CN114497720A - Biodegradable high-performance cellulose gel film and preparation method thereof - Google Patents
Biodegradable high-performance cellulose gel film and preparation method thereof Download PDFInfo
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- CN114497720A CN114497720A CN202111678575.5A CN202111678575A CN114497720A CN 114497720 A CN114497720 A CN 114497720A CN 202111678575 A CN202111678575 A CN 202111678575A CN 114497720 A CN114497720 A CN 114497720A
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- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 108010025899 gelatin film Proteins 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims description 48
- 239000001913 cellulose Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 239000000017 hydrogel Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000005518 polymer electrolyte Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a biodegradable high-performance cellulose gel film and a preparation method thereof, and the cellulose gel film with good mechanical properties and environmental protection is prepared by a one-step solution casting crosslinking method. The cellulose gel film prepared by the invention not only has good tensile breaking strength, but also shows excellent electrochemical properties, including electrolyte absorptivity up to 540%, high ionic conductivity, good compatibility with a lithium electrode and good electrochemical stability. The natural polymer membrane has great development potential as a lithium ion battery gel polymer electrolyte membrane with high safety, low cost and environmental protection.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery gel polymer films, and particularly relates to a biodegradable high-performance cellulose gel film and a preparation method thereof.
Background
Over the past several decades, rechargeable lithium ion batteries have attracted considerable attention from researchers due to their high energy density, high operating voltage, good stability and lack of memory effects. The hybrid vehicle and the method are explored and widely applied to the fields of energy storage and portable electronic equipment such as Hybrid Electric Vehicles (HEVs), all-Electric Vehicles (EVs), mobile phones, notebook computers, digital cameras and the like. But still has the potential safety hazards of internal short circuit, liquid leakage, flammability and even explosion. In order to solve the above problems, researchers have recently been working on replacing organic liquid electrolytes and separators with gel polymer electrolytes, which are based on a skeletal polymer material having a porous structure, and exhibit comprehensive performance advantages in terms of battery capacity, safety, ion transport, etc. by comparison with liquid electrolytes and solid polymer electrolytes, and are applicable to the field of lithium ion batteries.
To date, the most common synthetic polymers available for gel polymer electrolytes include poly (ethylene oxide) (PEO), poly (acrylonitrile) (PAN), poly (methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), and their derivatives. However, the use of these polymers as gel polymer electrolytes is limited due to poor mechanical strength and high cost. For example, polyvinylidene fluoride and its copolymers are based on their relatively good electrical conductivity, but many preparation methods and modifications have been attempted and their mechanical strength is still poor. Another potential risk of these polymers is non-degradability, which easily causes "white contamination" to the environment. Furthermore, some of these polymers require complex multi-step syntheses of toxic reagents for their preparation. Therefore, a natural high molecular material with good mechanical properties is sought to be used as a gel polymer electrolyte matrix, which is an effective way for solving the problem of environmental pollution and improving the comprehensive performance of the battery.
Cellulose is a biomass material which is most widely distributed and rich in content in nature, and is a polymer material which attracts attention due to the advantages of containing a large amount of polar hydroxyl, being biodegradable and renewable, good in thermal stability, environment-friendly, low in cost and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a cellulose gel film as a lithium ion battery gel polymer electrolyte by a one-step solution casting crosslinking method, so that the prepared lithium ion battery has good mechanical property and electrochemical property.
