of the polymer, reduce the oxidative degradation risk of the solid electrolyte under the high voltage environment, and further improve the high voltage resistance performance of the solid electrolyte.
In a fifth aspect, after polymerization of the polyfunctional monomer, the two ends of the carbamate group on the backbone chain are bonded with a bulky side group of the ester group, and specific intermolecular interactions exist between the carbamate group and the bulky side group of the ester group, so that the polymer cannot generate free ionic fragment groups under high voltage (> 4.5V), and the solid electrolyte can match with a high-voltage positive electrode and shows strong high-voltage resistance advantage. Taking lithium cobaltate as an example, in the charging process, positive tetravalent cobalt ions with high valence are formed after lithium cobaltate is removed, the high valence cobalt ions have high chemical activity and are easy to react with surrounding substances such as solvent molecules, so that the surface structure of the positive electrode active particles is unstable, and the surrounding substances of the high valence cobalt ions are easy to be oxidized and decomposed into ion fragments. The carbamate and ester side groups in the polymer molecular chain can generate better synergistic complexing effect with positive tetravalent cobalt ions, and the cobalt ions are fixed on the surface of positive electrode active particles through coordination chemical effect, so that the metal ions on the surface of the positive electrode active particles are effectively stabilized, the dissolution and migration of the metal ions are reduced, and the stability of the polymer molecular chain in a high-voltage field is improved. In addition, the intermolecular interaction between the carbamate group and the larger-volume ester group side group also obviously improves the complexation capability of a polymer molecular chain to lithium ions and solvents, and the distribution of the lithium ions is easily influenced by an electric field and chemical reaction under high voltage, so that the local aggregation phenomenon is caused. The polymer molecular chain forms a stable complex with lithium ions and a solvent, so that the lithium ions can be uniformly dispersed, the local aggregation of the lithium ions is reduced, and the lithium ions can be uniformly and efficiently transmitted in the polymer electrolyte, thereby improving the high voltage resistance of the polymer electrolyte and prolonging the service life of the battery.
In one embodiment, R 7 has a structure as shown in formula (2) or formula (3):
formula (2);
Formula (3);
wherein n1 is an integer from 0 to 10, n2 is an integer from 0 to 10, n3 is an integer from 0 to 3, and the sum of n1 and n2 is between 1 and 10;
n4 is selected from an integer of 0-5, n5 is selected from an integer of 0-5, n6 is selected from an integer of 0-3, n7 is selected from an integer of 0-3, and the sum of n4 and n5 is between 1 and 10.
In this embodiment, the sum of n1 and n2 is between 1 and 10, and/or the sum of n4 and n5 is between 1 and 10, so that the volume and molecular weight of the polyfunctional monomer can be ensured not to be too large, and the viscosity of the prepolymer can not be too large when the polyfunctional monomer is added into the prepolymer, thereby facilitating the infiltration of the prepolymer to the electrode.
In one embodiment, n1 is selected from integers from 3-10, n2 is selected from integers from 0-2, n3 is selected from integers from 0-1, and the sum of n1 and n2 is between 3-10.
In one embodiment, n4 is selected from integers from 0-2, n5 is selected from integers from 0-2, n6 is selected from integers from 0-1, n7 is selected from integers from 0-1, and the sum of n4 and n5 is 4.
In one embodiment, the polyfunctional monomer includes at least one of the following compounds:
、、、、、、、。
By adopting the polyfunctional monomer with the structure, R 1、R2、R3、R4、R5、R6 is independently selected from acrylate groups or hydroxyl groups, the number of the functionality is between 5 and 6, the crosslinking can be performed efficiently, the structural stability of the polymer is improved, the high-voltage stability of the solid electrolyte is further improved, and the high functionality can enable the polyfunctional monomer to undergo polymerization reaction to form a polymer network under a lower content, so that the solid electrolyte has better conductivity. The R 7 group adopts an alkyl and cycloalkyl structure, the numerical values of the related n1 to n6 are controlled, the volume and the molecular weight of the polyfunctional monomer are ensured not to be too large, and when the polyfunctional monomer is added into the prepolymer, the viscosity of the prepolymer is not too large, so that the infiltration of the prepolymer to the electrode is facilitated. In addition, the polyfunctional monomer has a basically symmetrical molecular structure, which is beneficial to more effectively approaching each other and generating reaction between polyfunctional monomer molecules, thereby promoting the formation of a cross-linked structure and improving the structural stability of the material. Therefore, the polyfunctional monomer has better effects on the performances of the viscosity of the prepolymer, the conductivity of the solid electrolyte, the high voltage resistance of the solid electrolyte and the like, and has better performance on the high voltage cycle performance of the battery.
