CN112864469A - Method for modifying polymer solid polyelectrolyte - Google Patents

Method for modifying polymer solid polyelectrolyte Download PDF

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CN112864469A
CN112864469A CN202110122226.9A CN202110122226A CN112864469A CN 112864469 A CN112864469 A CN 112864469A CN 202110122226 A CN202110122226 A CN 202110122226A CN 112864469 A CN112864469 A CN 112864469A
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peo
tio
membrane
polyelectrolyte
mass
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郭红霞
秦周阳
程一辰
李明晔
王子莹
刘孟茜
秦振平
李钒
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Beijing 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
    • H01M10/058—Construction or manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for modifying polymer solid polyelectrolyte belongs to the technical field of solid polyelectrolyte membranes. The invention adopts PEO modified nano TiO2Then the composite material is compounded with the poly alkylene oxide-polyphenylene ether copolymer, which effectively improves the compatibility of inorganic particles and a PEO polymer matrix, and leads TiO to2The nano particles are more uniformly dispersed in the organic polymer matrix, the movement capacity of the PEO chain segment is improved, the crystallinity of the polymer is effectively reduced, and the ionic conductivity of the polymer is improved.

Description

Method for modifying polymer solid polyelectrolyte
Technical Field
The invention relates to a method for modifying an all-solid-state polyelectrolyte membrane, in particular to a method for modifying a polyalkylene oxide-polyphenylene oxide copolymer all-solid-state polyelectrolyte membrane by utilizing surface-modified titanium oxide nanoparticles, belonging to the technical field of solid-state polyelectrolyte membranes.
Technical Field
Electrolytes are an important component of lithium ion batteries. The conventional lithium ion battery usually uses organic matters as electrolytes, and because the lithium ion battery can generate lithium dendrite in the use process, the lithium ion battery has the risk of explosion. Therefore, the improvement of the conductivity and the service life of the lithium ion battery on the premise of ensuring the safety performance is the main direction of the technical development of the lithium ion battery. The replacement of electrolyte with solid polyelectrolyte membranes is an effective way to solve the safety problem of lithium ion batteries and has received extensive attention from researchers in related fields.
The total solid polyelectrolyte mainly includes two main categories of inorganic substances and polymers. Polyethylene oxide (PEO) solid polyelectrolyte is the earliest and most studied polymer solid electrolyte, but its ionic conductivity at room temperature is low (about 10)-8-10-7S/cm) and a narrow electrochemical stability window, resulting in poor charge and discharge performance of the battery at low temperature. Researchers mostly adopt the modification of adding block copolymer or inorganic particles into a PEO matrix to reduce the crystallinity of the PEO matrix so as to achieve the purpose of improving the ionic conductivity. Patent CN110707355A blends and crosslinks polyalkylene oxide and polyphenylene oxide polymer to obtain polyalkylene oxide-polyphenylene ether copolymer, and compounds with lithium salt to obtain copolymer polyelectrolyte membrane with room temperature ionic conductivity of 2.38 × 10-6S/cm; patent CN109768320A forms copolymer of oxygen-containing polymer and units containing aromatic diacid chloride and aromatic diamide, then compounds with inorganic particles and adds lithium salt to obtain all-solid-state polymer electrolyte, the Young modulus reaches 3.9GPa and the breaking strength is 140MPa after film forming, the growth of negative lithium dendrite and pulverization can be effectively inhibited, and the ionic conductivity is (0.1-3) x 10 at room temperature-5S/cm. The patent CN110224141A combines calcined fly ash inorganic filler with PEO to prepare a cheap solid polymer electrolyte with room-temperature ionic conductivity of about 10-6S/cm. Patent CN103059326A discloses a solid polyelectrolyte membrane prepared by mixing PEO with polymethyl ethylene carbonate (PPC) and adding calcium fluoride and lithium salt, and having an ionic conductivity of 5.31 x 10 at room temperature-6S/cm. Patent CN110212239A PEO with lithium salt and MoSi modified by adding silane coupling agent2Or MoSi2The solid electrolyte obtained by compounding the PEO polymer solid electrolyte with the mixture of the inorganic oxide has excellent thermal stability and stability, improves the conductivity of the PEO polymer solid electrolyte and improves the cycle performance of the battery. Patent CN101276658A discloses a process for preparing a lithium perchlorate from PEO4And hydrotalcite nanosheet LDHNS, has good thermal stability and room temperature conductivity of 1.02 × 10-6S/cm, and the transference number of lithium ions is 0.20. The research of Croce et al (Nature, l 998, 394: 456-458) shows that the particle size of the inorganic particles is reduced from micron to nanometer, the performances of the inorganic modified polymer electrolyte are obviously improved in all aspects, and 10 percent of TiO with the particle size of 13.0nm is added into PEO2Or A1 with particle size of 5.8nm2O3Inorganic matter, the room temperature conductivity of the obtained composite polymer electrolyte is improved by 2 orders of magnitude compared with that of pure PEO polymer electrolyte, and the room temperature conductivity can reach 10-5S/cm. However, the inorganic nanoparticles are easy to agglomerate and are mixed with PEO polyelectrolyte to cause poor uniformity of the film, thereby influencing the use performance of the polymer electrolyte. Although the silane coupling agent modifies the inorganic nanoparticles, the technology is only physical modification and cannot effectively solve the problem of poor compatibility between the inorganic particles and the polymer electrolyte.