The technical scheme provided by the invention is as follows:
a preparation method of a biodegradable high-performance cellulose gel film comprises the following steps:
s1, preparation of cellulose crosslinked hydrogel: using a solution containing sodium hydroxide/urea/H2Taking the solution of O as a cellulose alkaline solvent, fully stirring and uniformly mixing, freezing the alkaline solvent in a refrigerator at the temperature of-20 ℃ overnight, dispersing cellulose powder into the prepared alkaline solvent, fully stirring to dissolve cellulose, and centrifuging to remove bubbles and undissolved cellulose particles to obtain a transparent cellulose solution; then slowly adding the cross-linking agent into the transparent cellulose solution, stirring vigorously for 30 minutes at room temperature, pouring into a polytetrafluoroethylene mold, and transferring into a drying oven at 40-60 ℃ to bake for 2-4 hours to obtain cellulose cross-linked hydrogel;
the sodium hydroxide/urea/H2The preferred mass ratio of O is 5-10: 10-15: 75-85;
the centrifugation condition is preferably 8000-10000rpm, and the centrifugation time is 5-10 minutes;
the cross-linking agent is preferably one or two of epichlorohydrin and epibromohydrin, wherein the dosage of the cross-linking agent is preferably 5-10% (weight/volume%) of the transparent cellulose solution;
s2, preparation of a cellulose crosslinked membrane: soaking and washing the obtained cellulose crosslinked hydrogel with distilled water to remove residual alkali and urea, and drying the washed cellulose crosslinked hydrogel in a vacuum drying oven at 40-60 ℃ to obtain a dried cellulose crosslinked membrane, wherein the prepared cellulose crosslinked membrane can be used for absorbing liquid electrolyte;
the soaking and washing time is preferably more than or equal to 12 hours;
s3, preparation of a cellulose gel film: cutting the prepared cellulose crosslinked film into round pieces, placing the round pieces in a vacuum drying oven at 40-60 ℃ to remove excessive water, transferring a sample into an argon-filled glove box, and soaking the sample in liquid electrolyte for a period of time to form a cellulose gel film;
the argon-filled glove box environment preferably has a water content of <1ppm and an oxygen content of <1 ppm;
the soaking time of the electrolyte is preferably more than or equal to 6 hours.
The invention has the advantages that:
the invention adopts a one-step solution casting crosslinking method to prepare a cellulose gel film which is used as a polymer electrolyte film of a lithium ion battery, and crosslinking agents with different weight percentages are added to adjust the mechanical property and the ionic conductivity of the lithium ion battery; the cellulose gel film prepared by the method has good mechanical properties, tensile breaking strength of 75.9MPa and high ionic conductivity (9.95 multiplied by 10)-4S/cm) and excellent electrochemical properties. In addition, the preparation method of the invention is simple and easy to operate, is easy to process, is very easy to prepare, does not relate to any toxic or polluted chemical substances, and is environment-friendly. Therefore, the green and environment-friendly gel film has better application prospect in the field of safe and high-performance lithium ion batteries.
The material used in the invention has wide source and low cost, belongs to a natural biomass material, and is biodegradable and renewable, and has good thermal stability.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
This example describes the preparation of a biodegradable high performance cellulose gel film as follows:
s1, preparation of cellulose crosslinked hydrogel: sodium hydroxide/urea/H with a mass ratio of 5: 10: 75 is used2The solution of O was used as a cellulose alkaline solvent, and after stirring and mixing the solution sufficiently, the alkaline solvent was frozen in a refrigerator at-20 ℃ overnight, 4.5g of cellulose powder was dispersed in 100mL of an aqueous alkaline solution prepared, and the solution was stirred sufficiently to dissolve cellulose, and after centrifuging the solution at 8000rpm for 10 minutes to remove air bubbles and undissolved cellulose particles, a transparent cellulose solution was obtained, and then 3% (weight/volume%) of epoxy chloride was addedThe propane crosslinker was slowly added to the cellulose solution and stirred vigorously at room temperature for 30 minutes. Pouring the obtained solution into a polytetrafluoroethylene mold, and transferring the polytetrafluoroethylene mold into a baking oven at 45 ℃ for baking for 4 hours to obtain cellulose crosslinked hydrogel;
s2, preparation of a cellulose crosslinked membrane: soaking and washing the obtained cellulose crosslinked hydrogel with distilled water for 1 day to remove residual alkali and urea, and drying the washed cellulose crosslinked hydrogel in a vacuum drying oven at 45 ℃ for 24 hours to obtain a dried cellulose crosslinked membrane, wherein the prepared cellulose crosslinked membrane can be used for absorbing liquid electrolyte;
s3, preparation of a cellulose gel film: the cellulose crosslinked film prepared above was cut into circular pieces and placed in a vacuum drying oven at 45 ℃ to remove excess moisture, the samples were transferred to an argon-filled glove box with a water content <1ppm and an oxygen content <1ppm, and then soaked in a liquid electrolyte for 6h to form a cellulose gel film.
