CN112072171B - Chitosan polyion liquid blended PEO-based solid electrolyte and preparation method and application thereof - Google Patents
Chitosan polyion liquid blended PEO-based solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a chitosan polyion liquid blended PEO-based solid electrolyte and a preparation method and application thereof. The invention firstly prepares the chitosan polyion liquid material through the ion exchange reaction of chitosan quaternary ammonium salt and bis-trifluoromethyl sulfimide lithium salt, and then prepares the HACC-TFSI blended PEO-based solid electrolyte material through dissolving and mixing into PEO-based solid electrolyte. The method has low cost, simple preparation method and environmental protection, and can be suitable for industrial large-scale production. The prepared all-solid-state electrolyte material has good conductivity, electrochemical stability, thermal stability and mechanical property, when the all-solid-state electrolyte material is used as a solid-state electrolyte material to be manufactured into an all-solid-state lithium ion battery, the rate capability and the cycle performance of the all-solid-state electrolyte material are remarkably improved compared with those of a control group at 60 ℃ and 150 ℃, and the all-solid-state electrolyte material can be applied to the all-solid-state lithium ion battery under the conditions of medium temperature and high temperature.
Description
Technical Field
The invention belongs to the technical field of chargeable and dischargeable all-solid-state lithium ion battery materials, and particularly relates to a chitosan polyion liquid blended PEO-based solid electrolyte, a preparation method and application thereof, in particular to a preparation method of a solid electrolyte material for a high-temperature all-solid-state lithium ion battery.
Background
Currently, research on solid-state lithium ion batteries is underway. Conventional lithium ion batteries use liquid organic electrolytes. Although having good ionic conductivity, it has serious battery safety problems, especially the problems of easy leakage and easy short circuit, which leads to the combustion and explosion of the battery, and compels people to find safer electrolyte materials. Among them, the solid electrolyte is widely considered as a fundamental method for fundamentally solving the safety problem of the lithium ion battery. PEO (polyethylene oxide) -based solid-state electrolysis has become one of the most studied solid-state electrolyte materials so far due to its superior ion conductivity, low cost and good flexibility.
However, the higher crystallinity of PEO in the PEO-based solid electrolyte material limits further increase of the lithium ion conductivity of the PEO-based solid electrolyte. In addition, the low ion transport number (0.2) and poor thermodynamic and electrochemical stability (3.8V at 60 ℃) of PEO-based solid state electrolytes severely limit the practical application of PEO-based solid state electrolyte materials. At present, methods for improving the performance of PEO-based solid electrolyte materials mainly include: preparing organic-inorganic composite solid electrolyte materials, doped inorganic nano materials, doped organic polymers and the like. Pan et al (publication No. CN 101431154A) and Xun et al (publication No. CN 101378119A) have carbon-coated lithium titanate by different methods, but the improvement of the performance is limited and the specific capacity cannot be improved. It is an effective solution to improve the performance of the solid electrolyte by blending an organic polymer with a PEO-based solid electrolyte material. However, there are two main types of organic materials currently mixed in. One is a polymer with a relatively low molecular weight, such as polyethylene glycol dimethyl ether, which can effectively reduce the crystallinity of the PEO-based solid electrolyte and improve the ionic conductivity thereof, but can significantly reduce the mechanical properties of the PEO-based solid electrolyte. The addition of plasticizers also increases the risk of leakage of the solid electrolyte material. The other is a high molecular weight organic polymer such as polyvinylidene fluoride, etc. The material can well improve the electrochemical stability of the PEO-based solid electrolyte, but the improvement on the ionic conductivity is small. In addition, most of the synthesis of organic polymers needs to be carried out in organic solvents, which is relatively expensive. Moreover, the current research on the blended PEO-based solid electrolyte is focused on the improvement of the ionic conductivity, and the research on the performance of the solid electrolyte at high temperature is less. The current PEO-based all-solid-state lithium ion battery has a higher working temperature because the working temperature is 60 ℃. Therefore, compared with a normal-temperature lithium battery, the lithium battery is more prone to thermal runaway caused by over-high temperature of the lithium battery due to heat accumulation caused by local micro short circuit of the lithium battery and the like. Therefore, for the research and application of the PEO-based solid electrolyte at higher temperature, the working temperature range of the PEO-based solid electrolyte can be increased, the thermal runaway phenomenon of the lithium battery can be inhibited, and the safety performance of the lithium battery is improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a chitosan polyion liquid blended PEO-based solid electrolyte.
