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CN103855423A - Liquid crystalline ionomer PEO/PMMA solid electrolyte and preparation method thereof - Google Patents

Liquid crystalline ionomer PEO/PMMA solid electrolyte and preparation method thereof Download PDF

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Publication number
CN103855423A
CN103855423A CN201210496588.5A CN201210496588A CN103855423A CN 103855423 A CN103855423 A CN 103855423A CN 201210496588 A CN201210496588 A CN 201210496588A CN 103855423 A CN103855423 A CN 103855423A
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peo
pmma
liquid crystalline
solution
crystalline ionomer
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张爱玲
那贵洲
李三喜
吕震乾
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Shenyang University of Technology
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Shenyang University of Technology
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

The invention relates to a liquid crystalline ionomer PEO/PMMA solid electrolyte and a preparation method thereof, which is characterized in that the liquid crystalline ionomer PEO/PMMA solid electrolyte is composed of PEO, PMMA, lithium salt, the liquid crystalline ionomer and an aprotic solvent; the preparation method comprises the following steps: taking PEO and PMMA as matrix, dissolving PEO and PMMA in a first anhydrous solvent to form a first solution; dissolving lithium salt and the liquid crystalline ionomer in a second anhydrous solvent to form a second solution; blending and uniformly stirring the first solution and the second solution to prepare a mixed solution; knifing the mixed solution to prepare an electrolyte membrane with certain thickness, and evaporating the solvent to form a solid polymer electrolyte. The liquid crystalline ionomer PEO/PMMA solid electrolyte solves the problem that the glass-transition temperature of current PEO is low and is not stable under room temperature, PMMA is stable and can not reach the requirement due to low conductivity at room temperature, the liquid crystalline ionomer is simultaneously added, the ionic transmission is increased, the ion conductivity is increased, and the matrix mechanical property is increased.

