CN111416147B - Composite solid polymer electrolyte and preparation method thereof - Google Patents
Composite solid polymer electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN111416147B CN111416147B CN202010152212.7A CN202010152212A CN111416147B CN 111416147 B CN111416147 B CN 111416147B CN 202010152212 A CN202010152212 A CN 202010152212A CN 111416147 B CN111416147 B CN 111416147B
- Authority
- CN
- China
- Prior art keywords
- lithium
- cyclic carbonate
- solid polymer
- nano
- polymer electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a solid polymer electrolyte doped with modified nano-filler and a preparation method thereof, belonging to the technical field of solid polymer electrolyte materials. The novel solid polymer electrolyte doped with the modified nano filler is prepared by mixing and drying cyclic carbonate modified silicon dioxide nano particles, lithium salt, polyethylene oxide and a solvent capable of dissolving the polyethylene oxide to form a film. The preparation method comprises the following steps: preparing cyclic carbonate modified silica nanoparticles, preparing electrolyte mixed solution and preparing electrolyte films. The preparation process is simple, the efficiency is high, the production cost is low, and the obtained lithium ion battery solid polymer electrolyte has good ionic conductivity, mechanical strength and excellent safety performance, and has a very high market prospect.
Description
Technical field:
the invention belongs to the technical field of solid polymer electrolyte materials, and particularly relates to a solid polymer electrolyte doped with modified nanofiller and a preparation method thereof.
The background technology is as follows:
the lithium ion battery electrolyte material is a material system with excellent ion conductivity and functional characteristics such as interface performance, electrochemical stability, thermal stability, safety, mechanical performance and the like. Currently, liPF widely used in commercial lithium ion batteries 6 The carbonate-based electrolyte has the defects of easy combustion, easy volatilization, insufficient oxidation resistance and the like, and severely restricts the further improvement of the safety and the energy density of the lithium ion battery, although the carbonate-based electrolyte has high ionic conductivity and good infiltration performance. In contrast, solid electrolyte materials have no or only a small amount of liquid components, and are expected to fundamentally solve the safety problem of batteries.
The organic-inorganic composite solid electrolyte is a type of electrolyte formed by introducing inorganic particles into a conventional polymer electrolyte. The polymer-based electrolyte can compensate for volume changes of the electrode during charge and discharge by elastic and plastic deformation; the inorganic filler is introduced into the polymer electrolyte, so that crystallization of the polymer substrate and interaction between the recombinant polymer and lithium ions can be inhibited, and the ion conduction performance, interface performance and mechanical strength of the electrolyte are effectively improved. However, the compatibility between the inorganic filler and the polymer matrix is to be improved, and the filler is easy to agglomerate in the polymer matrix, so that the performance of the electrolyte is affected. The related patent technology has CN03136183.3 which discloses a composite solid polymer electrolyte prepared from a polymer matrix, lithium salt and modified or unmodified inorganic nano particles, wherein the inorganic nano particles are respectively modified by silane coupling agents (KH 550, KH560, KH570 and KH 792) containing epoxy groups, amino groups and acrylate groups; CN03119735 discloses a composite solid polymer electrolyte prepared from a polymer matrix, lithium salt and modified inorganic nanoparticles, wherein the surface groups of the inorganic silica nanoparticles can be hydroxyl, trimethylsilyl, polydimethylsilane; CN201710059631 discloses that the mercapto silane coupling agent is mixed with the polymer substrate to form a film, then the mercapto group is oxidized into a sulfonic acid group, and then in-situ polymerized and lithiated to prepare a lithium salt-containing composite solid polymer electrolyte film; CN201810072837.5 discloses a composite gel polymer electrolyte membrane with ionic liquid modified nano silica as filler; CN201910269774.7 discloses that the self-healing polymer electrolyte is prepared by compounding UPy functionalized silica nanoparticles with UpyMA and PEGMA copolymers having self-healing function. The inorganic silica nanoparticles are used as the composite solid polymer electrolyte filler, and the inorganic silica nanoparticles or the inorganic nanoparticles with surface functionalization modification are introduced, so that the inorganic silica nanoparticles have better dispersibility in a polymer matrix, and can endow the composite solid polymer electrolyte with more functional characteristics.