Disclosure of Invention
Aiming at the defects of the technology and the problems of low ionic conductivity of a polyelectrolyte diaphragm of polyalkylene oxide-polyphenylene ether copolymer and the like, the invention provides a PEO modified TiO2A method for modifying polyelectrolyte of polyalkylene oxide-polyphenylene ether copolymer by nanoparticles. Mainly comprises the following steps:
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
Respectively adding 20-78 parts by mass of inorganic titanium salt and 0.1-20 parts by mass of polyethylene oxide (PEO) with the molecular weight of 400-1000 into deionized water, and fully stirring to uniformly mix the inorganic titanium salt and the PEO; then, the mixed solution is dripped into 2.1-10.0 wt% of sodium hydroxide solution for a certain timeCentrifugally separating out precipitate, placing the precipitate in 0.2-2.0 mol/L nitric acid solution, refluxing for 1-3 h at the temperature of 30-80 ℃, centrifugally separating the precipitate, fully washing with absolute ethyl alcohol, and completely drying to obtain the PEO modified TiO2Nanoparticle PEO-TiO2；
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
Dissolving 65-98 parts by mass of polyethylene oxide-polyphenylene oxide copolymer in an organic solvent, and adding 0.1-45 parts by mass of PEO-TiO prepared in the step 1)2And (2) fully stirring and uniformly dispersing the nano particles, adding lithium salt accounting for 5.0-55.0 wt% of the mass percent of the polyethylene oxide-polyphenyl ether copolymer, fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, performing vacuum defoamation on the casting solution, uniformly coating the casting solution on a polytetrafluoroethylene plate at a coating speed of 10-20 mm/s, standing until a solvent is volatilized, placing a membrane on the polytetrafluoroethylene plate in a vacuum oven, and performing vacuum drying at the temperature of 30-80 ℃ for 8-12 hours to obtain the titanium oxide nano particle modified polyalkylene oxide-polyphenyl ether copolymer all-solid polyelectrolyte membrane.
Further, the inorganic titanium salt mainly comprises titanyl sulfate, titanium tetrachloride and titanium acetate; the organic solvent is one or a mixture of two of dimethylbenzene, acetonitrile, chlorobenzene and N, N-dimethylformamide; the lithium salt mainly comprises lithium nitrate, lithium hexafluorophosphate, lithium perchlorate and lithium bis (difluorosulfonyl) imide (LiFSI).
The invention adopts PEO modified nano TiO2Compounded with the poly alkylene oxide-polyphenylene ether copolymer, the compatibility of inorganic particles and a PEO polymer matrix is effectively improved, so that TiO2The nano particles are more uniformly dispersed in the organic polymer matrix, the movement capacity of the PEO chain segment is improved, the crystallinity of the polymer is effectively reduced, and the ionic conductivity of the polymer is improved. As shown in examples 2 to 5, the ion conductivity of the separator at room temperature was 10-5S/cm, whereas the ion conductivity of the polyalkylene oxide-polyphenylene ether polyelectrolyte membrane in comparative example 1 was only 10-6S/cm. In addition, the PEO modification adopted by the inventionTiO 22The preparation process of the nano particles is simple, high-temperature sintering is not needed, the energy consumption is low, and the cost is low.