In one embodiment, the polyfunctional monomer has a number of functionalities between 5 and 6. Alternatively, the polyfunctional monomer has a functionality number of 5 or 6. Functionality refers to the number of functional groups in a monomer molecule that are capable of participating in a reaction, directly related to the reactivity of the reactants and the structural characteristics of the product. Generally, the greater the number of functionalities, the more active sites the monomer molecules are in the reaction, the faster the reaction rate, and the greater the probability of the monomer molecules participating in the polymerization reaction, the greater the degree of crosslinking of the resulting polymer. When the number of functionalities of the polyfunctional monomer is less than 5, the structural stability of the polymer is easily lowered and the solid electrolyte is easily decomposed. When the number of the functionalities of the polyfunctional monomer is more than 6, the crosslinking points are easily too dense, the molecular pores constructed by the polymer molecular chains are smaller, the electrolyte absorption and the shuttling and conduction of conductive ions among the molecular pores are not facilitated, the flexible movement of the molecular chains is seriously hindered, the flexibility of the polymer is greatly reduced, and the polymer becomes stiff and fragile. At the same time, the tightly crosslinked network structure also limits the transport of ions within the polymer, so that the ion transport properties of the solid electrolyte are deteriorated.
In the embodiment, the number of the functionalities of the polyfunctional monomer is set between 5 and 6, so that the generated polymer has proper crosslinking degree, and simultaneously, the carbamate groups on the polyfunctional monomer dry chain can endow monomer molecules with stronger flexibility, nitrogen atoms and carbonyl oxygen atoms in the carbamate groups have larger polarity, the carbamate groups can bring partial charges and steric hindrance weakening effects, and the carbamate groups can generate specific intermolecular interactions with the bulky ester group side groups at two ends, and the interactions reduce the energy barrier of the rotation peristaltic motion of the main chain of the polymer molecular chain, so that the rotation and the peristaltic motion of the polymer molecular chain can be generated to a certain extent when the polymer molecular chain is subjected to smaller external force, thereby improving the movement capability of the polymer molecular chain, and injecting a lubricant for the originally stiff polymer network structure, so that the problems of reduced flexibility and reduced absorption capability of the polymer molecular chain pore space caused by the high crosslinking degree of the side groups are effectively counteracted. Meanwhile, the carbamate group improves the movement capacity of the polymer molecular chain, indirectly improves the ion transmission performance, enhances the movement capacity of the polymer molecular chain, opens up a more smooth channel for the ion transmission in the polymer, enables the ions to migrate between the polymer molecular chains more freely, and improves the ion transmission efficiency of the solid electrolyte.
In one embodiment, the polyfunctional monomer has a symmetrical molecular structure. In this example, high functionality and structurally symmetrical polyfunctional monomers exhibit a significant propensity to form highly crosslinked polymer network structures during polymerization. High functionality monomer means that each monomer molecule possesses multiple active sites that are capable of rapidly and largely chemically reacting with adjacent monomer molecules to form multiple chemical bond linkages as polymerization occurs. The symmetrical structure allows the polyfunctional monomer molecules to have a spatially regular arrangement, which helps to more efficiently get closer to each other and react with each other during the polymerization process, thereby promoting the formation of a crosslinked structure.
The high functionality characteristic, the structural symmetry characteristic and the urethane groups in molecules of the polyfunctional monomer respectively play a unique role in the polymer, and are mutually cooperated, so that the advantages of the polyfunctional monomer can be fully exerted, the solid electrolyte material with excellent structural stability, high voltage resistance, good flexibility and high-efficiency ion transmission performance can be prepared, and the requirement of a battery on the high-performance material can be met.
The application also provides a preparation method of the polyfunctional monomer, which comprises the following steps:
s1, providing a trifunctional acrylate monomer and a diisocyanate compound;
S2, reacting a trifunctional acrylate monomer with a diisocyanate compound to obtain a polyfunctional monomer;
wherein the polyfunctional monomer has a structure as shown in formula (1):
Formula (1);
Wherein each R 1、R2、R3、R4、R5、R6 is independently selected from an acrylate group or a hydroxyl group, and at most only one of R 1、R2、R3、R4、R5、R6 is a hydroxyl group, R 7 is selected from an alkyl group or a cycloalkyl group.
In this embodiment, the trifunctional acrylate monomer refers to a monomer having a functionality number of 3, and the functionality groups are acrylate groups.
In one embodiment, the molar ratio between the trifunctional acrylate monomer and the diisocyanate is 2 (1-1.1).
In one embodiment, the trifunctional acrylate monomer and diisocyanate are reacted at a temperature of 20 ℃ to 50 ℃.
In one embodiment, the diisocyanate compound has a structural formula shown in formula (4):
o=c=n-R 7 -n=c=o formula (4);
Wherein R 7 is selected from alkyl or cycloalkyl.