Description

Liquid Crystalline Ionomer PEO/PMMA solid electrolyte and preparation method thereof
Technical field
The present invention relates to a kind of polymer dielectric and preparation method thereof, particularly relate to a kind of Liquid Crystalline Ionomer PEO/PMMA solid electrolyte and preparation method thereof, be applicable to electrochemical appliance, as the secondary cell of high-energy-density.
Background technology
Information, the energy and environmental protection are the major subjects of 21 century human society care.Green secondary lithium battery, with its high power capacity, almost pollution-free and security performance good and studied widely to environment, is developed rapidly over nearly 10 years.Lithium ion battery is divided into liquid lithium ionic cell and solid lithium ion battery, the leakage that outstanding problem be exactly electrolyte solution of liquid lithium ionic cell in application, in battery, include inflammable component, as organic electrolyte solution and charing lithium, after electrolyte leakage, can cause fire.If replace liquid electrolyte with polymer, can avoid electrolytical leakage, therefore, the research that many researchers are detailed polymer Li-ion battery.
The various advantages such as operating voltage is high except having for polymer Li-ion battery, energy density large, have extended cycle life, owing to adopting immobilising electrolyte, it has also made up many deficiencies of liquid lithium ionic cell, polymer Li-ion battery has flexible design, safe, the advantages such as packaged convenience.
Although the progress of polymer Li-ion battery is very fast, there is finished product battery production in batches, from the domestic and international present Research to the sub-battery of polymer lithium, the performance of existing polymer Li-ion battery is still not ideal enough.Compared with liquid organic bath lithium ion battery, the subject matter that polymer Li-ion battery exists shows as: (1) high-rate charge-discharge capability is not good enough.(2) poor performance at low temperatures.(3) production technology is constantly improved, and production line is not mature enough comparatively speaking.(4) change into and may occur inflatable problem, make technology of the package complexity.(5) basic research hysteresis application and development.To polymer dielectric electrical conduction mechanism; Polymer network microstructure and electrode performance relation; Electrode/polymer dielectric interfacial property and polymer and electrolyte interact; The research of the aspects such as the impact of non-electrochemical factor on battery performance is not mature enough.
Therefore, need to improve electrolyte.Improve electrolytic conductivity and have two kinds of approach: suppress the crystallization of polymer chain; Improve and carry ion concentration.Copolymerization, crosslinked, blend, plasticising and add the methods such as inorganic material, the degree of crystallinity that can effectively reduce polymer improves the ratio of amorphous domain, increased in system simultaneously and to have carried ion concentration, because of but the effective means [45] of raising polymer electrolyte system performance.Below some concrete introductions that how to improve the means of system performance.
1. copolymerization
(1) random copolymerization: be a kind of matrix polymer of the most successful use, the medium but indefinite group space of series length in this structure.The people such as Booth nineteen ninety reported first made the random copolymer of ethylene oxide-Oxymethylene structure, by itself and LiClO 4compound rear conductivity can reach 10-4S/cm.Reduce the degree of crystallinity of product by copolymerization, thereby reach the object that improves conductivity.
(2) block copolymerization: adopt block copolymerization can obtain the basic similarly effect of same random copolymerization.Graft copolymerization: because the electricity of copolymer solid electrolyte material is led the localized heat motion that depends on polymer segment, therefore, preparing the extremely submissive pectination of main chain and graft polymers is the method for comparatively commonly using, wherein especially take polysiloxane-grafted polyethylene glycol oxide as representative.
2. crosslinked
Crosslinked is the common method that improves mechanical properties of polymer, crosslinked mechanical performance and the thermal stability that can improve polymeric system.This is significant for improving sticky soft polyethers polymer sizes stability.Also be the effective means that suppresses polymer crystallization simultaneously.Crosslinked method comprises radiation, chemical crosslinking and heat treating process.Rhee, by UV polymerization, prepares polyethylene glycol two adipate esters (PEGDA) and LiCF 3sO 3cross-linked polymer electrolyte, conductivity can reach 10 -5s/cm.
3. blend