LiPF with high ionic conductivity and good wettability for commercial lithium ion batteries 6 Although the carbonate-based electrolyte has the defects of easy combustion, easy volatilization, insufficient oxidation resistance and the like, the cyclic carbonate group has the characteristics of higher dielectric constant, better solubility for lithium salt and contribution to ion conductivity, and the electrolyte functionalized by the cyclic carbonate group is still a hot spot for the development of the current commercial electrolyte, such as fluorocarbonate, vinyl functionalized carbonate, ionic liquid functionalized carbonate and sulfonic acid functionalized carbonateLong chain alkyl functionalized carbonates and silicone functionalized carbonates. The applicant has previously synthesized a series of alkoxysilane-substituted cyclic carbonates (RSC adv.,2015,5,17660-1766) and fluorosilicone-substituted cyclic carbonates (ZL 201210358351.0; PCT/CN 2012/084205) that exhibit excellent performance as high voltage electrolytes for lithium ion batteries. The preparation method comprises the steps of using silane functionalized cyclic carbonate as a silane coupling agent, performing functionalization modification on nano particles, and compounding the nano particles with polyethylene oxide and lithium salt to prepare a solid electrolyte material; the silicon dioxide nano particles modified by the cyclic carbonate have better dispersibility, better compatibility with polyethylene oxide and better dissociation capability for lithium salt; thus, the composite solid electrolyte material exhibits a higher ionic conductivity.
The invention comprises the following steps:
the invention aims to provide a composite solid polymer electrolyte doped with modified silica nano-filler and a preparation method thereof, wherein the cyclic carbonate modified silica nano-filler has better dispersibility, better compatibility with polyethylene oxide and better dissociation capability for lithium salt; the composite solid electrolyte material has better mechanical property and ion conductivity. The preparation method has simple process and low cost, and is beneficial to mass production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite solid polymer electrolyte comprises the following components: modified nano silicon dioxide particles, lithium salt and polyethylene oxide with lithium conducting capability.
The mass fraction of the cyclic carbonate modified nano silicon dioxide particles in the electrolyte is 1-50%, the mass fraction of the lithium salt in the electrolyte is 15-50%, and the mass fraction of the polyethylene oxide with lithium conducting capability in the electrolyte is 30-80%.
Further, the cyclic carbonate modified nano silica particles are prepared according to a method comprising the steps of:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the solvent in mass percent, and uniformly dispersing by ultrasonic;
step 2: under the condition of stirring, adding the cyclic carbonate modified silane coupling agent shown in the formula (1) according to the mass ratio of the nano silicon dioxide particles to the cyclic carbonate modified silane coupling agent of 10:1-1:10:
wherein R is 1 Selected from the following structural units: - (CH) 2 ) n - (n=1-3), or-CH 2 OCH 2 CH 2 CH 2 -；R 2 ，R 3 ，R 4 Selected from alkoxy or halogen substituents;
step 3: reacting for 0.5-12 hours at the temperature of 30-120 ℃, centrifugally separating, washing with absolute ethyl alcohol, and drying to obtain the silicon dioxide nano-particles modified by the cyclic carbonate.
Further, in the step 1, the nano silica is hydrophilic nano silica with a particle diameter of 7-40nm and a specific surface area of 380m 2 /g。
Further, in step 1, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, xylene and methylene dichloride.
Further, in step 2, the preparation method of the cyclic carbonate modified silane coupling agent comprises the following steps: prepared by cycloaddition reaction of silane coupling agent (KH 560) containing ethylene oxide group and carbon dioxide in the presence of quaternary ammonium salt, or by hydrosilation reaction of double bond-containing carbonate (vinyl ethylene carbonate) and silazane in the presence of chloroplatinic acid.
Further, in step 3, the conditions for the centrifugal separation are 8000-14000r/min.
The lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI),Lithium triflate (LiCF) 3 SO 3 ) One or more of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB) and lithium chloride (LiCl).
In order to achieve the above object, the present invention provides a method for preparing a composite solid polymer electrolyte, comprising the steps of:
step 1: polyethylene oxide is dissolved in a solvent to prepare a polymer solution with the mass percent concentration of 2% -20%, and lithium salt is added;
step 2: dispersing the cyclic carbonate modified silicon dioxide nano particles into the polymer solution obtained in the step 1, dispersing for 0.5-24 hours at the temperature of 20-90 ℃, uniformly dispersing, and then casting to form a film, wherein the polymer film is obtained after the solvent volatilizes, namely the lithium ion battery composite solid electrolyte film;
the solvent in the step 1 and the step 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or water.
After the composite solid polymer electrolyte is prepared into a film, the thickness of the film is 50-200 mu m.
The composite solid polymer electrolyte is characterized in that the ionic conductivity reaches 8.9X10 -6 S/cm, conductivity of the blank composite solid electrolyte material doped with the silicon dioxide nano particles without the cyclic carbonate modification under the same condition (3.5X10) -7 S/cm) is an order of magnitude higher.
The invention has simple operation and high safety, and is suitable for continuous mass production of composite solid polymer electrolyte. The solid polymer electrolyte prepared by the invention has high ionic conductivity, wide electrochemical stability window and good compatibility with the electrode, and is beneficial to improving the safety performance of the lithium ion battery. The solid polymer electrolyte membrane prepared by the electrolyte has high mechanical strength and good chemical stability, and is also suitable for the design and production of flexible batteries.
The invention has the following beneficial effects:
according to the modified silica nano filler, the cyclic carbonate groups are functionalized on the surface of the modified silica nano filler, and the introduction of the carbonate functional groups can further promote the dissociation of lithium salt, so that the improvement of the ionic conductivity of the solid polymer electrolyte is facilitated.
According to the modified silica nano filler, the surface of the modified silica nano filler is functionalized with the cyclic carbonate group, so that the problems of easy agglomeration of nano particles and poor compatibility with a polymer substrate can be effectively solved, and uniform dispersion of the filler in a matrix is facilitated.
After the polymer film prepared by the invention is assembled into a battery, electrochemical tests show that the solid polymer electrolyte has good particle conductivity and electrochemical stability: the particle conductivity at room temperature is higher than that of the composite polymer electrolyte without the cyclic carbonate modification by an order of magnitude, and the electrochemical stability window can reach more than 5V, so that the practical application requirement of the lithium ion battery can be met.
Description of the drawings:
FIG. 1 is an infrared contrast spectrum of a cyclic carbonate modified silica nanoparticle prepared in example 1 of the present invention.
FIG. 2 is a thermogravimetric plot of the cyclic carbonate modified silica nanoparticles prepared in example 1 of the present invention.
Fig. 3 is a graph comparing ionic conductivity of composite solid polymer electrolyte materials doped with silica nanoparticles modified with/without cyclic carbonate in examples 3 and 7 (blank) of the present invention.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention. After reading the present invention, those skilled in the art will recognize that modifications of various equivalent forms of the present invention are within the scope of what is defined in the claims appended hereto.
Example 1
The cyclic carbonate modified nano-silica particles are prepared according to the following steps: 0.5g of nano silicon dioxide particles are dispersed into 50mL of toluene solvent, and ultrasonic dispersion is uniform: under the condition of stirring, adding 0.2g of cyclic carbonate modified silane coupling agent (methyl dichloro silane substituted 4-ethyl-1, 3-dioxolan-2-one), reacting for 0.5 hours at the temperature of 120 ℃, centrifuging at 10000r/min, washing for 3 times by ethanol, and drying at 80 ℃ to obtain the cyclic carbonate modified silicon dioxide nano particles.