In one embodiment, the method of preparing the trifunctional acrylate monomer comprises:
s11, pentaerythritol and acrylic acid are provided;
S12, enabling pentaerythritol and acrylic acid to undergo esterification reaction under the condition of a catalyst to generate a trifunctional acrylate monomer.
In one embodiment, the molar ratio between pentaerythritol and acrylic acid is 1 (3-3.1).
In one embodiment, the reaction temperature of the esterification reaction is from 75 ℃ to 80 ℃.
In a specific embodiment, the polyfunctional monomer is prepared as follows:
S111, adding pentaerythritol, acrylic acid, p-toluenesulfonic acid, copper chloride and cyclohexane into a flask;
S112, introducing oxygen-containing gas (the volume percentage of oxygen is 5 percent and the volume percentage of nitrogen is 95 percent) into the flask, and simultaneously, carrying out dehydration and esterification reaction for 12 hours at 75-80 ℃, and discharging generated water to the outside of the system by using a fractionating tube during the reaction;
S113, after the reaction in the step S112 is finished, adding n-propyl acetate and distilled water into the reaction solution to dilute, fully stirring, standing to separate the reaction solution into a water phase (lower layer) and an organic solvent phase (upper layer), removing the water phase of the lower layer, then adding a 20wt% sodium hydroxide aqueous solution into the organic solvent phase to neutralize the acid component contained in the organic solvent phase, standing to separate the reaction solution into the water phase (lower layer) and the organic solvent phase (upper layer), removing the water phase of the lower layer, recovering the organic solvent phase, then adding distilled water into the recovered organic solvent phase to wash, standing, removing and separating the water phase (lower layer), and recovering the organic solvent phase of the upper layer;
s114, introducing dry air into the organic solvent phase finally recovered in the step S113, and heating to 70 ℃ under reduced pressure to distill off the solvent, thereby obtaining trifunctional acrylate;
s115, adding diisocyanate compound into the trifunctional acrylate, stirring and reacting for 5 hours at normal temperature, and stirring and reacting for 2 hours at 50 ℃ to obtain the polyfunctional monomer.
In this example, the polyfunctional monomer is prepared according to the general reaction scheme:
。
In the embodiment, the preparation method of the polyfunctional monomer is efficient and simple, and has the characteristics of low energy consumption, no pollution, easiness in production and the like.
The application also provides a solid electrolyte which is formed by solidifying the polyfunctional monomer in electrolyte, wherein the polyfunctional monomer adopts the polyfunctional monomer or the polyfunctional monomer obtained by adopting the preparation method.
In one embodiment, the solid state electrolyte has a conductivity of 4mS/cm to 10mS/cm. Since the main chain of the polymer molecules composing the solid electrolyte contains the carbamate group, the carbamate group has higher dielectric constant, which means that the group can conduct charges more effectively under the action of an electric field, local aggregation of the charges is avoided, and under a high-voltage environment, the high-efficiency ion conduction is helpful for maintaining the stability of the electrolyte and improving the conductivity of the solid electrolyte.
The application also provides a preparation method of the solid electrolyte, which comprises the following steps:
s21, providing a prepolymerization solution, wherein the prepolymerization solution comprises an electrolyte and a polyfunctional monomer;
S22, enabling polyfunctional monomers in the prepolymer to undergo an in-situ curing reaction to obtain a solid electrolyte;
Wherein the polyfunctional monomer is the polyfunctional monomer as described above or the polyfunctional monomer obtained by the preparation method as described above.
In one embodiment, the prepolymer has a viscosity of 2 Pa.s to 8mPa.s at ambient temperature. Alternatively, the viscosity of the prepolymer liquid at ordinary temperature may be in a range between any one or any two of 2mpa.s, 3mpa.s, 5mpa.s, 7mpa.s, 8mpa.s, and the like, without limitation. In this embodiment, the viscosity of the pre-polymerization solution at normal temperature is low, and the low-viscosity pre-polymerization solution has better flowing property, so that the pre-polymerization solution can better infiltrate the electrode pores and the diaphragm holes, and a uniform and stable gel structure and a continuous ion channel can be formed in the battery more easily, thereby improving the high voltage resistance and the ion transmission performance of the solid electrolyte.
In one embodiment, the curing reaction has a curing temperature of 40 ℃ to 80 ℃ and/or a curing time of 12 hours to 72 hours.
In one embodiment, the pre-polymerization solution further comprises an initiator, and the initiator can initiate polymerization reaction between the polyfunctional monomers, so that the efficiency of the polymerization reaction is improved.
In one embodiment, the mass percent of the initiator in the prepolymer solution is 0.003% -0.15%, alternatively, the mass percent of the initiator in the prepolymer solution may be any one or any two of 0.003%, 0.005%, 0.01%, 0.05%, 0.15%, etc., without limitation.