Example 2
This example was carried out for the preparation of a biodegradable high performance cellulose gel film using the same procedure as example 1, except that the epichlorohydrin crosslinking agent was added in an amount of 5% (w/v%).
Example 3
This example was carried out for the preparation of a biodegradable high performance cellulose gel film using the same procedure as example 1, except that the amount of epichlorohydrin crosslinking agent added was 7% (w/v%).
Example 4
This example was carried out for the preparation of a biodegradable high performance cellulose gel film using the same procedure as example 1, except that the amount of epichlorohydrin crosslinking agent added was 10% (w/v%).
Example 5
This example was carried out for the preparation of a biodegradable high performance cellulose gel film using the same procedure as example 1, except that the amount of epichlorohydrin crosslinking agent added was 15% (w/v%).
Example 6
This example is the same procedure as example 4 for the preparation of a biodegradable high performance cellulose gel film, except that sodium hydroxide/urea/H is used in a mass ratio of 8: 14: 822The solution of O is used as cellulose alkaline solvent.
Example 7
This example is the same procedure as example 4 for the preparation of a biodegradable high performance cellulose gel film, except that sodium hydroxide/urea/H is used in a mass ratio of 10: 15: 852The solution of O is used as cellulose alkaline solvent.
Comparative example
Comparative example No crosslinker was added and the other process conditions were consistent with those of example 4;
the examples 1-7 and the comparative example were tested for performance at room temperature;
the method for testing the ionic conductivity comprises the following steps: cross-linking impedance method;
instrument for testing ionic conductivity: the power transmission is strong, namely a 1287 constant potential rectifier and a 1260 frequency analyzer;
tensile strength test standard: GBT 228.1-2010;
tensile strength test instrument: an Instron 3340 single-column universal material testing machine;
table 1 below shows the results of the performance tests of examples 1 to 7 and comparative example:
TABLE 1 results of Performance test of examples 1-7 and comparative examples
From the test results in the above table, the cellulose gel film prepared without adding the crosslinking agent has significantly poor mechanical properties, and the ionic conductivity is significantly lower than that of the examples.
As seen from the test results of comparative examples 1 to 5, when the weight/volume ratio of the amount of the crosslinking agent to the cellulose solution is less than 5% or more than 10%, the tensile strength and ionic conductivity of the prepared cellulose gel film are low; when the amount of the cross-linking agent is 5-10% (weight/volume%) of the cellulose solution, the tensile strength and the ionic conductivity of the prepared cellulose gel film are increased along with the increase of the amount of the cross-linking agent; when the weight of the added cross-linking agent is 10 percent of the volume ratio of the cellulose solution, the mechanical strength and the ionic conductivity of the prepared cellulose gel film reach the best technical effect.
Comparing the performance test results of example 4 and examples 6 and 7, it is seen that when the amount of the cross-linking agent is in the optimum ratio, the cellulose alkaline solvents with different mass ratios have no significant effect on the performance of the prepared cellulose gel film; the performance of the cellulose gel films prepared in examples 6 and 7 is reduced compared with that of example 4; according to the performance test results of the above examples and comparative examples, the performance of the prepared cellulose gel film is optimal under the matching condition of the amount of the cross-linking agent and the amount of the cellulose alkaline solvent defined in example 4.
Although embodiments of the present invention have been shown and described, it is understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art may change, modify, replace and modify the above embodiments without departing from the scope of the present invention.