The method overcomes the defects of the prior art by preparing HACC-TSFI (chitosan quaternary ammonium salt polyionic liquid) and mixing the HACC-TSFI into PEO-based solid electrolyte, effectively improves the ionic conductivity, the electrochemical stability and the thermal stability of the PEO-based solid electrolyte, and particularly improves the cycle performance of the all-solid-state lithium ion battery.
The invention also aims to provide the chitosan polyion liquid blended PEO-based solid electrolyte prepared by the method.
The invention further aims to provide application of the chitosan polyionic liquid blended PEO-based solid electrolyte in a lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a chitosan polyion liquid blended PEO-based solid electrolyte comprises the following steps:
(1) slowly adding a chitosan quaternary ammonium salt aqueous solution into a bis (trifluoromethyl) sulfimide aqueous solution under a stirring state, stirring for 5-15 h for ion exchange reaction, performing centrifugal separation, re-dissolving the obtained chitosan quaternary ammonium salt polyion liquid hydrogel into water at 50-80 ℃, slowly adding the obtained chitosan quaternary ammonium salt polyion liquid hydrogel into the bis (trifluoromethyl) sulfimide aqueous solution again, stirring for 5-15 h, further purifying the chitosan quaternary ammonium salt polyion liquid hydrogel, performing centrifugal separation, repeating the operations of dissolving the chitosan quaternary ammonium salt polyion the basis of adding the bis (trifluoromethyl) sulfimide aqueous solution and stirring for 1-3 times, dialyzing, and performing freeze drying to obtain a purified chitosan quaternary ammonium salt polyion liquid (HACC-TFSI) aerogel material;
(2) dissolving the purified chitosan quaternary ammonium salt polyion liquid aerogel material in a solvent to obtain a chitosan quaternary ammonium salt polyion liquid solution, dissolving PEO and lithium bistrifluoromethylsulfonyl imide salt in the solvent to obtain a PEO-lithium salt solution, uniformly mixing the chitosan quaternary ammonium salt polyion liquid solution and the PEO-lithium salt solution, transferring the mixture into a mold, and drying to obtain a chitosan polyion liquid blending PEO-based solid electrolyte;
wherein the mass ratio of the chitosan quaternary ammonium salt polyion liquid aerogel material purified in the step (2) to PEO is 5-20: 100, the molar ratio of EO units in PEO to lithium ions in lithium bistrifluoromethylsulfonimide is 10: 1-30: 1.
preferably, the slow adding speed in the step (1) is 0.6-1.2 mL/min.
Preferably, the mass ratio of the chitosan quaternary ammonium salt polyion liquid aerogel material purified in the step (2) to the PEO is 5-12: 100, respectively; more preferably 8 to 10: 100.
preferably, the molar ratio of TFSI ions in the bis (trifluoromethyl) sulfonyl imide salt added in each step (1) to quaternary ammonium ions in the chitosan quaternary ammonium salt is 1.0-2.0: 1.
preferably, the concentration of the aqueous solution of bis (trifluoromethyl) sulfonyl imide salt in the step (1) is 100-500 mg/ml, and the concentration of the aqueous solution of chitosan quaternary ammonium salt is 10-100 mg/ml.
Preferably, the rotation speed of centrifugal separation in the step (1) is 1000-11000 r/min, and the time is 5-35 min.
Preferably, the bis (trifluoromethyl) sulfonyl imide salt in the step (1) is at least one of LiTFSI (bis (trifluoromethyl) sulfonyl imide lithium salt), NaTFSI (bis (trifluoromethyl) sulfonyl imide sodium salt) and KTFSI (bis (trifluoromethyl) sulfonyl imide potassium salt).
Preferably, in the step (1), the chitosan quaternary ammonium salt polyion liquid hydrogel is re-dissolved in water, and the ratio of the chitosan quaternary ammonium salt polyion liquid hydrogel to the water is 0.001-0.1 g/mL.
Preferably, the purpose of the dialysis in step (1) is to remove excess Li ions and TFSI ions.