In one embodiment, the initiator comprises at least one of azo-type initiator, peroxide initiator. For example, the initiator may include at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl peroxybenzoate.
In one embodiment, the mass percent of the polyfunctional monomer in the prepolymer is 1% to 5%. Alternatively, the mass percentage of the polyfunctional monomer in the prepolymer may be in a range between any one or any two of 1%, 2%, 3%, 4%, 5%, etc., without limitation. In this embodiment, the polyfunctional monomer is a high-functionality monomer, each functionality is a reaction site, and the dense reaction sites endow the polyfunctional monomer with higher reactivity, so that polymerization reaction can be performed to form a polymer network at a lower content, and the polymerized molecular chain has better high-voltage resistance.
In this embodiment, when the mass percentage of the polyfunctional monomer in the prepolymer is less than 1%, the polyfunctional monomer cannot be effectively cured, the structure of the formed solid electrolyte is loose, and the mechanical properties, ion transport properties and high voltage resistance of the solid electrolyte are reduced. When the mass percentage of the polyfunctional monomer in the prepolymer is more than 5%, the viscosity of the prepolymer is easily too high, the infiltration of the prepolymer to the battery electrode is not facilitated, and the electrochemical performance of the battery is reduced.
In one embodiment, the mass percentage of the electrolyte in the prepolymer is 94-98.997%. Alternatively, the mass percentage of the electrolyte in the prepolymer may be in a range between any one or any two of 94%, 95%, 96%, 97%, 98.997%, etc., without limitation.
In one embodiment, the electrolyte includes a solvent, a lithium salt, and/or an additive.
In one embodiment, the solvent is 79% -89% by mass of the electrolyte. Alternatively, the mass percentage of the solvent in the electrolyte may be in a range between any one or any two of 79%, 82%, 84%, 86%, 89%, etc., without limitation.
In one embodiment, the solvent comprises at least one of a carbonate solvent and a carboxylate solvent. For example, the solvent may include at least one of propyl propionate, dimethyl carbonate, methyl ethyl carbonate, ethyl propionate, ethylene carbonate, fluoroethylene carbonate. In this embodiment, the polyfunctional monomer contains a urethane group that is capable of enhancing the structural stability of the solid electrolyte by forming hydrogen bonds with the solvent as described above, and this enhanced structural stability helps the solid electrolyte maintain its structural integrity at high voltages and reduces degradation of battery performance due to structural failure of the solid electrolyte.
In one embodiment, the mass percentage of the lithium salt in the electrolyte is 10% -20%, alternatively, the mass percentage of the lithium salt in the electrolyte may be any one or any two of 10%, 12%, 14%, 16%, 20%, etc., without limitation.
In one embodiment, the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium trifluoromethane sulfonyl imide, lithium bis-fluoro sulfonyl imide, lithium bis-acetate borate, lithium tetrafluoroborate, lithium difluorophosphate.
In one embodiment, the additive is present in the electrolyte in an amount of 1% to 5% by mass. Alternatively, the mass percentage of the additive in the electrolyte may be in a range between any one or any two of 1%, 2%, 3%, 4%, 5%, etc., without limitation.
In one embodiment, the additive comprises at least one of propane sultone, vinyl sulfate, 1,3, 6-hexanetrinitrile.
The application also provides a lithium ion battery comprising the solid electrolyte or the solid electrolyte prepared by adopting the method.
The application also provides an electric device comprising the solid electrolyte, or the solid electrolyte prepared by the method, or the lithium ion battery. In this embodiment, the type of the electric device is not limited, and the electric device may be an automobile, a ship, an unmanned aerial vehicle, a fixed power supply, a portable power supply, or the like.
The application is further illustrated by the following examples. The experimental materials used in the following examples are all commercially available from conventional biochemical reagent companies unless otherwise specified.
Example 1
A method for preparing a polyfunctional monomer, comprising the steps of:
(1) Into a flask were charged 1mol of pentaerythritol, 3mol of acrylic acid, 6g of p-toluene sulfonic acid, 0.2g of cupric chloride, and 38g of cyclohexane;
(2) Introducing oxygen-containing gas (the volume percentage of oxygen is 5 percent and the volume percentage of nitrogen is 95 percent) into the flask, and simultaneously carrying out dehydration esterification reaction for 12 hours at 75-80 ℃, and discharging generated water outside the system by using a fractionating tube during the reaction;
(3) After the reaction of the step (2), adding 100g of n-propyl acetate and 8g of distilled water into the reaction solution to dilute, fully stirring, standing to separate the reaction solution into an aqueous phase (lower layer) and an organic solvent phase (upper layer), removing the aqueous phase of the lower layer, then adding a 20wt% sodium hydroxide aqueous solution into the organic solvent phase to neutralize the acid component contained in the organic solvent phase, standing to separate the reaction solution into the aqueous phase (lower layer) and the organic solvent phase (upper layer), removing the aqueous phase of the lower layer, recovering the organic solvent phase, then adding distilled water into the recovered organic solvent phase to wash, standing, removing the separated aqueous phase (lower layer), and recovering the organic solvent phase of the upper layer;
(4) Introducing dry air into the organic solvent phase finally recovered in the step (3), and heating to 70 ℃ under reduced pressure to distill off the solvent, thereby obtaining trifunctional acrylate;
(5) 1mol of the trifunctional acrylate is taken, 0.5mol of 1, 3-propylene diisocyanate is added, stirring reaction is carried out for 5 hours at normal temperature, and stirring reaction is carried out for 2 hours at 50 ℃ to obtain the polyfunctional monomer.