Drawings
FIG. 1 PEO-TiO2TEM images of nanoparticles (outer light colored part is coated PEO polymer);
FIG. 2 PEO-TiO2XRD pattern of nanoparticles;
detailed description of the invention
The following is a further description of the present modification method by means of specific embodiments, and with reference to the drawings, but the present invention includes, but is not limited to, the following examples. The reagents and instrumentation used in the following examples are conventional raw materials and conventional equipment.
Comparative example
1) Preparation of polyethylene oxide-polyphenyl ether copolymer polyelectrolyte casting solution
Respectively dissolving 98 parts by mass of polyethylene oxide and 24 parts by mass of polyphenylene oxide into 610 parts by mass of xylene, adding 12 parts by mass of Toluene Diisocyanate (TDI), fully stirring and dissolving, adding lithium bis (difluorosulfimide) accounting for 33.0 wt% of the mass of the ethylene oxide, fully mixing, and defoaming the mixed solution in vacuum to obtain a casting solution;
2) preparation of polyelectrolyte membranes
Uniformly coating the casting solution obtained in the step 1) on a polytetrafluoroethylene plate at a coating speed of 15mm/s, standing until the solvent is volatilized, putting the membrane on the polytetrafluoroethylene plate in a vacuum oven, and carrying out vacuum drying at the temperature of 40 ℃ for 12h to obtain the polyalkylene oxide-polyphenylene oxide copolymer all-solid-state polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Stainless Steel Sheet (SS) is used as an electrode, a SS | diaphragm | SS formed by solid polyelectrolyte diaphragms is symmetrically blocked by the battery for body impedance test, the measured body impedance is 23240 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 2.14 multiplied by 10-6S/cm。
Example 1
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
20 parts by mass of titanium sulfate and 0.1 part by mass of polyethylene oxide (PEO) having a molecular weight of 400 were added to 50mL of deionized water, and sufficiently stirred to be uniformly mixed. Then, the mixed solution is dripped into 2.1 wt% sodium hydroxide solution, after a certain time, precipitate is centrifugally separated, then the mixed solution is placed into 0.2mol/L nitric acid solution, after the mixed solution is refluxed for 1h at the temperature of 80 ℃, the precipitate is centrifugally separated, and is fully washed by absolute ethyl alcohol and completely dried to obtain PEO modified TiO2Nanoparticles (PEO-TiO)2)。
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
Dissolving 65 parts by mass of polyethylene oxide-polyphenylene ether copolymer in xylene, and adding 0.1 part by mass of PEO-TiO prepared in step 1)2And (2) fully stirring and uniformly dispersing the nano particles, then adding lithium bis (difluorosulfonimide) accounting for 5.0 wt% of the mass of the polyethylene oxide-polyphenylene ether copolymer (the same below), fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, performing vacuum defoamation on the casting solution, uniformly coating the casting solution on a polytetrafluoroethylene plate at a coating speed of 10mm/s, standing until a solvent is volatilized, placing a membrane on the polytetrafluoroethylene plate in a vacuum oven, and performing vacuum drying at the temperature of 30 ℃ for 12 hours to obtain the titanium oxide nano particle modified polyalkylene oxide-polyphenylene ether copolymer all-solid polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Stainless Steel Sheet (SS) is used as an electrode, a SS | | diaphragm | SS formed by solid polyelectrolyte diaphragms is symmetrically blocked by the battery for electrochemical performance test, the impedance of the body is 6703 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 2.72 multiplied by 10-6S/cm
Example 2
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
78 parts by mass of titanium sulfate and 20 parts by mass of PEO with a molecular weight of 1000 were added to 200mL of deionized water, and sufficiently stirred to be uniformly mixed. Then, the mixture was added dropwise to a 10.0 wt% sodium hydroxide solutionAfter a certain time, centrifugally separating out precipitate, placing the precipitate in 2.0mol/L nitric acid solution, refluxing for 3h at the temperature of 30 ℃, centrifugally separating the precipitate, fully washing with absolute ethyl alcohol, and completely drying to obtain the PEO modified TiO2Nanoparticles (PEO-TiO)2)。
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