Preferably, the freeze drying in step (1) is performed by fast freezing with liquid nitrogen and then conventional freeze drying.
Preferably, the concentration of the chitosan quaternary ammonium salt polyion liquid aerogel solution in the step (2) is 6-14.4 mg/ml; more preferably 9.6 to 12 mg/ml.
Preferably, the concentration of the PEO in the PEO-lithium salt solution in the step (2) is 30-150 mg/ml.
Preferably, the solvent in step (2) is DMF (dimethylformamide).
Preferably, the dissolution of the PEO and the lithium salt in the solvent in the step (2) is carried out at 50-80 ℃.
Preferably, the step (2) of moving into the mold is realized by a rubber head dropper.
Preferably, the drying in step (2) is: drying at 30-40 deg.C for 12 hr to remove solvent, and vacuum drying at 80-120 deg.C for more than 72 hr to remove residual solvent.
Preferably, the chitosan polyion liquid blended PEO-based solid electrolyte obtained in the step (2) is in a film shape, and the thickness of the chitosan polyion liquid blended PEO-based solid electrolyte is 80-200 um.
Preferably, the operation in step (2) is performed in a glove box.
The chitosan polyion liquid blending PEO-based solid electrolyte prepared by the method.
The application of the chitosan polyionic liquid blended PEO-based solid electrolyte in a lithium ion battery is provided.
The ion conductivity of the HACC-TFSI blended PEO-based solid electrolyte prepared by the method can reach 1.77 multiplied by 10 at 30 ℃ and 60 ℃ respectively-5S cm-1And 5.01X 10-4S cm-1. The voltage windows at 60 ℃ and 150 ℃ can reach about 5.26V and 3.71V respectively. The full battery assembled by taking lithium metal and LFP as the cathode and the anode respectively has excellent rate performance and cycle performance at 60 ℃. Still show cycle performance far superior to that of pure PEO solid electrolyte at high temperature of 150 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the biomass-based polyion material HACC-TFSI is doped into the PEO-based solid electrolyte to prepare the HACC-TFSI blended PEO-based all-solid electrolyte material, the preparation process is simple and environment-friendly, the prepared HACC-TFSI polyion liquid can be synthesized only in an aqueous solution system, and the dissolution injection molding method is matched with the traditional preparation process of the PEO-based solid electrolyte and is suitable for the modified production of the existing PEO-based solid electrolyte. The obtained solid electrolyte material has good conductivity, electrochemical stability and thermodynamic stability, and when the solid electrolyte material is used as an all-solid-state lithium ion battery, the rate capability and the cycle performance of the all-solid-state lithium ion battery are remarkably improved at 60 ℃ and 150 ℃ compared with those of a control group, so that the solid electrolyte material can be widely applied to various flexible all-solid-state lithium ion batteries, particularly lithium ion batteries operating under a high-temperature condition.
Drawings
FIG. 1 is impedance data of 10% HACC-TFSI PEO-based solid electrolyte obtained in example 1 at various temperatures, and the thickness of the solid electrolyte membrane is 0.15 mm.
FIG. 2 is a LSV test curve of 10% HACC-TFSI PEO-based solid electrolyte and PEO SPEs solid electrolyte (comparative example 1) obtained in example 1 at 60 ℃ and 150 ℃, respectively.
FIG. 3 is a graph showing the cycle performance of the 10% HACC-TFSI/SPEs solid electrolyte full cell obtained in example 1 at 60 ℃ at 0.1 ℃.
FIG. 4 is a graph of the cycling performance of the 10% HACC-TFSI/SPEs solid electrolyte obtained in example 1 at 0.2C at 60 ℃.
FIG. 5 is a graph of the cycling performance of the 10% HACC-TFSI/SPEs solid state electrolyte material obtained in example 1 at 60 ℃ at 1C.
FIG. 6 is a graph of the cycling performance of the 10% HACC-TFSI/SPEs and PEO SPEs solid electrolytes obtained in example 1 (comparative example 1) at 1C, respectively, at 150 ℃.
FIG. 7 is a graph of the cycling performance of a Li-Li symmetric cell at 60 ℃ for 10% HACC-TFSI/SPEs and PEO SPEs solid state electrolytes (comparative example 1) obtained in example 1.