In this embodiment, the structural formula of the polyfunctional monomer is:
。
A preparation method of a lithium ion battery comprises the following steps:
(6) 3g of the polyfunctional monomer prepared in the embodiment and 0.03g of azodiisobutyronitrile are dissolved in 96.97g of electrolyte to obtain a prepolymer, wherein the electrolyte comprises 39.97g of propyl propionate, 12g of methyl ethyl carbonate, 14g of ethylene carbonate, 11g of fluoroethylene carbonate, 1g of propane sultone, 1g of vinyl sulfate, 2g of 1,3, 6-hexanetrinitrile and 12g of lithium hexafluorophosphate, 3g of lithium difluorosulfimide and 1g of lithium difluorophosphate;
(7) Injecting the prepolymer into a dry cell formed by assembling a positive electrode plate, a negative electrode plate and a diaphragm at the inner room temperature of a drying room (the relative humidity is lower than 2 percent and the dew point is lower than-40 oC), pre-sealing the dry cell by using a thermoplastic sealing machine, standing the dry cell at room temperature for 24: 24h, putting the dry cell into a hot oven, slowly heating the dry cell to 50 ℃, reacting the dry cell at 24: 24h, and curing the prepolymer in the dry cell in the heating process to obtain a solid electrolyte through in-situ heat curing to prepare the lithium ion battery.
Example 2
The main difference between example 2 and example 1 is that:
1, 3-propanediol was replaced with hexamethylene diisocyanate, and the rest was the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 3
The main difference between example 3 and example 1 is that:
1, 3-propanediol is replaced with 1, 10-decane diisocyanate, and the rest is the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 4
The main difference between example 4 and example 1 is that:
1, 3-propanediol was replaced with 1-methylbutane-1, 4-diisocyanate, and the remainder was the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
example 5
The main difference between example 5 and example 1 is that:
1, 3-propanediol is replaced with 1, 2-diethylpentane-1, 5-diisocyanate, the remainder being the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 6
The main difference between example 6 and example 1 is that:
1, 3-propanediol is replaced with 1, 4-cyclohexanediisocyanate, the remainder being the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 7
The main difference between example 7 and example 1 is that:
1, 3-propanediol is replaced with 1, 4-dimethylene cyclohexane diisocyanate, and the rest is the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 8
The main difference between example 8 and example 1 is that:
adjusting the ratio of the added raw materials, namely adding pentaerythritol (1 mol) and acrylic acid (3 mol), heating and reacting to obtain trifunctional acrylic ester, simultaneously adding pentaerythritol (1 mol) and acrylic acid (2 mol), heating and reacting to obtain difunctional acrylic ester, stirring and reacting the two acrylic esters and 1, 3-propylene diisocyanate at normal temperature for 5h, stirring and reacting at 50 ℃ for 2 h to obtain a target product monomer, and the rest is the same as in example 1;
in this embodiment, the structural formula of the polyfunctional monomer is:
。
Example 9
The main difference between example 9 and example 1 is that:
In the prepolymerization solution, the polyfunctional monomer consists of the polyfunctional monomer (simply referred to as monomer 1) prepared in example 1 and the polyfunctional monomer (simply referred to as monomer 2) prepared in example 8, wherein the addition amount of the monomer 1 is 0.5mol, and the addition amount of the monomer 2 is 0.5mol;
The remainder was the same as in example 1.
Example 10
The main difference between example 10 and example 1 is that:
The preparation method of the prepolymer liquid comprises the following steps:
Dissolving 5g of the polyfunctional monomer prepared in example 1 and 0.05g of azodiisobutyronitrile in 94.95g of electrolyte to obtain a prepolymer, wherein the electrolyte comprises 37.95g of propyl propionate, 12g of methyl ethyl carbonate, 14g of ethylene carbonate, 11g of fluoroethylene carbonate, 1g of propane sultone, 1g of vinyl sulfate, 2g of 1,3, 6-hexanetrinitrile, 12g of lithium hexafluorophosphate, 3g of lithium difluorosulfimide and 1g of lithium difluorophosphate;
The remainder was the same as in example 1.