Dissolving 98 parts by mass of polyethylene oxide-polyphenylene ether copolymer in xylene, and adding 45 parts by mass of PEO-TiO prepared in step 1)2And (2) fully stirring and uniformly dispersing the nano particles, then adding lithium bis (difluorosulfonyl) imide accounting for 55.0 wt% of the mass of the polyethylene oxide-polyphenylene oxide copolymer, fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, performing vacuum defoamation on the membrane casting solution, uniformly coating the membrane casting solution on a polytetrafluoroethylene plate at a coating speed of 20mm/s, standing until a solvent is volatilized, placing the membrane on the polytetrafluoroethylene plate in a vacuum oven, and performing vacuum drying at the temperature of 80 ℃ for 8 hours to obtain the titanium oxide nano particle modified polyalkylene oxide-polyphenylene oxide copolymer all-solid polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Taking a stainless Steel Sheet (SS) as an electrode, forming a SS | diaphragm | SS by solid polyelectrolyte diaphragms to symmetrically block the battery for body impedance test, and measuring that the body impedance is 2013 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 2.47 multiplied by 10-5S/cm。
Example 3
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
55 parts by mass of titanium sulfate and 10 parts by mass of PEO with the molecular weight of 600 are respectively added into 120mL of deionized water and fully stirred to be uniformly mixed. Then, the mixed solution is dripped into 5.0 wt% sodium hydroxide solution, after a certain time, precipitate is centrifugally separated, then the mixed solution is placed into 1.0mol/L nitric acid solution, after refluxing for 2 hours at the temperature of 50 ℃, precipitate is centrifugally separated, and is fully washed by absolute ethyl alcohol and completely dried to obtain PEO modified TiO2Nanoparticles of (A)PEO-TiO2)。
2)PEO-TiO2Composition of nanoparticles and polyethylene oxide-polyphenylene oxide
Dissolving 80 parts by mass of polyethylene oxide-polyphenylene ether copolymer in xylene, and adding 30 parts by mass of PEO-TiO prepared in step 1)2And (2) fully stirring and uniformly dispersing the nano particles, then adding lithium bis (difluorosulfimide) which accounts for 33 wt% of the mass of the polyethylene oxide-polyphenyl ether copolymer, fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, performing vacuum defoamation on the membrane casting solution, uniformly coating the membrane casting solution on a polytetrafluoroethylene plate at a coating speed of 15mm/s, standing until a solvent is volatilized, placing the membrane on the polytetrafluoroethylene plate in a vacuum oven, and performing vacuum drying at the temperature of 40 ℃ for 10 hours to obtain the titanium oxide nano particle modified polyalkylene oxide-polyphenyl ether copolymer all-solid-state polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Stainless Steel Sheet (SS) is used as an electrode, a SS | diaphragm | SS formed by solid polyelectrolyte diaphragms is symmetrically blocked by the battery for body impedance test, the body impedance is 3048 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 1.63 multiplied by 10-5S/cm。
Example 4
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
48 parts by mass of titanium tetrachloride and 18 parts by mass of polyethylene oxide (PEO) having a molecular weight of 600 were added to 150mL of deionized water, and sufficiently stirred to be uniformly mixed. Then, the mixed solution is dripped into 8.0 wt% sodium hydroxide solution, after a certain time, precipitate is separated by centrifugation, then the mixed solution is placed into 1.5mol/L nitric acid solution, after reflux is carried out for 2.5h at the temperature of 45 ℃, the precipitate is separated by centrifugation, and the absolute ethyl alcohol is used for fully washing and completely drying the precipitate to obtain the PEO modified TiO2Nanoparticles (PEO-TiO)2)。
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
78 parts by mass of a polyethylene oxide-polyphenylene ether copolymer was dissolved in chlorineAdding 40 parts by mass of PEO-TiO prepared in the step 1) into benzene2And (2) fully stirring and uniformly dispersing the nano particles, then adding lithium hexafluorophosphate accounting for 38.0 wt% of the mass of the polyethylene oxide-polyphenylene oxide copolymer, fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, defoaming the membrane casting solution in vacuum, uniformly coating the membrane casting solution on a polytetrafluoroethylene plate at a coating speed of 15mm/s, standing for volatilizing a solvent, placing the membrane on the polytetrafluoroethylene plate in a vacuum oven, and performing vacuum drying at the temperature of 45 ℃ for 10 hours to obtain the titanium oxide nano particle modified polyalkylene oxide-polyphenylene oxide copolymer all-solid-state polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Stainless Steel Sheet (SS) is used as an electrode, a solid polyelectrolyte membrane is formed into a SS | barrier | SS symmetric blocking battery to carry out electrochemical performance test, the impedance of the body is 5703 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 3.02 multiplied by 10-5S/cm。