Example 2
The cyclic carbonate modified nano-silica particles are prepared according to the following steps: dispersing 0.5g of nano silicon dioxide particles into 20mL of ethanol solvent, and uniformly dispersing by ultrasonic: under the condition of stirring, 5g of cyclic carbonate modified silane coupling agent (trimethoxy silane substituted 4- [ (propoxy) methyl ] -1, 3-dioxolan-2-one) is added, the reaction is carried out for 12 hours at the temperature of 30 ℃, then centrifugation is carried out at the temperature of 10000r/min, ethanol is used for washing for 3 times, and the cyclic carbonate modified silicon dioxide nano particles are obtained after drying at the temperature of 80 ℃.
Example 3
Polyethylene oxide (PEO), cyclic carbonate modified silica nanoparticles prepared in example 1, lithium perchlorate (LiClO) in a mass ratio of 3:1:1 were combined in an argon glove box 4 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has the thickness of about 160um, the electrochemical window of more than 5.2V and the ionic conductivity of 8.9 multiplied by 10 at the temperature of 30 DEG C -6 S/cm。
Example 4
Polyethylene oxide (PEO) with the mass ratio of 5:4:4, the cyclic carbonate modified silica nanoparticle prepared in example 2 and lithium bisoxalato borate (LiBOB) were fully dissolved in acetonitrile in an argon glove box, a uniform viscous solution was obtained after stirring for 24 hours, then the electrolyte mixed solution was prepared by casting a film on a polytetrafluoroethylene plate, evaporating the solvent, and then drying for 48 hours at 80 ℃ in a vacuum drying oven. The thickness of the prepared solid polymer electrolyte membrane doped with nano-filler is about 100um, the electrochemical window is larger than 5.0V, and the ionic conductivity is 8.3 multiplied by 10 at 30 DEG C -6 S/cm。
Example 5
Polyethylene oxide (PEO), cyclic carbonate modified silica nanoparticles prepared in example 1, lithium hexafluorophosphate (LiPF) in a mass ratio of 3:5:4 were mixed in an argon glove box 6 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has the thickness of about 70um, the electrochemical window of more than 5.0V and the ionic conductivity of 7.8X10 at 30 DEG C -6 S/cm。
Example 6
Polyethylene oxide (PEO) with the mass ratio of 2:2:3, the cyclic carbonate modified silica nanoparticle prepared in example 1 and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) are fully dissolved in distilled water, and a uniform viscous solution is obtained after stirring for 24 hours, then an electrolyte mixed solution is prepared by casting a film on a polytetrafluoroethylene plate, evaporating the solvent, and then drying for 48 hours at 80 ℃ in a vacuum drying oven. The thickness of the prepared solid polymer electrolyte membrane doped with nano-filler is about 120um, the electrochemical window is larger than 5.0V, and the ionic conductivity is 9.7X10 at 30 DEG C -6 S/cm。
Example 7
Polyethylene oxide (PEO), silica nanoparticles, lithium perchlorate (LiClO) in a mass ratio of 3:1:1 in an argon glove box 4 ) Fully dissolved in acetonitrile, stirred for 24 hours to obtain a uniform viscous solution, then the electrolyte mixture is poured on a polytetrafluoroethylene plate to evaporate the solvent, and then dried in a vacuum drying oven at 80 ℃ for 48 hours. The prepared solid polymer electrolyte membrane doped with nano-filler has a thickness of about 160um, an electrochemical window of more than 5.0V and an ionic conductivity of 3.5X10 at 30 DEG C -7 S/cm。
Claims (5)
1. A composite solid polymer electrolyte comprises the following components: modified nano silicon dioxide particles, lithium salt and polyethylene oxide with lithium conducting capacity; the method is characterized in that: the composite solid polymer electrolyteThe nano silicon dioxide particles modified by the cyclic carbonate are used as the filler, and the nano particles modified by the cyclic carbonate are beneficial to improving the dispersibility and compatibility of the nano silicon dioxide particles in polyethylene oxide and the interaction of the nano silicon dioxide particles and lithium salt; 1-50% of cyclic carbonate modified nano silica particles, 15-50% of lithium salt and 30-80% of polyethylene oxide with lithium conducting capacity, wherein the cyclic carbonate modified nano silica is prepared by reacting nano silica particles with a cyclic carbonate modified silane coupling agent shown as a formula (1), R in the formula (1) 1 Selected from the following structural units: - (CH) 2 ) n - (n=1-3), or-CH 2 OCH 2 CH 2 CH 2 -；R 2 ，R 3 ，R 4 Selected from alkoxy or halogen substituents.