Example 11
The main difference between example 11 and example 1 is that:
The preparation method of the prepolymer liquid comprises the following steps:
3g of the polyfunctional monomer prepared in example 1 and 0.03g of azobisisobutyronitrile were dissolved in 96.97g of an electrolyte to obtain a prepolymer, wherein the electrolyte comprises 31.97g of propyl propionate, 10g of ethyl propionate, 10g of propylene carbonate, 10g of ethylene carbonate, 15g of fluoroethylene carbonate, 0.5g of vinylene carbonate, 1g of ethylene sulfate, 2.5g of 1,3, 6-hexanetrinitrile, 13g of lithium hexafluorophosphate, 2.5g of lithium difluorosulfonimide and 0.5g of lithium dioxaborate.
The remainder was the same as in example 1.
Example 12
The main difference between example 12 and example 1 is that:
The preparation method of the prepolymer liquid comprises the following steps:
1g of the polyfunctional monomer prepared in example 1 and 0.01g of azobisisobutyronitrile were dissolved in 98.99g of an electrolyte to obtain a prepolymer, wherein the electrolyte comprises 41.99g of propyl propionate, 12g of methylethyl carbonate, 14g of ethylene carbonate, 11g of fluoroethylene carbonate, 1g of propane sultone, 1g of vinyl sulfate, 2g of 1,3, 6-hexanetrinitrile, 12g of lithium hexafluorophosphate, 3g of lithium difluorosulfimide and 1g of lithium difluorophosphate;
The remainder was the same as in example 1.
Example 13
The main difference between example 13 and example 1 is that:
The preparation method of the prepolymer liquid comprises the following steps:
Dissolving 0.8g of the polyfunctional monomer prepared in example 1 and 0.008g of azodiisobutyronitrile in 99.192g of electrolyte to obtain a prepolymer, wherein the electrolyte comprises 42.192g of propyl propionate, 12g of methyl ethyl carbonate, 14g of ethylene carbonate, 11g of fluoroethylene carbonate, 1g of propane sultone, 1g of vinyl sulfate, 2g of 1,3, 6-hexanetrinitrile, 12g of lithium hexafluorophosphate, 3g of lithium difluorosulfimide and 1g of lithium difluorophosphate;
The remainder was the same as in example 1.
Example 14
The main difference between example 14 and example 1 is that:
The preparation method of the prepolymer liquid comprises the following steps:
dissolving 7.3g of the polyfunctional monomer prepared in example 1 and 0.073g of azobisisobutyronitrile in 92.627g of an electrolyte to obtain a prepolymer, wherein the electrolyte comprises 35.627g of propyl propionate, 12g of methyl ethyl carbonate, 14g of ethylene carbonate, 11g of fluoroethylene carbonate, 1g of propane sultone, 1g of vinyl sulfate, 2g of 1,3, 6-hexanetrinitrile, 12g of lithium hexafluorophosphate, 3g of lithium difluorosulfimide and 1g of lithium difluorophosphate;
The remainder was the same as in example 1.
Example 15
The main difference between example 15 and example 1 is that:
1, 3-propanediol is replaced with 1, 15-pentadecane diisocyanate, and the rest is the same as in example 1;
in this comparative example, the structural formula of the polyfunctional monomer is:
。
comparative example 1
The main difference between comparative example 1 and example 1 is that:
The polyfunctional monomer is replaced with a compound represented by the following formula (5):
Formula (5);
The remainder was the same as in example 1.
Comparative example 2
The main difference between comparative example 2 and example 1 is that:
step (1) is that 1mol of pentaerythritol, 2mol of acrylic acid, 6g of p-toluenesulfonic acid, 0.2g of cupric chloride and 38g of cyclohexane are added into a flask;
the remainder was the same as in example 1;
in this comparative example, the structural formula of the polyfunctional monomer is:
。
Comparative example 3
The main difference between comparative example 3 and example 1 is that:
The polyfunctional monomer is replaced with a compound represented by the following formula (6):
Formula (6);
The remainder was the same as in example 1.
The testing method comprises the following steps:
and (one) infrared spectrum test:
The polyfunctional monomer sample prepared in example 1 was placed on the surface of an optical platform crystal of an ATR (model is 20) element of an infrared spectrometer, infrared ATR test software was turned on, test parameters were set, the resolution was 4, and the number of scans was set to 32. After the testing instrument is started, the knob above the reflecting plate is rotated to compress the sample to be tested, so that the sample to be tested is fully contacted with the emitting hole below, and data collection is started. After the test is completed, infrared spectrum information of the sample is obtained as shown in fig. 1.