Example 5
1) PEO-modified TiO2Nanoparticles (PEO-TiO)2) Preparation of
36 parts by mass of titanium acetate and 16 parts by mass of polyethylene oxide (PEO) having a molecular weight of 400 were added to 250mL of deionized water, and sufficiently stirred to be uniformly mixed. Then, the mixed solution is dripped into 6.8 wt% sodium hydroxide solution, after a certain time, precipitate is centrifugally separated, then the mixed solution is placed into 1.6mol/L nitric acid solution, after reflux is carried out for 1.5h at the temperature of 42 ℃, precipitate is centrifugally separated, absolute ethyl alcohol is used for fully washing, and thorough drying is carried out, thus obtaining the PEO modified TiO2Nanoparticles (PEO-TiO)2)。
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
Dissolving 72 parts by mass of polyethylene oxide-polyphenylene oxide copolymer in N, N dimethylformamide, and adding 38 parts by mass of PEO-TiO prepared in step 1)2Fully stirring and uniformly dispersing nano particles, then adding lithium hexafluorophosphate accounting for 28.0 wt% of the polyethylene oxide-polyphenyl ether copolymer, fully stirring and uniformly obtaining the polyelectrolyteAnd (3) a membrane casting solution, namely, after the membrane casting solution is defoamed in vacuum, uniformly coating the membrane casting solution on a polytetrafluoroethylene plate at a coating speed of 12mm/s, standing the membrane casting solution until a solvent is volatilized, putting the membrane on the polytetrafluoroethylene plate in a vacuum oven, and drying the membrane in vacuum for 8 hours at the temperature of 35 ℃ to obtain the titanium oxide nanoparticle modified polyalkylene oxide-polyphenylene oxide copolymer all-solid-state polyelectrolyte membrane.
The membrane was cut into small pieces with a diameter of 16mm and stored in a glove box. Stainless Steel Sheet (SS) is used as an electrode, a SS | diaphragm | SS formed by solid polyelectrolyte diaphragms is symmetrically blocked by the battery for electrochemical performance test, the impedance of the body is 4302 omega, and the ionic conductivity of the polyelectrolyte membrane at room temperature is 1.16 multiplied by 10-5S/cm。

Claims (7)

1. A method for modifying polymer solid polyelectrolyte is characterized by comprising the following steps:
1) PEO-modified TiO2Nanoparticle PEO-TiO2Preparation of
Respectively adding 20-78 parts by mass of inorganic titanium salt and 0.1-20 parts by mass of polyethylene oxide (PEO) with the molecular weight of 400-1000 into deionized water, and fully stirring to uniformly mix the inorganic titanium salt and the PEO; then, dropwise adding the mixed solution into 2.1-10.0 wt% of sodium hydroxide solution, after a period of time, centrifugally separating out precipitate, then placing the precipitate into 0.2-2.0 mol/L nitric acid solution, refluxing for 1-3 h at the temperature of 30-80 ℃, centrifugally separating the precipitate, fully washing with absolute ethyl alcohol, and completely drying to obtain PEO modified TiO2Nanoparticle PEO-TiO2；
2)PEO-TiO2Preparation of nano-particle and polyethylene oxide-polyphenyl ether copolymer polyelectrolyte composite membrane
Dissolving 65-98 parts by mass of polyethylene oxide-polyphenylene oxide copolymer in an organic solvent, and adding 0.1-45 parts by mass of PEO-TiO prepared in the step 1)2Fully stirring and uniformly dispersing nano particles, then adding lithium salt accounting for 5.0-55.0 wt% of the mass percent of the polyethylene oxide-polyphenyl ether copolymer, fully stirring uniformly to obtain a polyelectrolyte membrane casting solution, defoaming the membrane casting solution in vacuum, and removing the lithium salt by using a stirrerUniformly coating the polytetrafluoroethylene plate at a coating speed of 10-20 mm/s, standing until the solvent is volatilized, and drying the membrane on the polytetrafluoroethylene plate in a vacuum oven to obtain the titanium oxide nanoparticle modified polyalkylene oxide-polyphenylene oxide copolymer all-solid-state polyelectrolyte membrane.