2. The composite solid polymer electrolyte of claim 1, wherein: the cyclic carbonate modified nano silica particles are prepared according to a method comprising the following steps:
step 1: dispersing nano silicon dioxide particles into a solvent, wherein the nano silicon dioxide accounts for 0.1-10% of the solvent in mass percent, and uniformly dispersing by ultrasonic;
step 2: under the condition of stirring, adding the cyclic carbonate modified silane coupling agent, wherein the mass ratio of the nano silicon dioxide particles to the cyclic carbonate modified silane coupling agent is 10:1-1:10;
step 3: reacting for 0.5-12 hours at the temperature of 30-120 ℃, centrifugally separating, washing with absolute ethyl alcohol, and drying to obtain the silicon dioxide nano-particles modified by the cyclic carbonate.
3. The composite solid polymer electrolyte of claim 1, which isIs characterized in that: the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethylsulfonate (LiCF) 3 SO 3 ) One or more of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiODFB) and lithium chloride (LiCl).
4. The method for preparing a composite solid polymer electrolyte according to claim 1, characterized in that the method comprises the steps of:
step 1: polyethylene oxide is dissolved in a solvent to prepare a polymer solution with the mass percent concentration of 2% -20%, and lithium salt is added;
step 2: dispersing the cyclic carbonate modified silicon dioxide nano particles into the polymer solution obtained in the step 1, dispersing for 0.5-24 hours at the temperature of 20-90 ℃, uniformly dispersing, and then casting to form a film, wherein the polymer film is obtained after the solvent volatilizes, namely the lithium ion battery composite solid electrolyte film.
5. The method for preparing a composite solid polymer electrolyte according to claim 4, wherein the solvent in the step 1 and the step 2 comprises acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), or water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010152212.7A CN111416147B (en) | 2020-03-06 | 2020-03-06 | Composite solid polymer electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010152212.7A CN111416147B (en) | 2020-03-06 | 2020-03-06 | Composite solid polymer electrolyte and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111416147A CN111416147A (en) | 2020-07-14 |
| CN111416147B true CN111416147B (en) | 2023-06-02 |
Family
ID=71494301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010152212.7A Active CN111416147B (en) | 2020-03-06 | 2020-03-06 | Composite solid polymer electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111416147B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113851709B (en) * | 2021-10-13 | 2023-03-17 | 上海电气集团股份有限公司 | Solid electrolyte, preparation method and application thereof |
| CN114335710B (en) * | 2021-12-17 | 2023-06-09 | 西安交通大学 | Preparation method and application of double-modified solid electrolyte membrane |
| CN114583254B (en) * | 2022-03-04 | 2023-07-11 | 西安交通大学 | Environment-adaptive solid composite electrolyte and preparation method and application thereof |
| US20240002639A1 (en) * | 2022-06-30 | 2024-01-04 | Saudi Arabian Oil Company | Sustainable approach to improve the toughness of thermoset materials and composites |
| CN117613360B (en) * | 2024-01-23 | 2024-03-29 | 江苏华富储能新技术股份有限公司 | Composite solid electrolyte film with ultrahigh NASICON ceramic content and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016208486A1 (en) * | 2015-06-24 | 2016-12-29 | ユニチカ株式会社 | Solid electrolyte reinforcement member and solid electrolyte film including reinforcement member |
| CN107069081A (en) * | 2016-12-27 | 2017-08-18 | 华中科技大学 | A kind of solid polyelectrolyte material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100531724B1 (en) * | 2004-02-26 | 2005-11-29 | 재단법인서울대학교산학협력재단 | Solvent-free polymer electrolytes with porous membranes filled with oligomeric viscous materials and secondary batteries employing the same |