The infrared spectrum test result of fig. 1 shows that the absorption peak at 3343cm -1 is the stretching vibration peak of the nitrogen-hydrogen bond in the carbamate group, the absorption peak at 1721cm -1 is the stretching vibration peak of the carbonyl group, which is the characteristic peak of the carbonyl group in the acrylic ester, the absorption peak at 1668cm -1 is the stretching vibration peak of the carbon-oxygen double bond of the carbamate group, the absorption peak at 1264cm -1 is the stretching vibration peak of the carbon-oxygen single bond of the carbamate group, and the absorption peak at 1172cm -1 is the stretching vibration of the ester group, which all prove the chemical structure of the polyfunctional monomer.
(II) viscosity test:
The prepolymer solutions prepared in examples 1 to 15 and comparative examples 1 to 3 were tested for viscosity using an NDJ-5S digital display rotary viscometer. During testing, the pre-polymerized liquid sample is poured into a flat bottom container with the diameter larger than 60mm, the temperature of the pre-polymerized liquid is maintained at25 ℃, and the operation table top is stable and free from vibration. The instrument protection frame is reversely screwed into the lower end of the instrument, the L0 rotor is screwed into the universal joint of the instrument anticlockwise, and the lifting button is rotated, so that the rotor is slowly immersed into the prepolymerization liquid until the liquid level mark of the rotor, namely the groove scale, and the liquid level form the same plane, and the instrument level is adjusted again. Pressing the rotor selection key, selecting the rotation speed and then pressing the determination key. And the rotor starts to rotate, and after the display value is stable, the viscosity value is read by pressing a stop key. The test results are shown in table 1 below.
(III) electrochemical stability window test:
the stainless steel sheet was placed in a 2016 type battery case, the pre-polymerization liquid samples prepared in examples 1 to 15 and comparative examples 1 to 3 were dropped, the lithium sheet and the battery case were covered and clamped, and the CR2016 type button battery assembly was completed in a glove box filled with high purity argon gas, and 4 batteries were prepared for each group of samples. And heating the sample to 50 ℃ for reaction for 24 hours, and carrying out linear voltammetric scanning by using an electrochemical workstation (BioLogic Science Instruments) to measure an electrochemical stability window, wherein the initial potential is 2.5V, the highest potential is 6V, the scanning speed is 10 mV/s, and the voltage value corresponding to the intersection point of the tangent line of the current slope increasing area and the horizontal transverse axis in the read curve is a high-voltage resistant window. The test results are shown in table 1 and fig. 2 below.
In fig. 2, the electrochemical stability window scanning curve of the solid electrolyte of embodiment 1 of the present application is shown in fig. 2, and it can be seen that the solid electrolyte of embodiment 1 has a higher electrochemical stability window, and the electrochemical stability window reaches 4.71V, which can bear a higher voltage and is helpful for improving the high voltage resistance of the battery.
(IV) conductivity test:
Placing an electrode ring for fixing an electrolyte container and a polytetrafluoroethylene single ring serving as the electrolyte container at the bottom of a battery shell, dripping the pre-polymerization liquid samples prepared in examples 1-15 and comparative examples 1-3 into the electrolyte container to enable the pre-polymerization liquid to completely fill a cavity of the electrolyte container, covering a stainless steel electrode plug to form a blocking electrode, covering an upper cover of the battery shell, and screwing a butterfly nut to complete the assembly of the battery. And (3) directly connecting the assembled opposite blocking battery with an electrochemical workstation (VMP-3 e, bio-Logic), placing the battery in a 50 ℃ incubator, curing the battery at high temperature, performing alternating current impedance test at a frequency of 1 MHz-0.03 Hz, and performing EIS test on the battery. According to Σ is ion conductivity, L is electrolyte thickness, S is the contact area of electrolyte membrane and electrode, R is impedance measured by impedance meter, and the ion conductivity (σ, mS/cm) of solid electrolyte is calculated by using the above formula. The test results are shown in table 1 below.
(V) high voltage cycle test:
The preparation of the positive pole piece comprises the steps of grinding and mixing 95-99% of lithium cobaltate material and 1-5% of conductive agent acetylene black, adding 1-5% of polyvinylidene fluoride, grinding and dispersing in 1-methyl-2-pyrrolidone (NMP), mixing to obtain positive pole slurry, wherein the NMP is used for mixing and dispersing, adjusting the viscosity of the slurry, volatilizing during drying so as not to account for the mass percentage of the positive pole material, coating the positive pole material on the surface of an aluminum foil, and drying to obtain the positive pole piece.