2. The method of claim 1, wherein the inorganic titanium salt is selected from the group consisting essentially of titanyl sulfate, titanium tetrachloride and titanium acetate.
3. The method as claimed in claim 1, wherein the organic solvent is one or a mixture of xylene, acetonitrile, chlorobenzene, and N, N-dimethylformamide.
4. The method of claim 1, wherein the lithium salt is selected from the group consisting of lithium nitrate, lithium hexafluorophosphate, lithium perchlorate, lithium bis (difluorosulfonimide) (LiFSI).
5. A polymeric solid polyelectrolyte obtained by the process according to any one of claims 1 to 4.
6. A solid polyelectrolyte according to any one of claims 1 to 4, characterised in that it has an ionic conductivity of not less than 10 at room temperature-5S/cm。
7. Use of a polymeric solid polyelectrolyte prepared according to the process of any one of claims 1-4 as a solid polyelectrolyte membrane.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040200991A1 (en) * 2003-04-10 2004-10-14 Po-Jen Chu [composition of nano-tube composite polymer electrolyte and fabrication method thereof]
CN102005611A (en) * 2010-10-21 2011-04-06 中国科学院化学研究所 Polymer electrolyte and preparation method and application thereof
CN103515649A (en) * 2012-06-14 2014-01-15 东丽先端材料研究开发（中国）有限公司 Organic/inorganic composite electrolyte and preparation method thereof
CN104538670A (en) * 2014-11-24 2015-04-22 深圳华中科技大学研究院 All-solid polymer electrolyte, and preparation method and application of all-solid polymer electrolyte
CN106992311A (en) * 2017-05-26 2017-07-28 淄博火炬能源有限责任公司 full solid state polymer electrolyte film and preparation method thereof
CN108550906A (en) * 2018-04-24 2018-09-18 珠海光宇电池有限公司 A kind of preparation method of compound all-solid polymer electrolyte film
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
CN110212239A (en) * 2019-05-21 2019-09-06 东莞东阳光科研发有限公司 A kind of full solid state polymer solid electrolyte and preparation method thereof
CN110600797A (en) * 2019-09-29 2019-12-20 天津空间电源科技有限公司 Preparation method of polymer-inorganic composite electrolyte
CN110707355A (en) * 2019-10-09 2020-01-17 北京工业大学 All-solid-state polyelectrolyte diaphragm and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040200991A1 (en) * 2003-04-10 2004-10-14 Po-Jen Chu [composition of nano-tube composite polymer electrolyte and fabrication method thereof]
CN102005611A (en) * 2010-10-21 2011-04-06 中国科学院化学研究所 Polymer electrolyte and preparation method and application thereof
CN103515649A (en) * 2012-06-14 2014-01-15 东丽先端材料研究开发（中国）有限公司 Organic/inorganic composite electrolyte and preparation method thereof
CN104538670A (en) * 2014-11-24 2015-04-22 深圳华中科技大学研究院 All-solid polymer electrolyte, and preparation method and application of all-solid polymer electrolyte
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
CN106992311A (en) * 2017-05-26 2017-07-28 淄博火炬能源有限责任公司 full solid state polymer electrolyte film and preparation method thereof
CN108550906A (en) * 2018-04-24 2018-09-18 珠海光宇电池有限公司 A kind of preparation method of compound all-solid polymer electrolyte film
CN110212239A (en) * 2019-05-21 2019-09-06 东莞东阳光科研发有限公司 A kind of full solid state polymer solid electrolyte and preparation method thereof
CN110600797A (en) * 2019-09-29 2019-12-20 天津空间电源科技有限公司 Preparation method of polymer-inorganic composite electrolyte
CN110707355A (en) * 2019-10-09 2020-01-17 北京工业大学 All-solid-state polyelectrolyte diaphragm and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨蕊等: "聚电解质-TiO2改性PVDF多孔膜及其电化学性能", 《膜科学与技术》 *

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Application publication date: 20210528