CN111430790A - Semi-solid electrolyte and preparation method and application thereof - Google Patents
Semi-solid electrolyte and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a semi-solid electrolyte and a preparation method and application thereof, wherein the semi-solid electrolyte comprises a hydroxyl-terminated hyperbranched polymer, 1, 4-phenyl diboronic acid and ionic liquid. The semi-solid electrolyte has the excellent characteristics of high conductivity of ionic liquid, good electrochemical stability, difficult combustion and the like, and can also effectively solve the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to face in the production and use processes of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries and application thereof, and particularly relates to a semi-solid electrolyte and a preparation method and application thereof.
Background
The lithium ion battery has the excellent characteristics of high voltage, long storage and cycle life, strong charge retention capacity, no environmental pollution, wide working range and the like, and is widely applied to the field of new energy electric automobiles at present. However, the safety performance of the existing lithium ion battery can not be effectively solved due to the instability and easy combustion and explosion of the carbonate organic electrolyte.
Therefore, developing a safe, stable and efficient electrolyte has become an important direction for the development of future lithium ion batteries.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a semi-solid electrolyte, a method for preparing the same and use thereof. The semi-solid electrolyte has the excellent characteristics of high conductivity of ionic liquid, good electrochemical stability, difficult combustion and the like, and can also effectively solve the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to face in the production and use processes of the battery.
In one aspect of the invention, the invention provides a semi-solid electrolyte comprising, in accordance with an embodiment of the invention: hydroxyl-terminated hyperbranched polymer, 1, 4-phenyl diboronic acid and ionic liquid. According to the semi-solid electrolyte provided by the embodiment of the invention, the hydroxyl-terminated hyperbranched polymer and 1, 4-phenyl diboronic acid can generate a dehydration condensation reaction in ionic liquid to generate a polymer with reversible self-repairing boron ester bonds, and the chemical reaction formula is as follows:
the polymer can seal ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of the dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced by the battery in the production and use processes can be effectively solved, and the performances of the lithium ion battery in all aspects are integrally improved.
In addition, the semi-solid electrolyte according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the ionic liquid is selected from at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-ethoxymethylimidazolium bistrifluoromethylsulphonimide salt, 1-methyl-3-butylimidazolium bistrifluoromethylsulphonimide salt, N-butyl-N-methylpyrrolidine bistrifluoromethylsulphonimide salt, N-ethoxyethyl-N-methylpyrrolidine bistrifluoromethylsulphonimide salt.
In some embodiments of the invention, the mass ratio of the hydroxyl-terminated hyperbranched polymer to the ionic liquid is 20 to 50: 80-50.
In some embodiments of the invention, the ratio of the amount of the substance of 1, 4-benzenediboronic acid to the number of hydroxyl groups contained in the hydroxyl-terminated hyperbranched polymer is 0.125 to 0.25.
In some embodiments of the present invention, the hydroxyl-terminated hyperbranched polymer contains 10 to 48 hydroxyl groups.
In some embodiments of the invention, the hydroxyl-terminated hyperbranched polymer has the formula
In yet another aspect of the present invention, the present invention provides a method of preparing the above semi-solid electrolyte, according to an embodiment of the present invention, the method comprising: heating and dissolving the hydroxyl-terminated hyperbranched polymer, the 1, 4-phenyl diboronic acid and the ionic liquid, and then drying in a vacuum atmosphere to obtain the semi-solid electrolyte.
According to the method for preparing the semi-solid electrolyte, provided by the embodiment of the invention, the mixture in which the hydroxyl-terminated hyperbranched polymer, the 1, 4-phenyl diboronic acid and the ionic liquid are dissolved is sent to a vacuum atmosphere for reaction, and the hydroxyl-terminated hyperbranched polymer and the 1, 4-phenyl diboronic acid are subjected to dehydration condensation reaction in the ionic liquid to generate the polymer with reversible self-repairing boron ester bonds and water. The polymer can seal ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of the dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced by the battery in the production and use processes can be effectively solved, and the performances of the lithium ion battery in all aspects are integrally improved. The water obtained is removed after drying to avoid the reaction going backwards.
In addition, the method of preparing a semi-solid electrolyte according to the above-described embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the temperature of the heated dissolution is 30-60 ℃.
In some embodiments of the invention, the reaction is carried out at a temperature of 70 to 120 ℃ under a vacuum of 100KPa for a period of 4 hours.
In some embodiments of the invention, the temperature of the drying is 40-80 ℃.
In yet another aspect of the present invention, the present invention provides a lithium battery having the above semi-solid electrolyte or the semi-solid electrolyte prepared by the above method for preparing a semi-solid electrolyte, according to an embodiment of the present invention. According to the lithium battery provided by the embodiment of the invention, the lithium battery has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and also has the semi-solid electrolyte of the dynamic reversible self-repairing boron ester bond chemical bond, which can effectively solve the safety problem caused by uncontrollable factors such as bending, falling and impact and the like which are bound to be faced in the production and use processes of the battery, so that the lithium battery becomes a lithium battery with a safe, stable and efficient electrolyte, and the performances of all aspects are improved.
In yet another aspect of the invention, the invention provides an automobile, which is provided with the lithium battery according to the embodiment of the invention. According to the automobile provided by the embodiment of the invention, because the automobile is provided with the lithium battery with the safe, stable and efficient electrolyte, the safety performance and the power performance of the automobile are improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In one aspect of the invention, the invention provides a semi-solid electrolyte comprising, in accordance with an embodiment of the invention: hydroxyl-terminated hyperbranched polymer, 1, 4-phenyl diboronic acid and ionic liquid. The inventor finds that the hydroxyl-terminated hyperbranched polymer and 1, 4-phenyl diboronic acid can generate a dehydration condensation reaction in ionic liquid to generate a polymer with reversible self-repairing boron ester bonds, and the polymer can seal the ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of a dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced in the production and use processes of the battery can be effectively solved, and the performance of each aspect of the lithium ion battery is integrally improved.
According to an embodiment of the present invention, the specific type of the ionic liquid is not particularly limited, and may be selected according to actual needs by those skilled in the art, and may be, for example, at least one selected from 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-ethoxymethylimidazolium bistrifluoromethylsulfonyl imide salt, 1-methyl-3-butylimidazolium bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine bistrifluoromethylsulfonyl imide salt, and N-ethoxyethyl-N-methylpyrrolidine bistrifluoromethylsulfonyl imide salt. The inventor finds that the ionic liquid has higher ionic conductivity which can reach 10 at most-2S·cm-1Further, the mass ratio of the hydroxyl-terminated hyperbranched polymer to the ionic liquid is not particularly limited, and may be, for example, 20 to 50: 80-50, in particular, such as 20/25/30/35/40/45/50: 80/75/70/65/60/55/50. The inventors found that when the content of the ionic liquid is too high, crosslinking formation is not easily caused, and when the content is too low, the ionic conductivity is lowered; further, the quality of the 1, 4-benzenediboronic acid is not particularly limited, and for example, the ratio of the amount of the 1, 4-benzenediboronic acid to the number of hydroxyl groups contained in the hydroxyl-terminated hyperbranched polymer may be 0.125 to 0.25, preferably 0.125. The inventors have found that by controlling the reaction molar ratio, further, the number of hydroxyl groups contained in the hydroxyl-terminated hyperbranched polymer is not particularly limited, and may be 10 to 48, specifically, 10 or 16 or 24 or 36 or 48. Further, the specific type of the hydroxyl-terminated hyperbranched polymer is not particularly limited, and the hydroxyl-terminated hyperbranched polymer may have a chemical formula of
Abbreviated HBP-OH. The inventor finds that the polymer is easy to synthesize, controllable in reaction, large in hydroxyl number and capable of generating various functional reactions, so that the polymer has wide application prospects in the fields of lithium ion batteries, biological medicines and the like.
According to the semi-solid electrolyte provided by the embodiment of the invention, the hydroxyl-terminated hyperbranched polymer and 1, 4-phenyl diboronic acid can generate a dehydration condensation reaction in ionic liquid to generate a polymer with reversible self-repairing boron ester bonds, and the chemical reaction formula is as follows:
the polymer can seal ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of the dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced by the battery in the production and use processes can be effectively solved, and the performances of the lithium ion battery in all aspects are integrally improved.
In yet another aspect of the present invention, the present invention provides a method of preparing the above semi-solid electrolyte, according to an embodiment of the present invention, the method comprising: heating and dissolving the hydroxyl-terminated hyperbranched polymer, the 1, 4-phenyl diboronic acid and the ionic liquid, and then drying in a vacuum atmosphere to obtain the semi-solid electrolyte. The inventor finds that by sending a mixture dissolved with hydroxyl-terminated hyperbranched polymer, 1, 4-phenyl diboronic acid and ionic liquid to a vacuum atmosphere for reaction, the hydroxyl-terminated hyperbranched polymer and the 1, 4-phenyl diboronic acid undergo a dehydration condensation reaction in the ionic liquid to generate the polymer with reversible self-repairing boron ester bonds and water. The polymer can seal ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of the dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced by the battery in the production and use processes can be effectively solved, and the performances of the lithium ion battery in all aspects are integrally improved. The water obtained is removed after drying to avoid the reaction going backwards. Specifically, the hydroxyl hyperbranched polymer and the 1, 4-phenyl diboronic acid can be added into the ionic liquid, the ionic liquid is heated and dissolved completely at a certain temperature, the obtained solution is sent into a mold, the mold and the solution are sent into a vacuum oven, the temperature is controlled, the vacuum oven is vacuumized to promote the dehydration condensation reaction, and after the reaction is finished, the temperature is controlled to remove water obtained by the reaction, so that the semi-solid electrolyte with the shape and size of the mold is obtained.
According to an embodiment of the present invention, the temperature for heating and dissolving is not particularly limited, and may be selected by those skilled in the art according to actual needs, such as 30-60 ℃, preferably 50 ℃. The inventor finds that local reaction can occur at a high temperature to cause incomplete dissolution, and the dissolution speed is slow if the temperature is too low, thereby influencing the experimental progress. Further, the specific conditions of the reaction are not particularly limited, and for example, the reaction temperature may be 70 to 120 ℃, preferably 80 ℃, the degree of vacuum may be 100KPa, and the time may be 4 hours. The inventors found that, when the temperature and the vacuum degree are too high, the longer the reaction time is, the polymer is decomposed; if the temperature and the degree of vacuum are too low and the reaction time is short, the reaction is insufficient, and various properties of the electrolyte are affected. Further, the temperature for drying is also not particularly limited, and may be, for example, 40 to 80 ℃, preferably 50 ℃. The inventors found that if the temperature is too low, the moisture cannot be completely dried, and if the temperature is too high, the performance of the electrolyte is affected.
According to the method for preparing the semi-solid electrolyte, provided by the embodiment of the invention, the mixture in which the hydroxyl-terminated hyperbranched polymer, the 1, 4-phenyl diboronic acid and the ionic liquid are dissolved is sent to a vacuum atmosphere for reaction, and the hydroxyl-terminated hyperbranched polymer and the 1, 4-phenyl diboronic acid are subjected to dehydration condensation reaction in the ionic liquid to generate the polymer with reversible self-repairing boron ester bonds and water. The polymer can seal ionic liquid in a network structure of the polymer, so that the semi-solid electrolyte has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and meanwhile, due to the existence of the dynamic reversible self-repairing boron ester bond chemical bond, the safety problem caused by uncontrollable factors such as bending, falling, impact and the like which are bound to be faced by the battery in the production and use processes can be effectively solved, and the performances of the lithium ion battery in all aspects are integrally improved. The water obtained is removed after drying to avoid the reaction going backwards.
In yet another aspect of the present invention, the present invention provides a lithium battery having the above semi-solid electrolyte or the semi-solid electrolyte prepared by the above method for preparing a semi-solid electrolyte, according to an embodiment of the present invention. According to the lithium battery provided by the embodiment of the invention, the lithium battery has the excellent characteristics of high conductivity, good electrochemical stability, difficult combustion and the like of the ionic liquid, and also has the semi-solid electrolyte of the dynamic reversible self-repairing boron ester bond chemical bond, which can effectively solve the safety problem caused by uncontrollable factors such as bending, falling and impact and the like which are bound to be faced in the production and use processes of the battery, so that the lithium battery becomes a lithium battery with a safe, stable and efficient electrolyte, and the performances of all aspects are improved.
In yet another aspect of the invention, the invention provides an automobile, which is provided with the lithium battery according to the embodiment of the invention. According to the automobile provided by the embodiment of the invention, because the automobile is provided with the lithium battery with the safe, stable and efficient electrolyte, the safety performance and the power performance of the automobile are improved.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Adding 0.5g of HBP-OH with 16 hydroxyl groups and 0.108g of 1, 4-benzenediboronic acid into a bottle containing 2.0g of 1-butyl-3-methylimidazolium tetrafluoroborate reagent, heating at 50 ℃ to completely dissolve, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 2 varying the quality of the components
Adding 0.75g of HBP-OH with 16 hydroxyl groups and 0.163g of 1, 4-benzenediboronic acid into a 1.75g of 1-butyl-3-methylimidazolium tetrafluoroborate reagent bottle, heating at 50 ℃ to completely dissolve the mixture, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 3 varying the quality of the components
1.0g of HBP-OH with 16 hydroxyl groups and 0.217g of 1, 4-benzenediboronic acid are added into a 1.5g of 1-butyl-3-methylimidazolium tetrafluoroborate reagent bottle, and are heated and dissolved completely at 50 ℃, the obtained solution is poured into a fixed mould, and is put into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa for reaction for 240min, and after the reaction is finished, the semi-solid electrolyte with fixed shape and size is obtained after drying at 50 ℃.
Example 4
Adding 0.75g of HBP-OH with the number of 16 hydroxyl groups and 0.163g of 1, 4-phenyl diboronic acid into a reagent bottle containing 1.75g of 1-methyl-3-ethoxymethylimidazolium bistrifluoromethanesulfonylimide salt, heating at 50 ℃ to completely dissolve the solution, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 5
Adding 0.75g of HBP-OH with the number of 16 hydroxyl groups and 0.163g of 1, 4-phenyl diboronic acid into a reagent bottle containing 1.75g of 1-methyl-3-butyl imidazole bistrifluoromethylsulfonyl imide salt, heating at 50 ℃ to completely dissolve the solution, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 6
Adding 0.75g of HBP-OH with the number of 16 hydroxyl groups and 0.163g of 1, 4-benzenediboronic acid into a reagent bottle containing 1.75g N-butyl-N-methylpyrrolidine bistrifluoromethylsulfonyl imide salt, heating at 50 ℃ to completely dissolve the mixture, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 7
Adding 0.75g of HBP-OH with the number of 16 hydroxyl groups and 0.163g of 1, 4-benzenediboronic acid into a reagent bottle containing 1.75g N-ethoxyethyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide salt, heating at 50 ℃ to completely dissolve the HBP-OH and the 1, 4-benzenediboronic acid, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 8
Adding 0.75g of HBP-OH with 24 hydroxyl groups and 0.121g of 1, 4-benzenediboronic acid into a 1.75g of 1-butyl-3-methylimidazolium tetrafluoroborate reagent bottle, heating at 50 ℃ to completely dissolve the mixture, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
Example 9
Adding 0.75g of HBP-OH with 48 hydroxyl groups and 0.081g of 1, 4-benzenediboronic acid into a 1.75g of 1-butyl-3-methylimidazolium tetrafluoroborate reagent bottle, heating at 50 ℃ to completely dissolve the mixture, pouring the obtained solution into a fixed mold, placing the fixed mold into a vacuum oven with the temperature of 80 ℃ and the vacuum degree of 100KPa to react for 240min, and drying at 50 ℃ after the reaction is finished to obtain the semi-solid electrolyte with fixed shape and size.
The semi-solid electrolytes obtained in examples 1 to 9 were subjected to the following tests in order:
(1) self-repairing performance test: the repair process was observed by a polarizing microscope and the repair time was recorded.
(2) And (3) testing electrical properties: the semi-solid electrolyte is clamped between two platinized stainless steel electrodes, and the alternating current impedance test is carried out on the semi-solid electrolyte through an electrochemical workstation, so that the ionic conductivity is calculated.
(3) Testing thermal stability: the thermal decomposition temperature was measured by TGA thermogravimetric analyzer.
The test results are shown in table 1:
table 1 results of performance test of semi-solid electrolytes obtained in examples 1 to 9
As can be seen from Table 1: the semi-solid electrolytes prepared in examples 1 to 9 all had an ionic conductivity of 10-4S·cm-1Above, up to 2.1 × 10-3S·cm-1The repair time is within 1h, the lithium ion battery has super-strong self-repair performance, and the thermal decomposition temperature is over 200 ℃, which is far superior to the thermal stability of the existing lithium ion battery.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The semi-solid electrolyte is characterized by comprising a hydroxyl-terminated hyperbranched polymer, 1, 4-phenyl diboronic acid and ionic liquid.
2. The semi-solid electrolyte of claim 1, wherein the ionic liquid is selected from at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-ethoxymethylimidazolium bistrifluoromethylsulphonimide salt, 1-methyl-3-butylimidazolium bistrifluoromethylsulphonimide salt, N-butyl-N-methylpyrrolidine bistrifluoromethylsulphonimide salt, N-ethoxyethyl-N-methylpyrrolidine bistrifluoromethylsulphonimide salt.
3. The semi-solid electrolyte of claim 1 or 2, wherein the mass ratio of the hydroxyl-terminated hyperbranched polymer to the ionic liquid is 20-50: 80-50.
4. The semi-solid electrolyte of claim 1, wherein the ratio of the amount of the substance of 1, 4-benzenediboronic acid to the number of hydroxyl groups contained in the hydroxyl-terminated hyperbranched polymer is 0.125 to 0.25.
5. The semi-solid electrolyte of claim 1, wherein the hydroxyl-terminated hyperbranched polymer has a number of hydroxyl groups of 10 to 48;
optionally, the hydroxyl-terminated hyperbranched polymer has a chemical formula of
6. A method of preparing the semi-solid electrolyte of any one of claims 1-5, comprising: heating and dissolving the hydroxyl-terminated hyperbranched polymer, the 1, 4-phenyl diboronic acid and the ionic liquid, then reacting in a vacuum atmosphere, and drying to obtain the semi-solid electrolyte.
7. The method of claim 6, wherein the temperature of the heated dissolution is 30-60 ℃.
8. The method according to claim 6, wherein the reaction temperature is 70-120 ℃, the vacuum degree is 100KPa, and the reaction time is 4 h;
optionally, the temperature of the drying is 40-80 ℃.
9. A lithium battery characterized in that it has the semi-solid electrolyte of any one of claims 1 to 5 or a semi-solid electrolyte prepared by the method of preparing a semi-solid electrolyte of any one of claims 6 to 8.
10. An automobile, characterized in that it has a lithium battery as claimed in claim 9.
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Citations (17)
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