The preparation of the negative electrode plate comprises the steps of uniformly mixing silicon particles and graphite according to a mass ratio of 9:1 to obtain a silicon-carbon composite negative electrode material, adding the silicon-carbon composite negative electrode material with a mass ratio of 80% -95% into conductive carbon black with a mass ratio of 1% -10%, grinding and mixing, adding sodium carboxymethyl cellulose with a mass ratio of 1% -5%, polystyrene butadiene copolymer with a mass ratio of 1% -5% and water, grinding, dispersing and mixing, coating on the surface of a copper foil, and drying to obtain the negative electrode plate.
The diaphragm is a porous supporting material for isolating the anode and the cathode, and a polyethylene diaphragm is adopted.
And injecting the pre-polymerized liquid samples prepared in the examples 1-15 and the comparative examples 1-3 into a battery system of a positive electrode plate, a diaphragm and a negative electrode plate, pre-sealing, standing at normal temperature, soaking for 24-72h, and heating and curing for 12-72 h at 40-80 ℃ to prepare the solid-state battery.
Solid state soft package full battery high voltage cycle test:
The battery is firstly formed, 0.02C constant current charge is carried out for 60min,0.05C constant current charge is carried out for 60min,0.1C constant current charge is carried out for 120min,0.2C constant current charge is carried out for 180min, heating is carried out at 45 ℃ for 24h, cooling is carried out to room temperature, 0.01C constant current is carried out again at constant voltage, charging is carried out to upper limit voltage of 4.58V, cut-off current is carried out for 0.02C, the battery is put aside for 10min, constant current discharge is carried out to 3V by using the current of 0.1C, the battery is put aside for 10min, namely, normal temperature circulation is carried out for 4 times in a CC-CV mode, then 1C current constant voltage charge is carried out at normal temperature, 1C current constant current discharge is carried out, charge-discharge cut-off voltage is carried out for 3V to 4.58V, the battery is circulated for 500 circles, capacity retention (%) after 500 circles of high voltage circulation are obtained, and test results refer to FIG. 3 and table 1.
Wherein fig. 3 is a high voltage cycle graph of the solid state soft pack full battery of example 1 and comparative example 1 of the present application, wherein the red curve in fig. 3 is a high voltage cycle curve of the solid state soft pack full battery of example 1, and the black curve in fig. 3 is a high voltage cycle curve of the solid state soft pack full battery of comparative example 1. As can be seen from fig. 3, the battery capacity of the solid-state battery corresponding to example 1 decays to 94.6% of the original value after 500 cycles of high-voltage cycling, and the battery capacity of the solid-state battery corresponding to comparative example 1 decays to 85.0% of the original value after 500 cycles of high-voltage cycling, which indicates that the solid-state electrolyte of example 1 can still maintain the normal operation inside the battery during the cycle of full-battery high-voltage charge and discharge, and the solid-state electrolyte of example 1 can withstand higher voltage, has higher voltage stability, and further improves the cycle life of the battery.
TABLE 1
From the test results of table 1, it is understood that the batteries containing the solid electrolytes of examples 1 to 15 have a high capacity retention rate and electrochemical stability window after 500 cycles of high voltage cycle. The method for preparing the solid electrolyte by using the polyfunctional monomer as the raw material is described, and the high voltage resistance of the solid electrolyte can be improved.
Comparison of examples 1-12, example 13 and example 14 shows that the mass percentage of the polyfunctional monomer in the prepolymer is controlled within the range of 1% -5%, so that the battery can be further ensured to have better high voltage resistance.
Comparison of examples 1-3, example 4, example 5 and example 8 shows that when R 7 in the polyfunctional monomer is alkyl and the structure of the polyfunctional monomer is a symmetrical molecular structure, the battery can be further ensured to have better high voltage resistance and wider electrochemical stability window.
As can be seen from comparison of examples 1 to 7 and example 15, R 7 has a structure as shown in formula (2) or formula (3), and the sum of n1 and n2 is between 1 and 10, and/or the sum of n4 and n5 is between 1 and 10, it is possible to further ensure that the battery has better high voltage resistance, a wider electrochemical stability window, and higher conductivity.
The foregoing has outlined rather broadly the more detailed description of embodiments of the application, wherein the principles and embodiments of the application are explained in detail using specific examples, the above examples being provided solely to facilitate the understanding of the method and core concepts of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (10)
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| DE2064079C2 (en) * | 1970-12-28 | 1982-09-09 | Hoechst Ag, 6000 Frankfurt | Photopolymerizable mixture |
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| WO2007105381A1 (en) * | 2006-03-13 | 2007-09-20 | Fujifilm Corporation | Photosensitive resin composition for photospacer, method for producing photospacer, substrate for liquid crystal display, liquid crystal display element, and liquid crystal display |
| KR100788162B1 (en) * | 2006-08-24 | 2007-12-21 | 성균관대학교산학협력단 | Electrolyte for lithium secondary battery containing high temperature stability additive and lithium secondary battery employing same |
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