CN102653624A - Organic rectorite composite polymethyl methacrylate block polystyrene copolymer gel polymer electrolyte and preparation method thereof - Google Patents
Organic rectorite composite polymethyl methacrylate block polystyrene copolymer gel polymer electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic rectorite composite polymethyl methacrylate block polystyrene copolymer gel polymer electrolyte and preparation method of the electrolyte; the organic rectorite composite polymethyl methacrylate block polystyrene copolymer gel polymer electrolyte is characterized by comprising the following raw material components: block copolymer matrix, organic rectorite clay, plasticizer and lithium salt, wherein the total mass percent of the block copolymer matrix and the organic rectorite clay is 30-60%, and the total mass percent of the plasticizer and the lithium salt is 40-70%; the mass ratio between the organic rectorite clay and the block copolymer matrix is 1:(200-1):10; the concentration of the lithium salt in the plasticizer is 1 mol/L; and the molar ratio between polymethyl methacrylate and polystyrene chain segment in the block copolymer matrix is 1:(0.5-1):4. The organic rectorite composite polymethyl methacrylate block polystyrene copolymer gel polymer electrolyte provided by the invention has satisfactory electric conductivity; and the preparation method of the electrolyte is simple in needed conditions, thus being direct, wide in applicability and simple in operation.
Description
Technical field
The present invention relates to the compound polymethylmethacrylablock block polystyrene copolymer of a kind of organic rectorite gel polymer electrolyte and preparation method thereof.
Background technology
Gel polymer electrolyte (GPE) is the system that is composited by polymkeric substance, electrolytic salt and softening agent.In GPE; Ion mainly is in the softening agent liquid phase, to transmit; Solid polymer plays a film forming skeleton supporting role; So GPE not only has the high ionic conductivity characteristics of liquid electrolyte, and have the stable and dry state characteristics of solid state electrolyte, therefore show good prospects for application at numerous areas such as lithium ion battery, solar cell, electrical condenser and electrochromic devices.
Carbonyl side group in polymethylmethacrylate (PMMA) structural unit and the oxygen in the carbonates softening agent have very strong interaction; Can contain a large amount of liquid electrolytes; Can give GPE good ion transmission performance, add the PMMA abundant raw material, low price; Interface stability to lithium electrode is good, so become one of more matrix of gel polymer electrolyte research.But mechanical strength, thermostability and the film forming properties of pure PMMA base GPE are relatively poor, have influenced its through engineering approaches and have used.
In the gel polymer electrolyte field, people are making great efforts to have high ionic conductivity and gel polymer electrolyte better hot, mechanical property simultaneously through the whole bag of tricks exploitation.Research direction mainly concentrates on the blend of various polymerization thing material, copolymerization at present, or through adding preparation composite polymer electrolytes such as inorganic nano-filler or mesopore molecular sieve.Add inorganic nano-particle in the gel polymer electrolyte and obtain the inorganic nanometer composite gel polymer dielectric; Not only can improve its mechanical property; Improve its stability; Can also reduce crystallization superpolymer second-order transition temperature and percent crystallinity through destroying the regularity of polymer molecular chain to the crystal polymer thing, improve ionic conductivity; Another kind of research direction is exactly the new polymeric system of development; Prepare comb-shaped polymer like grafting on polymer molecular chain; Or another molecule of insertion prepares the block polymer ionogen between polymer chain, and this is because the special construction of hyperbranched polymer system and block polymer molecule is more conducive to the ionic conduction.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes the compound polymethylmethacrylablock block polystyrene copolymer of a kind of organic rectorite gel polymer electrolyte and preparation method thereof; From synthetic segmented copolymer polymethylmethacrylablock block PS matrix, add organic rectorite and prepare the nano-composite gel polymer dielectric.
Technical scheme
The compound polymethylmethacrylablock block polystyrene copolymer of a kind of organic rectorite gel polymer electrolyte; It is characterized in that material component is: segmented copolymer matrix and organic rectorite clay total mass mark are 30%～60%, and softening agent and lithium salts total mass mark are 40%～70%; The mass ratio of said organic rectorite clay and segmented copolymer matrix is 1: 200～1: 10; The concentration of said lithium salts in softening agent is 1mol/L; Polymethylmethacrylate and PS segment mol ratio are 1: 0.5～1: 4 in the said segmented copolymer matrix.
Said softening agent is one or more in propylene carbonate, NSC 11801, diethyl carbonate, methylcarbonate, Methyl ethyl carbonate, the Witcizer 300.