Blend also can be used as to reduce the method for high polymer Tg and degree of crystallinity the means that improve conductivity.As PEO and the blend of polypropylene phthalein amine for Przyluski etc., then with LiClO 4the complex compound room-temperature conductivity that reaction forms is higher than 10-4S/cm.Although can improve the room-temperature conductivity of copolymer solid electrolyte material by blend, its mechanical property has certain loss.
4. plasticising
Plasticising also can reduce polyethers Tg and degree of crystallinity greatly, reaches the object that improves room-temperature ion conductivity, is the good method of current raising solid polymer electrolyte room-temperature ion conductivity used.Plasticizer used should have larger dielectric constant, to promote salt to dissociate; Must there is good compatibility with polymer.
5. add inorganic material
Inorganic material is added in polymer electrolyte system, can upset polymer chain, suppresses the crystal property of polymer, and the polymer architecture aspect of particle surface group around change filler also plays a positive role.Inorganic powder additive has a variety of explanations to the effect of polymer electrolyte system conductivity.Wherein the application of EMT (Effective Medium Theory) theoretical model is comparatively extensive.Model thinks that polymer electrolyte system adulterated after inorganic particles, inorganic microparticle-dispersed is in polymer dielectric, on polymer-alloy interface, have the cover layer that a kind of conductivity is higher, the conductivity of polymer dielectric is mainly made up of three aspects:: the self-conductance of polymer dielectric, the electricity of discrete particles are led with the height electricity on discrete particles surface and led cover layer.
Conventionally lithium ion battery polymer electrolyte matrix adopting PEO or PMMA, because PEO glass transition temperature is lower, at room temperature unstable.PMMA is more stable but room-temperature conductivity is lower, does not reach requirement.
Summary of the invention
The object of the invention is to solve prior art above shortcomings, provide a kind of Liquid Crystalline Ionomer PEO/PMMA solid electrolyte and preparation method thereof, PEO and PMMA are jointly done matrix by the present invention, adopts the method for blend, and the electrolyte making can solve above 2 deficiencies.Add Liquid Crystalline Ionomer simultaneously, increased the transmission of ion, improve ionic conductivity, also improved the mechanical property of matrix.
The technical scheme providing is to achieve the object of the present invention:
This Liquid Crystalline Ionomer PEO/PMMA solid electrolyte, has been characterized in PEO, PMMA, and lithium salts, Liquid Crystalline Ionomer and aprotic solvent, wherein each components based on weight percentage is:
PEO：30％～70％；PMMA：70％～30％；
Lithium salts: 2%～10%; Liquid Crystalline Ionomer: 0.2%～2.0%;
Aprotic solvent: 10%～20%.
Described PEO viscosity average molecular weigh scope is between 450,000 to 750,000.
Described PMMA viscosity average molecular weigh scope is between 80,000 to 200,000.
Described lithium salts is selected from LiPF 6, LiAsF 6, LiBF 4, LiClO 4in one.
Described Liquid Crystalline Ionomer is selected from the one in main chain liquid crystal ionomer, Side-Chain Thermotropic Liquid Crystalline Ionomer.
Described aprotic solvent is selected from the one in oxolane, carrene, acetone.
This Liquid Crystalline Ionomer PEO/PMMA method for preparing solid electrolyte that the present invention provides, is characterized in that described Liquid Crystalline Ionomer PEO/PMMA solid electrolyte makes by solution film casting method, wherein:
Take PEO and PMMA as matrix, PEO and PMMA are dissolved in the first anhydrous solvent, form the first solution, the time that course of dissolution needs is 18 to 36 hours, the mass ratio of PEO and PMMA is between 0.4 to 2.4, and the first anhydrous solvent is selected from the one in oxolane, acetonitrile, acetone, carrene;
Lithium salts and Liquid Crystalline Ionomer are dissolved in and in the second anhydrous solvent, form the second solution, the second anhydrous solvent is simultaneously as plasticizer, to improve electrolytical performance, the ratio of lithium salts accounts for the mass percent of matrix in the first solution between 0 to 20, the ratio of Liquid Crystalline Ionomer accounts for the mass fraction of matrix in the first solution between 0 to 4, the second anhydrous solvent is selected from the one in ethylene carbonate, butyl acetate, nitrogen methyl pyrrolidone, the rare ester of acetic acid second, course of dissolution needs heating, and temperature is at 50 to 90 degrees Celsius;
By the first solution and the second solution blending, stir, make mixed solution;
By I-shaped spreader knifing or whirler for mixed solution, make the certain dielectric film of thickness, after solvent slow evaporation, form solid polymer electrolyte, be 18 to 36 hours drying time, baking temperature is 40 to 70 degrees Celsius, adopts AC impedance method to measure its conductivity and reaches 0.001S.cm -1.