Claims (8)
1. A preparation method of a biodegradable high-performance cellulose gel film is characterized by comprising the following steps:
s1, preparation of cellulose crosslinked hydrogel: using a solution containing sodium hydroxide/urea/H2Taking the solution of O as a cellulose alkaline solvent, fully stirring and uniformly mixing, and freezing the alkaline solvent in a refrigerator at the temperature of-20 ℃ overnight; dispersing cellulose powder into a prepared alkaline solvent, fully stirring to dissolve cellulose, and centrifuging to remove bubbles and undissolved cellulose particles to obtain a transparent cellulose solution; then slowly adding the cross-linking agent into the transparent cellulose solution, violently stirring for 30 minutes at room temperature, pouring into a polytetrafluoroethylene mould, transferring into an oven at 40-60 ℃ and baking for 2-4 hours to obtain the cellulose cross-linked hydrogel；
S2, preparation of a cellulose crosslinked membrane: soaking and washing the obtained cellulose crosslinked hydrogel with distilled water, and drying the washed cellulose crosslinked hydrogel in a vacuum drying oven at 40-60 ℃ to obtain a dried cellulose crosslinked membrane;
s3, preparation of a cellulose gel film: the cellulose crosslinked film prepared above was cut into circular pieces, and placed in a vacuum drying oven at 40-60 ℃ to remove excess moisture, and the samples were transferred to an argon-filled glove box and then immersed in an electrolyte to prepare a cellulose gel film.
2. The method for preparing biodegradable high-performance cellulose gel film according to claim 1, wherein in step S1, the sodium hydroxide/urea/H is added2The mass ratio of O is 5-10: 10-15: 75-85.
3. The method for preparing a biodegradable high performance cellulose gel film as defined in claim 1, wherein in step S1, the centrifugation condition is 8000-10000rpm, and the centrifugation time is 5-10 minutes.
4. The method for preparing a biodegradable high-performance cellulose gel film according to claim 1, wherein in step S1, the crosslinking agent is one or two of epichlorohydrin and epibromohydrin;
wherein the ratio of the weight of the added cross-linking agent to the volume of the transparent cellulose solution is 5-10%.
5. The method for preparing biodegradable high-performance cellulose gel film according to claim 1, wherein in step S2, the soaking and washing time is not less than 12 h.
6. The method of claim 1, wherein in step S3, the argon filled glove box environment has a water content of <1ppm and an oxygen content of <1 ppm.
7. The method for preparing biodegradable high-performance cellulose gel film according to claim 1, wherein in step S3, the soaking time of the electrolyte is not less than 6 h.
8. A biodegradable high-performance cellulose gel film produced by the production method according to any one of claims 1 to 7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN104393339A (en) * | 2014-10-24 | 2015-03-04 | 西南石油大学 | Matrix gel polymer electrolyte adopting plant cellulose membrane and preparation method thereof |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN111934005A (en) * | 2020-07-22 | 2020-11-13 | 广西大学 | Crosslinked nanocellulose-based gel polymer electrolyte for lithium ion battery and preparation method and application thereof |
| CN113150314A (en) * | 2021-01-26 | 2021-07-23 | 上海工程技术大学 | Composite gel electrolyte material with interpenetrating network porous structure and preparation and application thereof |
-
2021
- 2021-12-31 CN CN202111678575.5A patent/CN114497720A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN104393339A (en) * | 2014-10-24 | 2015-03-04 | 西南石油大学 | Matrix gel polymer electrolyte adopting plant cellulose membrane and preparation method thereof |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN111934005A (en) * | 2020-07-22 | 2020-11-13 | 广西大学 | Crosslinked nanocellulose-based gel polymer electrolyte for lithium ion battery and preparation method and application thereof |
| CN113150314A (en) * | 2021-01-26 | 2021-07-23 | 上海工程技术大学 | Composite gel electrolyte material with interpenetrating network porous structure and preparation and application thereof |
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