FIG. 8 is a graph of the effect of different ratios of HACC-TFSI doping levels on the ionic conductivity of HACC-TFSI/SPEs solid electrolyte in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) According to the mass ratio of 1: 1.5, accurately weighing 500mg of chitosan quaternary ammonium salt and 750mg of LiTFSI, respectively dissolving in 20mL and 5mL of deionized water, after the solution is completely dissolved, adding the chitosan quaternary ammonium salt polyion liquid solution into the LiTFSI solution at the speed of 0.6mL/min under rapid stirring, and generating a large amount of gel substances. After the addition was completed, the mixed solution was stirred for 9 hours to allow the ion exchange reaction to be complete as much as possible. Then the mixed solution is centrifuged for 25min in a high-speed centrifuge of 11000r/min, so that the generated HACC-TFSI is completely settled, the supernatant is poured off, about 20mL of deionized water is added, stirring at 70 deg.C for 2h to completely dissolve the generated HACC-TFSI gel, then 5mL of LiTFSI aqueous solution with the concentration of 100mg/mL was added at the rate of 0.6mL/min to form a gelatinous precipitate again, and after stirring for 9 hours, and centrifuging the mixture in a high-speed centrifuge at 11000r/min for 25min again to separate the precipitate from the supernatant, finally, dissolving the HACC-TFSI in water again, adding the LiTFSI solution again, centrifuging, transferring the HACC-TFSI gel obtained finally into a dialysis bag (with the molecular weight of 3000), continuously changing water for dialysis for 1 week to remove redundant LiTFSI salt, and finally freezing and drying the gel at the temperature of minus 80 ℃ by liquid nitrogen to obtain the HACC-TFSI aerogel material.
(2) The HACC-TFSI aerogel is transferred into a glove box, 60mg of HACC-TFSI material is accurately weighed in a 20mL glass bottle, 5mL of anhydrous DMF is added by a rubber head dropper, magnetons are added, and the mixture is magnetically stirred for 2 hours at 500r/min, so that a uniform DMF solution (marked as solution A) of HACC-TFSI can be obtained. In addition, 600mg of PEO and 193mg of LiTFSI (EO: Li ═ 20:1) were accurately weighed into another 20mL glass bottle, 8mL of anhydrous DMF and small magnetons were added, and the glass bottle was sufficiently stirred at 60 ℃ for 5 hours to obtain a uniform solution B. And finally, mixing the solution A and the solution B by using a rubber head dropper, and fully stirring for 1h to ensure that the solutions are uniformly mixed. Spreading the mixed solution in a prepared polytetrafluoroethylene mold by using a rubber head dropper, drying at 40 ℃ for 12h to primarily remove the DMF solvent, and then drying at 80 ℃ in vacuum for more than 72h to fully remove the residual DMF solvent. And cooling to room temperature, and taking the membrane out of the mold to obtain the HACC-TFSI blended PEO-based solid electrolyte material. Finally, the prepared solid electrolyte material is cut into a solid electrolyte membrane by a punching machine with the diameter of 19 for standby.
In order to test the ionic conductivity of the solid electrolyte material, a stainless steel sheet symmetric cell was prepared in the order of CR2016 positive electrode case-stainless steel sheet-solid electrolyte material-stainless steel sheet-CR 2016 negative electrode case, and the prepared stainless steel sheet symmetric cell was placed in an oven, the impedance changes of the solid electrolyte at temperatures ranging from 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ were tested with an electrochemical workstation, and the ionic conductivity of the solid electrolyte was calculated by the following formula:
in the present example, the ionic conductivity of 10% HACC-TFSI/SPEs all-solid electrolyte can reach 1.77X 10 at 30 ℃ and 60 ℃ respectively-5S cm-1And 5.01X 10-4S cm-1. The test results are shown in FIG. 1
To test the electrochemical stability of the solid electrolyte material, a steel sheet/SPE/Li cell was assembled in the order of CR2016 positive casing-stainless steel sheet-solid electrolyte membrane-lithium sheet-gasket-CR 2016 negative casing in a glove box and the cell was placed in an oven at 60 ℃ and 150 ℃ with an electrochemical workstation at 10mV s-1The LSV curve of the scanning speed test shows that the voltage windows of the prepared HACC/SPEs solid electrolyte material at 60 ℃ and 150 ℃ can respectively reach 5.26V and 3.71V test results, which are shown in figure 2.
To test the full cell cycle performance of the solid state electrolyte material, first, 80mg of LiFePO was accurately weighed4And 10mg of conductive carbon black (super P) were put into a mortar and sufficiently ground for 15min so that the two were sufficiently and uniformly mixed; adding 200mg of pre-prepared NMP solution containing 5% PVDF, adding about 200mg of NMP solution to make the solution into flowing asphalt state, adding small magnetons, stirring for 7 hr, and stirringAnd uniformly spreading the mixed solution on an aluminum foil, uniformly scraping the mixed solution by using a scraper of 100 mu m, and drying the membrane in a vacuum drying oven at the temperature of 80 ℃ for 24 hours to obtain the cathode material. And finally, punching the anode material into a circular sheet with the diameter of 12mm by using a punching machine. The obtained positive electrode material, solid electrolyte material and lithium sheet glove box were combined to form a solid electrolyte full cell, and the cycle performance of the full cell was tested at 60 ℃ at 0.1C, 0.2C and 1C rates, respectively, and the test results are shown in fig. 3, 4 and 5, respectively.
The preparation method of the solid electrolyte full cell is the same as that of the solid electrolyte full cell, the solid electrolyte full cell is placed in an oven at 150 ℃ to test the cycle performance of the solid electrolyte full cell under 1C, and the first-circle capacity of the solid electrolyte full cell can reach 150mA h-1And the average coulombic efficiency in 100 circles is more than 97%. After 100 cycles, the capacity can still retain 73% of the original capacity. Whereas the control group had lost almost all of its capacity within 15 cycles. The test results are shown in fig. 6.
Assembling the lithium symmetric battery in the order of CR2032 positive electrode shell-lithium sheet-solid electrolyte material-lithium sheet-gasket-shrapnel-CR 2032 negative electrode shell in a glove box, and at 60 deg.C at 0.25mA cm-1The current density of the lithium symmetrical battery is measured, and the long-cycle performance of the lithium symmetrical battery is tested under the condition that the lithium symmetrical battery is charged for 30min and then discharged for 30 min. The prepared battery has no obvious increase of polarization voltage within 1000 circles and can stably cycle for more than 2500 times. The test results are shown in fig. 7.
Comparative example 1
600mg PEO and 193mg LiTFSI (EO: Li 20:1) were weighed out accurately and added to another 20mL glass bottle, 8mL of anhydrous DMF and small magnetons were added, then the glass bottle was stirred sufficiently at 60 ℃ for 5 hours, after mixing uniformly, the mixed solution was spread in a previously prepared polytetrafluoroethylene mold with a rubber-tipped dropper, dried at 40 ℃ for 12 hours, the DMF solvent was removed initially, and further dried under vacuum at 80 ℃ for 72 hours or more, and the remaining DMF solvent was removed sufficiently. After cooling to room temperature, the membrane was removed from the mold to obtain a PEO SPEs solid electrolyte material. Finally, the prepared solid electrolyte material was cut into a solid electrolyte membrane by a 19-diameter die cutter for later use, and performance test was conducted under the same method conditions as in example 1.
Example 2
The other conditions were the same as in example 1 except that the amounts of HACC-TFSI added in step (2) were 30mg, 48mg, 60mg, and 72mg, respectively, to obtain solid electrolyte materials, and the ion conductivities of the solid electrolyte materials at different temperatures were tested in accordance with the method of example 1. The highest ionic conductivity was found at 60mg, as shown in fig. 8.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a chitosan polyion liquid blended PEO-based solid electrolyte is characterized by comprising the following steps:
(1) slowly adding a chitosan quaternary ammonium salt aqueous solution into a bis (trifluoromethyl) sulfonyl imide aqueous solution under a stirring state, stirring for 5-15 h for ion exchange reaction, performing centrifugal separation to obtain a chitosan quaternary ammonium salt polyion liquid hydrogel, re-dissolving the obtained chitosan quaternary ammonium salt polyion liquid hydrogel into water at 50-80 ℃, slowly adding the bis (trifluoromethyl) sulfonyl imide aqueous solution again and stirring for 5-15 h to further purify the chitosan quaternary ammonium salt polyion liquid hydrogel, performing centrifugal separation, repeating the operations of dissolving the chitosan quaternary ammonium salt polyion liquid hydrogel, adding the bis (trifluoromethyl) sulfonyl imide aqueous solution, stirring and performing centrifugal separation for 1-3 times, dialyzing, and freeze-drying to obtain a purified chitosan quaternary ammonium salt polyion liquid aerogel material;
(2) dissolving the purified chitosan quaternary ammonium salt polyion liquid aerogel material in a solvent to obtain a chitosan quaternary ammonium salt polyion liquid solution, dissolving PEO and lithium bistrifluoromethylsulfonyl imide salt in the solvent to obtain a PEO-lithium salt solution, uniformly mixing the chitosan quaternary ammonium salt polyion liquid solution and the PEO-lithium salt solution, transferring the mixture into a mold, and drying to obtain a chitosan polyion liquid blending PEO-based solid electrolyte;
wherein the mass ratio of the chitosan quaternary ammonium salt polyion liquid aerogel material purified in the step (2) to PEO is 1: 10, the molar ratio of EO units in PEO to lithium ions in lithium bistrifluoromethylsulfonimide is 10: 1-30: 1.
2. the preparation method of the chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1, wherein the slow addition speed in step (1) is 0.6-1.2 mL/min; the molar ratio of TFSI ions in the bis-trifluoromethyl sulfimide salt added in the step (1) to quaternary ammonium ions in the chitosan quaternary ammonium salt is 1.0-2.0: 1.
3. the preparation method of the chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1 or 2, wherein the concentration of the chitosan quaternary ammonium salt polyion liquid solution in the step (2) is 6-14.4 mg/ml; the concentration of PEO in the PEO-lithium salt solution is 30-150 mg/ml.
4. The preparation method of the chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1, wherein the concentration of the aqueous solution of bis (trifluoromethyl) sulfonyl imide salt in step (1) is 100-500 mg/ml, and the concentration of the aqueous solution of chitosan quaternary ammonium salt is 10-100 mg/ml; in the step (1), the chitosan quaternary ammonium salt polyion liquid hydrogel is dissolved in water again, and the ratio of the chitosan quaternary ammonium salt polyion liquid hydrogel to the water is 0.001-0.01 g/ml.
5. The preparation method of chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1 or 2, wherein the bis-trifluoromethylsulfonyl imide salt in step (1) is at least one of LiTFSI, NaTFSI and KTFSI.
6. The preparation method of the chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1 or 2, wherein the chitosan polyion liquid blended PEO-based solid electrolyte obtained in the step (2) is in a film shape, and the thickness of the chitosan polyion liquid blended PEO-based solid electrolyte is 80-200 μm.
7. The preparation method of the chitosan polyion liquid blended PEO-based solid electrolyte as claimed in claim 1 or 2, wherein the rotation speed of centrifugal separation in the step (1) is 1000-11000 r/min, and the time is 5-35 min; in the step (2), the solvent is DMF; the drying in the step (2) comprises the following steps: drying at 30-40 deg.C for 12 hr to remove solvent, and vacuum drying at 80-120 deg.C for 72 hr to remove residual solvent.
8. A chitosan polyion liquid blended PEO-based solid electrolyte prepared by the method of any one of claims 1 to 7.
9. The application of the chitosan polyionic liquid blended PEO-based solid electrolyte in a lithium ion battery as claimed in claim 8.
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| CN108428931A (en) * | 2018-04-17 | 2018-08-21 | 中国科学院宁波材料技术与工程研究所 | A kind of ion liquid polymer composite solid electrolyte, preparation method and lithium ion battery |
| CN109004270A (en) * | 2018-06-22 | 2018-12-14 | 南昌航空大学 | A kind of preparation method of chitosan quaternary ammonium salt/ionic liquid gel type polyeletrolyte |
| CN110299557A (en) * | 2019-05-07 | 2019-10-01 | 南京工业大学 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
| CN110707356A (en) * | 2019-10-16 | 2020-01-17 | 广东工业大学 | Chitosan derivative doped polymer solid electrolyte membrane and preparation method and application thereof |
| CN110729514A (en) * | 2019-10-25 | 2020-01-24 | 东莞理工学院 | Biopolymer chitosan-based composite polymer solid electrolyte and preparation method thereof |
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