| US8492033B2 (en) * | 2009-06-18 | 2013-07-23 | Uchicago Argonne, Llc | Fast cure gel polymer electrolytes |
| JP2012089399A (en) * | 2010-10-21 | 2012-05-10 | Konica Minolta Holdings Inc | Electrode plate for lithium-ion secondary battery and lithium-ion secondary battery |
| JP6257034B2 (en) * | 2014-02-28 | 2018-01-10 | 日本化学工業株式会社 | Proton conductive gel and method for producing the same |
| JP6786783B2 (en) * | 2015-09-30 | 2020-11-18 | Jsr株式会社 | Silicon-containing film forming composition and pattern forming method for multilayer resist process |
-
2020
- 2020-03-06 CN CN202010152212.7A patent/CN111416147B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016208486A1 (en) * | 2015-06-24 | 2016-12-29 | ユニチカ株式会社 | Solid electrolyte reinforcement member and solid electrolyte film including reinforcement member |
| CN107069081A (en) * | 2016-12-27 | 2017-08-18 | 华中科技大学 | A kind of solid polyelectrolyte material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111416147A (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111416147B (en) | Composite solid polymer electrolyte and preparation method thereof | |
| Wang et al. | Siloxane-based polymer electrolytes for solid-state lithium batteries | |
| Yang et al. | Review of ionic liquids containing, polymer/inorganic hybrid electrolytes for lithium metal batteries | |
| Xu et al. | Gel polymer electrolyte based on PVDF-HFP matrix composited with rGO-PEG-NH2 for high-performance lithium ion battery | |
| EP2842194B1 (en) | Fluoropolymer film | |
| EP2780404B1 (en) | Method for manufacturing a polymer electrolyte separator and polymer electrolyte separator therefrom | |
| CN110380114B (en) | Organic-inorganic composite solid electrolyte and preparation method and application thereof | |
| Shang et al. | A novel polyhedral oligomeric silsesquioxane based ionic liquids (POSS-ILs) polymer electrolytes for lithium ion batteries | |
| CN102044702B (en) | Composite polymer electrolyte for lithium ion battery and preparation method thereof | |
| CN107078267B (en) | Composite electrode | |
| Tsao et al. | Stable lithium deposition generated from ceramic-cross-linked gel polymer electrolytes for lithium anode | |
| CN111253521B (en) | Organic-inorganic-ionic liquid composite solid electrolyte, preparation method and application thereof | |
| CN102723528B (en) | Amphion liquid electrolyte material and preparation thereof and application in lithium battery electrolytes | |
| CN110444807B (en) | Composite gel polymer electrolyte, preparation method and application thereof | |
| TWI453972B (en) | Solid polymer electrolyte composition | |
| CN111416148B (en) | Composite solid polymer electrolyte doped with modified nano silicon dioxide particles and preparation method thereof | |
| CN110034329B (en) | Preparation method of garnet coordinated Lewis base induced in-situ crosslinked fluoropolymer gel electrolyte membrane | |
| CN114031777B (en) | Silicon-containing polymer electrolyte material and lithium battery prepared by using same | |
| KR20180072469A (en) | Organic-inorganic composite solid electrolyte, lithium secondary cell comprising the same, and manufacturing method for the lithium secondary cell | |
| CN111416146B (en) | Modified nano silicon dioxide and preparation method and application thereof | |
| Cheng et al. | Preparation of SiO2 grafted polyimidazole solid electrolyte for lithium-ion batteries | |
| CN108598376B (en) | Functionalized ionic liquid/S-C composite material, preparation method thereof and composite anode material | |
| CN116284740A (en) | Sulfide-polymer composite solid electrolyte membrane prepared by molecular hybridization and preparation method and application thereof | |
| CN113410516B (en) | Organic silicon electrolyte and preparation method and application thereof | |
| CN114006028B (en) | Modified inorganic fast ion conductor and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |