CN115172868A - Self-healing gel polymer electrolyte and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a gel polymer electrolyte with a self-healing function, a preparation method and application thereof, belonging to the technical field of electrolyte materials. The gel polymer electrolyte comprises lithium salt, imidazole ionic liquid, a polymer with quadruple hydrogen bonds, a second polymer monomer and an initiator. The electrolyte forms a three-dimensional cross-linked network structure through an in-situ thermal initiation polymerization method, wherein the ionic liquid electrolyte is uniformly distributed in network gaps. 2- (3- (6-methyl-4-oxo-1,4-dihydropyrimidine-2) carbamido) ethyl methacrylate forms reversible non-covalent bonds through hydrogen bonds to endow the electrolyte material with self-healing characteristics; the second polymer monomer is polymerized to form a rigid network skeleton, and provides a supporting function for the electrolyte material. The gel polymer electrolyte with the self-healing function has good oxidation stability, good interface compatibility with various anode and cathode materials and high ionic conductivity, and can realize long-life stable circulation of the battery; the method realizes the synchronous operation of the preparation of the polymer electrolyte and the assembly of the battery, effectively reduces the cost and has wide application prospect in the aspects of portable flexible electronic devices and the like.
Description
Technical Field
The invention relates to a gel polymer electrolyte with a self-healing function, a preparation method and application thereof, belonging to the technical field of electrolyte materials.
Background
With the increasing demands of people on portable wearable electronic equipment and high-safety energy storage devices, extensive attention is paid to research and development of lithium batteries with high energy density and flexibility. The electrolyte material is used as an important component of a lithium battery, and the stability, flexibility, safety and the like of the electrolyte material are crucial to the overall performance of the battery. The solid electrolyte can be selected to fundamentally avoid accidents such as combustion, explosion and the like caused by the electrolyte, and has higher safety. However, increasing the operational durability of lithium batteries still faces significant challenges.
The development of inorganic solid electrolytes is limited by low fracture elasticity and ceramic rigidity, making them more brittle in the face of external impacts; conventional polymer solid electrolytes transport ions through polymer chain motion, and their ionic conductivity and electrochemical window are limited by the polymer structure. The gel polymer electrolyte has high ion conductivity, certain flexibility and assemblability, and becomes a current research hotspot. The gel polymer electrolyte material with certain self-healing characteristics can heal spontaneously when being damaged by external force or uncontrollable factors, so that the service life and the safety of the lithium battery are improved. The design and preparation of polymers with self-healing properties is a key step to improve the operational durability of batteries. When the polymer material matrix with multiple hydrogen bonds is damaged by external force, a large number of hydrogen bonds at the microcrack interface can be recombined to form a cross-linked dynamic supermolecular network structure, and the healing of the material structure is automatically realized.
Therefore, there is a need to design a self-healing gel polymer electrolyte based on multiple hydrogen bonds to improve battery safety and operational durability.
Disclosure of Invention
In view of the problems in the prior art, it is an object of the present invention to provide a polymer monomer having quadruple hydrogen bonds and a method for preparing the same. The polymer monomer is prepared by adopting a reversible addition-fragmentation chain transfer polymerization method, and internal dynamic hydrogen bonds provide self-healing characteristics for the electrolyte material.
The invention also aims to provide a gel polymer electrolyte based on quadruple hydrogen bonds and a lithium battery based on the gel polymer electrolyte. The synchronous implementation of the preparation of the polymer electrolyte and the assembly of the battery is realized by the in-situ built-in thermal initiation technology, the process is simple, and the large-scale production can be realized. The electrolyte introduces a polymer monomer with quadruple hydrogen bonds and an ionic liquid electrolyte into a rigid polymer network structure to form a three-dimensional cross-linked network structure and electrolyte/electrode cross-linking integration, so that the quick response and healing after the electrolyte is damaged are realized.
The technical scheme for realizing the purpose of the invention is as follows:
the self-healing gel polymer electrolyte and the preparation method and the application thereof are characterized in that: the self-healing gel polymer electrolyte comprises lithium salt, imidazole ionic liquid, a polymer with quadruple hydrogen bonds, a second polymer monomer and an initiator, and is of a three-dimensional cross-linked network structure.
The self-healing gel polymer electrolyte and the preparation method and the application thereof are characterized in that: the polymer with quadruple hydrogen bonds is 2- (3- (6-methyl-4-oxo-1,4-dihydropyrimidine-2) ureido) ethyl methacrylate (UPyMA), and is characterized in that the method is as follows:
the lithium salt in the self-healing gel polymer electrolyte is a lithium salt conventionally used in the technical field of lithium secondary batteries, and preferably lithium bistrifluoromethanesulfonylimide (LiTFSI); the imidazole ionic liquid is an ionic liquid conventionally used in an electrolyte for a lithium secondary battery, and is preferably 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide (EMITFSI); the polymer monomer is a polymer which can provide a rigid skeleton network structure support after polymerization, and is preferably one of pentaerythritol tetraacrylate (PEPETEA) and polyethylene glycol dimethacrylate (PEGMA); the initiator is a thermal initiator conventionally used in lithium secondary batteries, and is preferably Azobisisobutyronitrile (AIBN).
The invention provides a preparation method of a polymer with quadruple hydrogen bonds, which is characterized by comprising the following steps:
And 3, drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
The invention also provides a preparation method of the self-healing gel polymer electrolyte, which is characterized by comprising the following steps: the method comprises the following specific steps:
and 2, in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3 hours at 80 ℃ after the battery is packaged, and finishing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the self-healing gel polymer electrolyte-based lithium battery.
Specifically, the method for preparing the self-healing gel polymer electrolyte is characterized in that the concentration of the lithium salt in the step 1 is 0.5 to 1.5M, preferably 1M.
Specifically, the preparation method of the self-healing gel polymer electrolyte is characterized in that the content of UPyMA in the step 1 is 1-3 wt%.
Specifically, the preparation method of the self-healing gel polymer electrolyte is characterized in that the content of the second polymer in the step 1 is 3wt%.
Specifically, the preparation method of the self-healing gel polymer electrolyte is characterized in that the AIBN content in the step 1 is 0.1-0.5wt%.
The self-healing gel polymer electrolyte and the lithium battery based on the self-healing gel polymer electrolyte can be prepared according to the self-healing gel polymer electrolyte and the preparation method thereof.
According to the self-healing gel polymer electrolyte and the preparation method thereof, the near-anhydrous oxygen-free environment can be a glove box filled with protective gas of argon or nitrogen and with the moisture content of less than or equal to 0.1 ppm.
The invention has the beneficial effects that:
1. the invention provides a preparation method of UPyMA, the polymer has quadruple hydrogen bonds, the combination of dynamic hydrogen bonds can realize the self-healing function of an electrolyte material when the electrolyte material is damaged by external force, and the safety and the operation durability of a battery are effectively improved;
2. the invention provides a preparation method of a self-healing gel polymer electrolyte, wherein a rigid polymer network is used as a three-dimensional skeleton structure of the electrolyte, and imidazole ionic liquid electrolyte and dynamic hydrogen bonds are uniformly distributed in the network structure. The electrolyte has excellent chemical and electrochemical properties, including wide electrochemical stability window, good thermal stability, good compatibility with a high-voltage anode material/metal lithium cathode interface, and can realize long-time stable circulation of the battery;
3. the invention provides a preparation method of a lithium battery based on the self-healing gel polymer electrolyte, wherein the electrolyte is not easy to leak in the battery, and can heal automatically after microcracks exist, so that the safety performance of the battery is effectively improved; the precursor solution of the electrolyte can initiate polymerization in situ at high temperature, is simple to operate, green and environment-friendly in preparation process, and is suitable for large-scale batch production.
Drawings
FIG. 1 is a nuclear magnetic spectrum of UPyMA prepared in examples 1-3 of the present invention.
FIG. 2 is an infrared spectrum of UPyMA prepared in examples 1-3 of the present invention.
Fig. 3 is a micro-topography of the self-healing gel polymer electrolyte prepared in example 2 of the present invention.
Fig. 4 is a linear sweep voltammogram of the self-healing gel polymer electrolyte prepared in examples 1-3 of the present invention.
Fig. 5 is an arrhenius curve between the ion conductivity and the temperature of the self-healing gel polymer electrolyte prepared in examples 1 to 3 of the present invention.
Fig. 6 is a graph showing the cycle performance of the self-healing gel polymer electrolyte prepared in example 2 of the present invention in a Li | LFP battery.
Fig. 7 is the cycle performance of the self-healing gel polymer electrolyte prepared in example 2 of the present invention in Li | NCM622 battery.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The following examples:
(1) Nuclear magnetic resonance spectroscopy: nuclear magnetic resonance apparatus, 1H spectrum, model Bruker AV400;
(2) Infrared spectrum test: fourier transform infrared spectrometer, model Nicolet iS50, sreiser usa. Test range: 2000-400 cm -1 ；
(3) And (3) testing by a scanning electron microscope: scanning electron microscope, model S-4800;
(4) Linear Sweep Voltammetry (LSV) test: electrochemical workstation, model number: CHI660e, shanghai chenhua instruments ltd. The specific method comprises the following steps: assembling a stainless steel | polyether electrolyte | lithium sheet type battery system, and setting the scanning speed to be 0.1mV/s;
(5) Arrhenius curve test: electrochemical workstation, model CHI660E, shanghai Chenghua instruments, inc. The specific method comprises the following steps: assembling a stainless steel sheet | polyether electrolyte | stainless steel sheet type battery system, and carrying out EIS impedance test at-10-80 ℃ and in the range of 0.1-100000 Hz;
(6) And (3) testing the cycle performance: blue battery test system, model: CT2001A, wuhanjinuo electronics, inc. The specific method comprises the following steps: assembling the positive electrode gel polymer electrolyte lithium plate battery system, and carrying out constant current charge and discharge test on the battery at the temperature of 60 ℃.
Example 1
(1) In a glove box filled with a protective gas of argon gas having a purity of 99% or more and a moisture content of less than 0.1ppm, 1g of 2-amino-4-hydroxy-6-methylpyrimidine was added to 25mL of dimethyl sulfoxide (DMSO) and stirred at 150 ℃ for 10 minutes to obtain a transparent A solution. 1.32g of isopropyl methacrylate was added to the solution A, and when the solution was cooled to room temperature, a white solid B precipitated, which was collected and washed several times with methanol or acetone to remove the residual DMSO. And (3) drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
(2) In a glove box filled with a protective gas of argon with the purity of more than or equal to 99 percent and the moisture content of less than 0.1ppm, 0.566g of LiTFSI is dissolved in 3g of EMITFSI and stirred to obtain a transparent ionic liquid electrolyte C with the lithium salt concentration of 1M, 0.03g of quadruple hydrogen bonding polymer UPyMA is added into the electrolyte C, the mixture is heated and stirred to be completely dissolved, and then 0.09g of second polymer monomer PETEEA is added and stirred to be dissolved. After the temperature of the solution is reduced to room temperature, 0.003g of thermal initiator AIBN is added, and the mixture is stirred to obtain a precursor solution D; and in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3-6 hours at 70-80 ℃ after the battery is packaged, and completing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the lithium battery based on the self-healing gel polymer electrolyte.
The quadruple hydrogen bonding polymer and the self-healing gel polymer electrolyte prepared in the example were tested, and the results are as follows:
(1) Nuclear magnetic testing: the nuclear magnetic spectrum of UPyMA prepared in the example is shown in figure 1;
(2) Infrared spectrum test: the infrared spectrogram of UPyMA prepared in this example is shown in fig. 2;
(3) And (3) testing by a scanning electron microscope: the micro-topography of the self-healing gel polymer electrolyte prepared by the embodiment is shown in fig. 3;
(4) Linear Sweep Voltammetry (LSV) test: the electrochemical stability window of the self-healing gel polymer electrolyte prepared in the embodiment is shown as EUP-1 in figure 4, the oxidative decomposition potential of the self-healing gel polymer electrolyte is as high as 5V, and the self-healing gel polymer electrolyte can be matched with a high-voltage positive electrode material.
(5) Arrhenius curve test: an arrhenius curve of the self-healing gel polymer electrolyte prepared in the embodiment of the invention with respect to ion conductivity and temperature is shown as EUP-1 in fig. 5, and the activation energy of the electrolyte is calculated and deduced to be 0.273 eV;
(6) And (3) testing the cycle performance: the self-healing gel polymer electrolyte prepared by the embodiment is matched with the cycle performances of the LFP and NCM622 anodes respectively, as shown in fig. 6 and fig. 7, and good cycle stability shows that the electrolyte has excellent performances and good compatibility with a high-voltage anode and a lithium metal cathode.
Example 2
(1) In a glove box filled with a protective gas of argon gas having a purity of 99% or more and a moisture content of less than 0.1ppm, 1g of 2-amino-4-hydroxy-6-methylpyrimidine was added to 25mL of dimethyl sulfoxide (DMSO) and stirred at 150 ℃ for 10 minutes to obtain a transparent A solution. 1.32g of iso-ethyl methacrylate is added to the solution A, a white solid B precipitates out when the solution is cooled to room temperature, and the precipitate is collected and washed several times with methanol or acetone to remove residual DMSO. And (3) drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
(2) In a glove box filled with protective gas with the purity of more than or equal to 99% argon and the moisture content of less than 0.1ppm, 0.566g of LiTFSI is dissolved in 3g of EMITFSI and stirred to obtain a transparent ionic liquid electrolyte C with the lithium salt concentration of 1M, 0.06g of quadruple hydrogen bonding polymer UPyMA is added into the electrolyte C, the mixture is heated and stirred until the solution is completely dissolved, and then 0.09g of second polymer monomer PETEEA is added and stirred until the solution is dissolved. After the temperature of the solution is reduced to room temperature, 0.003g of thermal initiator AIBN is added, and the mixture is stirred to obtain a precursor solution D; and in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3-6 hours at 70-80 ℃ after the battery is packaged, and completing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the lithium battery based on the self-healing gel polymer electrolyte.
The quadruple hydrogen bonding polymer and the self-healing gel polymer electrolyte prepared in the example were tested, and the results are as follows:
(1) Nuclear magnetic testing: the nuclear magnetic spectrum of UPyMA obtained in this example is shown in fig. 1;
(2) Infrared spectrum test: the infrared spectrogram of UPyMA prepared in this example is shown in fig. 2;
(3) Linear Sweep Voltammetry (LSV) test: the electrochemical stability window of the self-healing gel polymer electrolyte prepared in the embodiment is shown as EUP-2 in fig. 4, the oxidative decomposition potential of the self-healing gel polymer electrolyte is as high as 5.1V, and the self-healing gel polymer electrolyte can be matched with a high-voltage positive electrode material.
(4) Arrhenius curve test: an arrhenius curve of the ion conductivity and the temperature of the self-healing gel polymer electrolyte prepared in this example is shown as EUP-2 in fig. 5, and the activation energy of the electrolyte is calculated and deduced to be 0.273eV.
Example 3
(1) In a glove box filled with a protective gas of argon gas having a purity of 99% or more and a moisture content of less than 0.1ppm, 1g of 2-amino-4-hydroxy-6-methylpyrimidine was added to 25mL of dimethyl sulfoxide (DMSO) and stirred at 150 ℃ for 10 minutes to obtain a transparent A solution. 1.32g of isopropyl methacrylate was added to the solution A, and when the solution was cooled to room temperature, a white solid B precipitated, which was collected and washed several times with methanol or acetone to remove the residual DMSO. And (3) drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
(2) In a glove box filled with protective gas with the purity of more than or equal to 99% argon and the moisture content of less than 0.1ppm, 0.566g of LiTFSI is dissolved in 3g of EMITFSI and stirred to obtain a transparent ionic liquid electrolyte C with the lithium salt concentration of 1M, 0.09g of quadruple hydrogen bonding polymer UPyMA is added into the electrolyte C, the mixture is heated and stirred until the solution is completely dissolved, and then 0.09g of second polymer monomer PETEEA is added and stirred until the solution is dissolved. After the temperature of the solution is reduced to room temperature, 0.003g of thermal initiator AIBN is added, and the mixture is stirred to obtain a precursor solution D; and in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3-6 hours at 70-80 ℃ after the battery is packaged, and finishing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the self-healing gel polymer electrolyte-based lithium battery.
The quadruple hydrogen bonding polymer and the self-healing gel polymer electrolyte prepared in the example were tested, and the results are as follows:
(1) Nuclear magnetic testing: the nuclear magnetic spectrum of UPyMA obtained in this example is shown in fig. 1;
(2) Infrared spectrum test: the infrared spectrogram of UPyMA prepared in this example is shown in fig. 2;
(3) Linear Sweep Voltammetry (LSV) test: the electrochemical stability window of the self-healing gel polymer electrolyte prepared in the embodiment is shown as EUP-3 in fig. 4, the oxidative decomposition potential of the self-healing gel polymer electrolyte is as high as 5.1V, and the self-healing gel polymer electrolyte can be matched with a high-voltage positive electrode material.
(4) Arrhenius curve test: an arrhenius curve of the ion conductivity and the temperature of the self-healing gel polymer electrolyte prepared in this example is shown in EUP-3 in fig. 5, and the activation energy of the electrolyte is calculated and deduced to be 0.317eV.
Example 4
(1) In a glove box filled with a protective gas of argon gas having a purity of 99% or more and a moisture content of less than 0.1ppm, 1g of 2-amino-4-hydroxy-6-methylpyrimidine was added to 25mL of dimethyl sulfoxide (DMSO) and stirred at 150 ℃ for 10 minutes to obtain a transparent A solution. 1.32g of iso-ethyl methacrylate is added to the solution A, a white solid B precipitates out when the solution is cooled to room temperature, and the precipitate is collected and washed several times with methanol or acetone to remove residual DMSO. And (3) drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
(2) In a glove box filled with a protective gas with the purity of more than or equal to 99% argon and the moisture content of less than 0.1ppm, 0.566g of LiTFSI is dissolved in 3g of EMITFSI and stirred to obtain a transparent ionic liquid electrolyte C with the lithium salt concentration of 1M, 0.06g of quadruple hydrogen bonding polymer UPyMA is added into the electrolyte C, the mixture is heated and stirred until the solution is completely dissolved, and then 0.09g of second polymer monomer PEGMA is added and stirred until the solution is dissolved. After the temperature of the solution is reduced to room temperature, 0.003g of thermal initiator AIBN is added, and the mixture is stirred to obtain a precursor solution D; and in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3-6 hours at 70-80 ℃ after the battery is packaged, and finishing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the self-healing gel polymer electrolyte-based lithium battery.
The quadruple hydrogen bonding polymer and the self-healing gel polymer electrolyte prepared in the example were tested, and the results are as follows:
(1) Nuclear magnetic testing: the nuclear magnetic spectrum of UPyMA obtained in this example is shown in fig. 1;
(2) Infrared spectrum test: the infrared spectrogram of UPyMA prepared in this example is shown in fig. 2;
(3) Self-healing test: the prepared gel polymer electrolyte generates cracks through external force, and the microcracks can be automatically healed within 1 minute.
Claims (11)
1. The self-healing gel polymer electrolyte and the preparation method and the application thereof are characterized in that: the self-healing gel polymer electrolyte comprises lithium salt, imidazole ionic liquid, a polymer with quadruple hydrogen bonds, a second polymer monomer and an initiator, and is of a three-dimensional cross-linked network structure.
2. A self-healing gel polymer electrolyte as claimed in claim 1, and the preparation method and application thereof, wherein: the polymer with quadruple hydrogen bonds is 2- (3- (6-methyl-4-oxo-1,4-dihydropyrimidine-2) ureido) ethyl methacrylate (UPyMA), and is characterized in that the method is as follows:
3. a self-healing gel polymer electrolyte as claimed in claim 1, and the preparation method and application thereof, wherein: the lithium salt is a lithium salt conventionally used in the technical field of lithium secondary batteries, preferably lithium bistrifluoromethanesulfonylimide (LiTFSI); the imidazole ionic liquid is an ionic liquid conventionally used in an electrolyte for a lithium secondary battery, and is preferably 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt (EMITFSI); the polymer monomer is a polymer which can provide a rigid skeleton network structure support after polymerization, and is preferably one of pentaerythritol tetraacrylate (PETEA) and polyethylene glycol dimethacrylate (PEGMA); the initiator is a thermal initiator conventionally used in lithium secondary batteries, and is preferably Azobisisobutyronitrile (AIBN).
4. The method for preparing a polymer with quadruple hydrogen bonding according to claim 2, characterized by comprising the following steps:
step 1. 2-amino-4-hydroxy-6-methylpyrimidine was added to dimethyl sulfoxide (DMSO) and stirred at 150 ℃ for 10 minutes to obtain solution A.
Step 2, add iso-ethyl methacrylate to solution a, precipitate a white solid B when the solution is cooled to room temperature, collect the precipitate and wash several times with methanol and acetone to remove residual DMSO.
And 3, drying the precipitate B at 30-60 ℃ for 3-8 hours in vacuum, and collecting white powder, namely UPyMA.
5. A self-healing gel polymer electrolyte and a method for preparing the same according to claim 1, wherein: the method comprises the following specific steps:
step 1, dissolving lithium salt in imidazole ionic liquid in a nearly anhydrous and oxygen-free environment, stirring to obtain a transparent ionic liquid electrolyte C, adding a quadruple hydrogen bond polymer UPyMA into the electrolyte C, heating and stirring until the four-hydrogen bond polymer UPyMA is completely dissolved, then adding a second polymer monomer, and stirring until the second polymer monomer is dissolved. After the temperature of the solution is reduced to room temperature, adding a thermal initiator AIBN, and stirring to obtain a precursor solution D;
and 2, in a nearly anhydrous and anaerobic environment, dripping the precursor solution D into a glass fiber membrane in the battery assembling process, standing for 3 hours at 80 ℃ after the battery is packaged, and finishing the built-in thermal initiation polymerization reaction of the polymer gel electrolyte to obtain the self-healing gel polymer electrolyte-based lithium battery.
6. The self-healing gel polymer electrolyte and the preparation method thereof according to claim 5, wherein the concentration of the lithium salt in step 1 is 0.5-1.5M, preferably 1M.
7. A self-healing gel polymer electrolyte according to claim 5, wherein the UPyMA content in step 1 is 1 to 3wt%.
8. A self-healing gel polymer electrolyte according to claim 5, wherein the second polymer content in step 1 is 3wt%.
9. The self-healing gel polymer electrolyte according to claim 5, wherein the AIBN content in step 1 is 0.1-0.5wt%.
10. The self-healing gel polymer electrolyte and the preparation method thereof according to claims 1 to 9 can be used for preparing the self-healing gel polymer electrolyte and the lithium battery based on the self-healing gel polymer electrolyte.
11. A self-healing gel polymer electrolyte and a preparation method thereof according to claim 5, wherein the nearly anhydrous and oxygen-free environment is a glove box filled with a protective gas such as argon or nitrogen and having a moisture content of 0.1ppm or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115732770A (en) * | 2022-12-07 | 2023-03-03 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
| CN116154280A (en) * | 2023-04-23 | 2023-05-23 | 远景动力技术(鄂尔多斯市)有限公司 | Gel electrolyte of lithium battery and application thereof |
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2022
- 2022-07-06 CN CN202210797329.XA patent/CN115172868A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115732770A (en) * | 2022-12-07 | 2023-03-03 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
| CN116154280A (en) * | 2023-04-23 | 2023-05-23 | 远景动力技术(鄂尔多斯市)有限公司 | Gel electrolyte of lithium battery and application thereof |
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