Compared with prior art, the invention has the beneficial effects as follows:
PEO and PMMA are jointly done matrix by the present invention.Adopt the method for blend, it is lower at room temperature unstable that the electrolyte making can solve PEO glass transition temperature of the prior art, the lower deficiency that does not reach requirement of room-temperature conductivity and PMMA is more stable, add Liquid Crystalline Ionomer simultaneously, increased the transmission of ion, improve ionic conductivity, also improved the mechanical property of matrix.Concrete data are in table 1.
Table 1 the present invention and prior art performance comparison
Figure DEST_PATH_GDA00002812802500051
Embodiment
A kind of Liquid Crystalline Ionomer PEO/PMMA solid electrolyte, has PEO, PMMA, and lithium salts, Liquid Crystalline Ionomer and aprotic solvent, wherein each components based on weight percentage is:
PEO：30％～70％；PMMA：70％～30％；
Lithium salts: 2%～10%; Liquid Crystalline Ionomer: 0.2%～2.0%;
Aprotic solvent: 10%～20%.
Concrete preparation process is as follows:
1.PEO: PMMA by mass percentage (30-70,50-50,70-30) weighs, and wherein the molecular weight of PEO is 450,000～750,000, and the molecular weight of PMMA is 80,000～200,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution, i.e. the first solution.
2. take lithium perchlorate (2%-10%), Liquid Crystalline Ionomer (0.2%-2.0%), by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration, be the second solution, Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
The first solution in the second solution in step 2 and step 1 is even with the volume ratio blending and stirring of 1: 50 3., obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -4-10 -3s.cm -1.
Embodiment 1
1.PEO: PMMA by mass percentage (30-70) weighs, and the molecular weight that wherein molecular weight of PEO is 480,000, PMMA is 90,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 0.5%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -4s.cm -1.
Embodiment 2
1.PEO: PMMA by mass percentage (30-70) weighs, and the molecular weight that wherein molecular weight of PEO is 520,000, PMMA is 100,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 0.8%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -4s.cm -1.
Embodiment 3
1.PEO: PMMA by mass percentage (50-50) weighs, and the molecular weight that wherein molecular weight of PEO is 600,000, PMMA is 110,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 1.0%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -4s.cm -1.
Embodiment 4
1.PEO: PMMA by mass percentage (50-50) weighs, and the molecular weight that wherein molecular weight of PEO is 650,000, PMMA is 120,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 1.5%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -4s.cm -1.
Embodiment 5
1.PEO: PMMA by mass percentage (70-30) weighs, and the molecular weight that wherein molecular weight of PEO is 500,000, PMMA is 100,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 1.0%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -3s.cm -1.
Embodiment 6
1.PEO: PMMA by mass percentage (70-30) weighs, and the molecular weight that wherein molecular weight of PEO is 600,000, PMMA is 130,000, is configured to the dichloromethane solution of 30g/L, stirs sealing.Place one day to two days, treat the whole solvents of solid, form homogeneous phase solution.
2. take lithium perchlorate 10%, Liquid Crystalline Ionomer 2.0%, by 80 ℃ of heating stirring and dissolving of 1-METHYLPYRROLIDONE, preparation is respectively the solution of 0.03-0.15g/L and 0.003-0.03g/L containing lithium perchlorate and Liquid Crystalline Ionomer concentration.Liquid Crystalline Ionomer is the main chain liquid crystal macromolecule containing azochlorosulfonate acid ion.
3. by even with the volume ratio blending and stirring of 1: 50 to the solution in 2 and Matrix Solution, obtain gelatinous liquid, knifing or revolve film with whirler on glass plate or tetrafluoroethene plate, make thickness at the thick homogeneous film of 0.1-0.5mm, the film that makes is adopted after 45 ℃ of vacuumize 24h, peel off matrix with blade.
4. reach 10 by the room-temperature conductivity that AC impedance method records film -3s.cm -1.
By to electrolytical infrared spectrum analysis, illustrate that LCI is to LiClO 4there is the effect of conduction, can strengthen the conduction of lithium ion, increase conductivity, in table 2～table 5.
Table 2PEO: PMMA=30: 70 serial conductivity
Figure DEST_PATH_GDA00002812802500091
Figure DEST_PATH_GDA00002812802500101
Table 3PEO: PMMA=50: 50 serial conductivity
Figure DEST_PATH_GDA00002812802500102
Table 4PEO: PMMA=70: 30 serial conductivity
Figure DEST_PATH_GDA00002812802500103
Table 5 relatively
Figure DEST_PATH_GDA00002812802500104
Figure DEST_PATH_GDA00002812802500111

Claims (7)

1. a Liquid Crystalline Ionomer PEO/PMMA solid electrolyte, is characterized in that there is PEO, PMMA, and lithium salts, Liquid Crystalline Ionomer and aprotic solvent, wherein each components based on weight percentage is:
PEO：30％～70％；PMMA：70％～30％；
Lithium salts: 2%～10%; Liquid Crystalline Ionomer: 0.2%～2.0%;
Aprotic solvent: 10%～20%.
2. Liquid Crystalline Ionomer PEO/PMMA solid electrolyte according to claim 1, is characterized in that described PEO viscosity average molecular weigh scope is between 450,000 to 750,000.
3. Liquid Crystalline Ionomer PEO/PMMA solid electrolyte according to claim 1, is characterized in that described PMMA viscosity average molecular weigh scope is between 80,000 to 200,000.
4. Liquid Crystalline Ionomer PEO/PMMA solid electrolyte according to claim 1, is characterized in that described lithium salts is selected from LiPF 6, LiAsF 6, LiBF 4, LiClO 4in one.
5. Liquid Crystalline Ionomer PEO/PMMA solid electrolyte according to claim 1, is characterized in that described Liquid Crystalline Ionomer is selected from the one in main chain liquid crystal ionomer, Side-Chain Thermotropic Liquid Crystalline Ionomer.
6. Liquid Crystalline Ionomer PEO/PMMA solid electrolyte according to claim 1, is characterized in that described aprotic solvent is selected from the one in oxolane, carrene, acetone.
7. Liquid Crystalline Ionomer PEO/PMMA method for preparing solid electrolyte described in claim 1, is characterized in that described Liquid Crystalline Ionomer PEO/PMMA solid electrolyte makes by solution film casting method, wherein:
Take PEO and PMMA as matrix, PEO and PMMA are dissolved in the first anhydrous solvent, form the first solution, the time that course of dissolution needs is 18 to 36 hours, the mass ratio of PEO and PMMA is between 0.4 to 2.4, and the first anhydrous solvent is selected from the one in oxolane, acetonitrile, acetone, carrene;
Lithium salts and Liquid Crystalline Ionomer are dissolved in and in the second anhydrous solvent, form the second solution, the second anhydrous solvent is simultaneously as plasticizer, to improve electrolytical performance, the ratio of lithium salts accounts for the mass percent of matrix in the first solution between 0 to 20, the ratio of Liquid Crystalline Ionomer accounts for the mass fraction of matrix in the first solution between 0 to 4, the second anhydrous solvent is selected from the one in ethylene carbonate, butyl acetate, nitrogen methyl pyrrolidone, the rare ester of acetic acid second, course of dissolution needs heating, and temperature is 50 to 90 degrees Celsius of left and right;
By the first solution and the second solution blending, stir, make mixed solution;
By I-shaped spreader knifing or whirler for mixed solution, make the certain dielectric film of thickness, after solvent slow evaporation, form solid polymer electrolyte, be 18 to 36 hours drying time, baking temperature is 40 to 70 degrees Celsius of left and right, adopts AC impedance method to measure its conductivity and reaches 0.001S.cm -1.
CN201210496588.5A 2012-11-29 2012-11-29 Liquid crystalline ionomer PEO/PMMA solid electrolyte and preparation method thereof Pending CN103855423A (en)

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CN106876784A (en) * 2017-01-04 2017-06-20 沈阳工业大学 A kind of PEO bases solid polymer electrolyte membrane and preparation method thereof
CN104650375B (en) * 2015-03-17 2017-08-11 长沙理工大学 Preparation method of composite polymer electrolyte membrane
CN108963327A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of compound PEO solid electrolyte material of inorganic filler and preparation method and all-solid-state battery
CN109755630A (en) * 2017-11-03 2019-05-14 深圳格林德能源集团有限公司 A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery
CN111477951A (en) * 2020-04-14 2020-07-31 宁德新能源科技有限公司 Composite electrolyte and electrochemical and electronic device using the same
WO2020207450A1 (en) * 2019-04-10 2020-10-15 深圳新宙邦科技股份有限公司 Solid electrolyte and polymer lithium ion battery
CN113451645A (en) * 2021-07-20 2021-09-28 武汉海翎化学工业有限公司 High-conductivity polyethylene oxide electrolyte material and preparation method thereof
WO2022076520A1 (en) * 2020-10-06 2022-04-14 Brightvolt, Inc. Solid polymer matrix electrolytes (pme) and methods and uses thereof
US11715863B2 (en) 2018-08-08 2023-08-01 Brightvolt, Inc. Solid polymer matrix electrolytes (PME) and methods and uses thereof

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