Said lithium salts is one or more in lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium.
Said organic rectorite clay is through tensio-active agent C
12-C
18The organic rectorite clay of long chain quaternary modification.
A kind of method for preparing the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite gel polymer electrolyte is characterized in that step is following:
Polymetylmethacrylate-Br the macromole evocating agent of step 1 preparation band bromine end group: monomers methyl methacrylate MMA, initiator 2-isobutyl ethyl bromide and catalystsystem cuprous bromide-PMDETA is mixed; The add-on of reaction solvent THF is 1～3 times of reaction raw materials total mass; Through freezing vacuumizing-fill nitrogen to vacuum tightness is 0 3～6 times; Under nitrogen atmosphere, reacted 4～6 hours then, temperature of reaction is 50～70 ℃; After reaction finished, solution was crossed the neutral alumina post, revolved the steaming solvent after having crossed pillar, and methanol wash precipitates then, and suction filtration is put into vacuum drying oven with product at last and is dried to constant weight for 40 ℃, obtains white PMMA-Br macromole evocating agent;
Step 2 preparation segmented copolymer polymethylmethacrylablock block PS: reaction monomers vinylbenzene St, step 1 synthetic PMMA-Br and catalystsystem cuprous bromide-PMDETA is mixed; Reaction solvent N; The add-on of dinethylformamide is 1～3 times of reaction raw materials total mass; Nitrogen atmosphere is reaction 8～12h down, and temperature of reaction is 70～110 ℃; Reaction is diluted reaction solution after finishing with THF, cross the neutral alumina post; Revolve the steaming solvent; With behind methanol extraction, the process suction filtration, product is put into vacuum drying oven be dried to constant weight for 40 ℃ then, obtain segmented copolymer polymethylmethacrylablock block PS;
Step 3: lithium salts is dissolved in the softening agent, is made into the solution that concentration is 1mol/L;
Step 4: adopt the high speed shear appearance organic rectorite to be dispersed in the plasticizer solution of concentration 1mol/L lithium salts in the step 3;
Step 5: the polymethylmethacrylablock block polystyrene copolymer that step 2 is obtained is dissolved in a certain amount of THF; After treating that polymkeric substance fully dissolves, add the solution of step 4 gained, ultra-sonic dispersion 30～60min mixes solution under the room temperature; Solution-cast legal system film then; Leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 10～30h, make the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite gel polymer electrolyte.
The mol ratio of required monomers methyl methacrylate, initiator 2-isobutyl ethyl bromide, catalyzer cuprous chloride and four kinds of materials of part PMDETA is 60: 1: 1 in the said step 1: 2～100: 1: 1: 2.
The mol ratio of the polymethylmethacrylate of required monomer styrene, band bromine end group, catalyzer cuprous chloride and four kinds of materials of part PMDETA is 50: 100: 1 in the said step 2: 2～400: 100: 1: 2.
Beneficial effect
The compound polymethylmethacrylablock block polystyrene copolymer of a kind of organic rectorite gel polymer electrolyte that the present invention proposes combines preparation block copolymer system and interpolation nanoparticle two aspects to improve heat, mechanical stability and the specific conductivity of PMMA base gel polymer electrolyte simultaneously.Rigid polystyrene segment in the polymethylmethacrylablock block polystyrene copolymer plays the supporting role of physical crosslinking in gelling system; For gel electrolyte provides stronger heat, mechanical stability; Thereby being had preferably with liquid electrolyte, flexible polymethylmethacrylate segment combines, for gel electrolyte provides higher ionic conduction performance; Organic rectorite after the modification and block polymer have good consistency; It is added in the gel electrolyte; Block polymer can insert the nano-composite gel polymer dielectric (NGPE) that its interlayer forms intercalation or part delaminating structure, and this particular structural can be given NGPE excellent conductivity.
The compound polymethylmethacrylablock block polystyrene copolymer of the organic rectorite gel polymer electrolyte that the present invention proposes has gratifying specific conductivity, can satisfy as the requirement of lithium ion battery electrolyte to ionic conductivity.The required condition of the prepared of this gel electrolyte is simple, and common lab can reach, and is a kind of direct, suitability method for preparing gel electrolyte wide, simple to operate.
Description of drawings
Fig. 1: be gel electrolyte matrix polymethylmethacrylablock block polystyrene copolymer synthetic route of the present invention;
Fig. 2: be matrix polymethylmethacrylablock block polystyrene copolymer aftertreatment schema of the present invention;
Fig. 3: be preparation technology's schema of the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite of the present invention gel polymer electrolyte;
Fig. 4: for the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite of the present invention gel polymer electrolyte (adds the alternating-current impedance spectrogram of different amount organic rectorites in (lithium perchlorate/propylene carbonate: 1mol/L)).
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Embodiment 1:
Synthesizing of polymethylmethacrylate (PMMA-Br) macromole evocating agent of step 1 band bromine end group: monomers methyl methacrylate MMA, initiator 2-isobutyl ethyl bromide, catalystsystem cuprous bromide-PMDETA; Four kinds of material mol ratios are 60: 1: 1: 2～100: 1: 1: 2; After placing there-necked flask, add a certain amount of THF, behind freezing vacuumizing-fill nitrogen 3～6 times; Reaction is 4～6 hours under nitrogen atmosphere, and temperature of reaction is 50～70 ℃.After reaction finished, solution was crossed the neutral alumina post, had crossed to revolve steaming behind the pillar and fall a part of solvent, and methanol wash precipitates then, and suction filtration is put into vacuum drying oven with product at last and is dried to constant weight for 40 ℃, obtains white PMMA-Br macromole evocating agent.
Synthesizing of step 2 polymethylmethacrylablock block polystyrene copolymer matrix: reaction monomers vinylbenzene St, step 1 synthetic PMMA-Br, catalystsystem cuprous bromide-PMDETA; Four mol ratios are 50: 100: 1: 2～100: 100: 1: 2; Reaction solvent is N; Dinethylformamide, nitrogen atmosphere be reaction 8～12h down, and temperature of reaction is 70～110 ℃.Reaction is diluted reaction solution after finishing with THF, cross the neutral alumina post; Revolve and steam partial solvent; With behind methanol extraction, the process suction filtration, product is put into vacuum drying oven be dried to constant weight for 40 ℃ then, obtain the polymethylmethacrylablock block polystyrene copolymer.
Step 3: lithium perchlorate is dissolved in the propylene carbonate, is made into the solution that concentration is 1mol/L.
Step 4: take by weighing the 0.006g organic rectorite, adopting the high speed shear appearance is in the carbonic allyl ester solution of 1mol/L lithium perchlorate with its concentration that is evenly dispersed in 0.909g step 3.
Step 5: take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it is dissolved in the THF of 4～6mL; After treating fully dissolving; Add the solution of step 4, at room temperature ultrasonic 30～60min mixes solution, uses solution-cast legal system film then; Leave standstill 12h under the room temperature; Treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h, making organic rectorite content is 1phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 2:
Step 1, step 2 and step 3 are the same with embodiment 1.
Step 4: take by weighing the 0.012g organic rectorite, adopting the high speed shear appearance is in the carbonic allyl ester solution of 1mol/L lithium perchlorate with its concentration that is evenly dispersed in 0.918g step 3.
Step 5: similar basically with embodiment 1; The polymethylmethacrylablock block polystyrene copolymer of getting 0.6g is dissolved in it in THF of 4～6mL, after treating fully to dissolve, adds the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 2phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 3:
Step 1, step 2 and step 3 are the same with embodiment 1.
Step 4: take by weighing the 0.018g organic rectorite, adopting the high speed shear appearance is in the carbonic allyl ester solution of 1mol/L lithium perchlorate with its concentration that is evenly dispersed in 0.927g step 3.
Step 5: similar basically with embodiment 1; The polymethylmethacrylablock block polystyrene copolymer of getting 0.6g is dissolved in it in THF of 4～6mL, after treating fully to dissolve, adds the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 3phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 4:
Step 1, step 2 and step 3 are the same with embodiment 1.
Step 4: take by weighing the 0.024g organic rectorite, adopting the high speed shear appearance is in the carbonic allyl ester solution of 1mol/L lithium perchlorate with its concentration that is evenly dispersed in 0.936g step 3.
Step 5: similar basically with embodiment 1; The polymethylmethacrylablock block polystyrene copolymer of getting 0.6g is dissolved in it in THF of 4～6mL, after treating fully to dissolve, adds the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 4phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 5:
Step 1, step 2 and step 3 are the same with embodiment 1.
Step 4: take by weighing the 0.030g organic rectorite, adopting the high speed shear appearance is in the carbonic allyl ester solution of 1mol/L lithium perchlorate with its concentration that is evenly dispersed in 0.945g step 3.
Step 5: similar basically with embodiment 1; The polymethylmethacrylablock block polystyrene copolymer of getting 0.6g is dissolved in it in THF of 4～6mL, after treating fully to dissolve, adds the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 5phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 6:
Step 1 is the same with embodiment 1 with step 2.
Step 3: lithium hexafluoro phosphate is dissolved in NSC 11801 and the methylcarbonate (both volume ratios 1: 1), is made into the solution that concentration is 1mol/L.
Step 4: take by weighing the 0.006g organic rectorite, adopting the high speed shear appearance is in the NSC 11801 and methylcarbonate solution of 1mol/L lithium hexafluoro phosphate with its concentration that is evenly dispersed in 0.909g step 3.
Step 5: take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it is dissolved in the THF of 4～6mL; After treating fully dissolving; Add the solution of step 4, at room temperature ultrasonic 30～60min mixes solution, uses solution-cast legal system film then; Leave standstill 12h under the room temperature; Treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h, making organic rectorite content is 1phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 7:
Step 1, step 2 and step 3 are the same with embodiment 6.
Step 4: take by weighing the 0.012g organic rectorite, adopting the high speed shear appearance is in the NSC 11801 and methylcarbonate solution of 1mol/L lithium hexafluoro phosphate with its concentration that is evenly dispersed in 0.918g step 3.
Step 5: similar basically with embodiment 6; Take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it be dissolved in the THF of 4～6mL, treat fully dissolving after, add the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 2phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 8:
Step 1, step 2 and step 3 are the same with embodiment 6.
Step 4: take by weighing the 0.018g organic rectorite, adopting the high speed shear appearance is in the NSC 11801 and methylcarbonate solution of 1mol/L lithium hexafluoro phosphate with its concentration that is evenly dispersed in 0.927g step 3.
Step 5: similar basically with embodiment 6; Take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it be dissolved in the THF of 4～6mL, treat fully dissolving after, add the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 3phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 9:
Step 1, step 2 and step 3 are the same with embodiment 6.
Step 4: take by weighing the 0.024g organic rectorite, adopting the high speed shear appearance is in the NSC 11801 and methylcarbonate solution of 1mol/L lithium hexafluoro phosphate with its concentration that is evenly dispersed in 0.936g step 3.
Step 5: similar basically with embodiment 6; Take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it be dissolved in the THF of 4～6mL, treat fully dissolving after, add the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 4phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
Embodiment 10:
Step 1, step 2 and step 3 are the same with embodiment 6.
Step 4: take by weighing the 0.030g organic rectorite, adopting the high speed shear appearance is in the NSC 11801 and methylcarbonate solution of 1mol/L lithium hexafluoro phosphate with its concentration that is evenly dispersed in 0.945g step 3.
Step 5: similar basically with embodiment 6; Take by weighing 0.6g polymethylmethacrylablock block polystyrene copolymer and it be dissolved in the THF of 4～6mL, treat fully dissolving after, add the solution of step 4; At room temperature ultrasonic 30～60min mixes solution; Use solution-cast legal system film then, leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF partly volatilizees and dry by the fire 24h; Making organic rectorite content is 5phr, and solid content (polymeric matrix, both massfractions of organic rectorite) is 40% polymethylmethacrylablock block polystyrene copolymer gel polymer electrolyte.
The electrical property of the compound polymethylmethacrylablock block polystyrene copolymer of the organic rectorite gel polymer electrolyte film of embodiment 1～5 gained is as shown in table 1.
Claims (7)
1. the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite gel polymer electrolyte; It is characterized in that material component is: segmented copolymer matrix and organic rectorite clay total mass mark are 30%～60%, and softening agent and lithium salts total mass mark are 40%～70%; The mass ratio of said organic rectorite clay and segmented copolymer matrix is 1: 200～1: 10; The concentration of said lithium salts in softening agent is 1mol/L; Polymethylmethacrylate and PS segment mol ratio are 1: 0.5～1: 4 in the said segmented copolymer matrix.
2. organic rectorite modified composite gel type electrolyte according to claim 1 is characterized in that said organic rectorite clay is the organic rectorite clay through the long chain quaternary modification of tensio-active agent C12-C18.
3. according to the compound polymethylmethacrylablock block polystyrene copolymer of the said organic rectorite of claim 1 gel polymer electrolyte, it is characterized in that said softening agent is one or more in propylene carbonate, NSC 11801, diethyl carbonate, methylcarbonate, Methyl ethyl carbonate, the Witcizer 300.
4. according to the compound polymethylmethacrylablock block polystyrene copolymer of the said organic rectorite of claim 1 gel polymer electrolyte, it is characterized in that said lithium salts is one or more in lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium.
5. one kind prepares the compound polymethylmethacrylablock block polystyrene copolymer of each described organic rectorite of claim 1～4 gel polymer electrolyte, it is characterized in that step is following:
Polymetylmethacrylate-Br the macromole evocating agent of step 1 preparation band bromine end group: monomers methyl methacrylate MMA, initiator 2-isobutyl ethyl bromide and catalystsystem cuprous bromide-PMDETA is mixed; The add-on of reaction solvent THF is 1～3 times of reaction raw materials total mass; Through freezing vacuumizing-fill nitrogen to vacuum tightness is 0 3～6 times; Under nitrogen atmosphere, reacted 4～6 hours then, temperature of reaction is 50～70 ℃; After reaction finished, solution was crossed the neutral alumina post, revolved the steaming solvent after having crossed pillar, and methanol wash precipitates then, and suction filtration is put into vacuum drying oven with product at last and is dried to constant weight for 40 ℃, obtains white PMMA-Br macromole evocating agent;
Step 2 preparation segmented copolymer polymethylmethacrylablock block PS: reaction monomers vinylbenzene St, step 1 synthetic PMMA-Br and catalystsystem cuprous bromide-PMDETA is mixed; Reaction solvent N; The add-on of dinethylformamide is 1～3 times of reaction raw materials total mass; Nitrogen atmosphere is reaction 8～12h down, and temperature of reaction is 70～110 ℃; Reaction is diluted reaction solution after finishing with THF, cross the neutral alumina post; Revolve the steaming solvent; With behind methanol extraction, the process suction filtration, product is put into vacuum drying oven be dried to constant weight for 40 ℃ then, obtain segmented copolymer polymethylmethacrylablock block PS;
Step 3: lithium salts is dissolved in the softening agent, is made into the solution that concentration is 1mol/L;
Step 4: adopt the high speed shear appearance organic rectorite to be dispersed in the plasticizer solution of concentration 1mol/L lithium salts in the step 3;
Step 5: the polymethylmethacrylablock block polystyrene copolymer that step 2 is obtained is dissolved in THF; After treating that polymkeric substance fully dissolves, add the solution of step 4 gained, ultra-sonic dispersion 30～60min mixes solution under the room temperature; Solution-cast legal system film then; Leave standstill 12h under the room temperature, treat to insert in 40 ℃ of baking ovens after THF volatilizees and dry by the fire 10～30h, make the compound polymethylmethacrylablock block polystyrene copolymer of organic rectorite gel polymer electrolyte.
6. preparation method according to claim 5 is characterized in that: the mol ratio of required monomers methyl methacrylate, initiator 2-isobutyl ethyl bromide, catalyzer cuprous chloride and four kinds of materials of part PMDETA is 60: 1: 1 in the said step 1: 2～100: 1: 1: 2.
7. preparation method according to claim 5 is characterized in that: the mol ratio of the polymethylmethacrylate of required monomer styrene, band bromine end group, catalyzer cuprous chloride and four kinds of materials of part PMDETA is 50: 100: 1 in the said step 2: 2～400: 100: 1: 2.
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| WO2024119495A1 (en) * | 2022-12-09 | 2024-06-13 | Ses (Shanghai) Co. Ltd. | Gel polymer electrolytes, and energy-storage cells and batteries made therewith |
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| CN114639856A (en) * | 2020-12-16 | 2022-06-17 | 中国科学院宁波材料技术与工程研究所 | Composite gel polymer electrolyte for lithium-air battery, preparation method of composite gel polymer electrolyte and lithium-air battery |
| CN114639856B (en) * | 2020-12-16 | 2024-05-31 | 中国科学院宁波材料技术与工程研究所 | Composite gel polymer electrolyte for lithium-air battery, preparation method of composite gel polymer electrolyte and lithium-air battery |
| WO2024119495A1 (en) * | 2022-12-09 | 2024-06-13 | Ses (Shanghai) Co. Ltd. | Gel polymer electrolytes, and energy-storage cells and batteries made therewith |
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Application publication date: 20120905 |