CN114388885A - Asymmetric composite solid electrolyte membrane and preparation method and application thereof - Google Patents

Asymmetric composite solid electrolyte membrane and preparation method and application thereof Download PDF

Info

Publication number
CN114388885A
CN114388885A CN202111572790.7A CN202111572790A CN114388885A CN 114388885 A CN114388885 A CN 114388885A CN 202111572790 A CN202111572790 A CN 202111572790A CN 114388885 A CN114388885 A CN 114388885A
Authority
CN
China
Prior art keywords
lithium
solid electrolyte
composite solid
electrolyte membrane
asymmetric composite
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.)
Pending
Application number
CN202111572790.7A
Other languages
Chinese (zh)
Inventor
王秀丽
蔡丹
夏新辉
涂江平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN202111572790.7A priority Critical patent/CN114388885A/en
Publication of CN114388885A publication Critical patent/CN114388885A/en
Pending legal-status Critical Current

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
    • 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)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an asymmetric composite solid electrolyte membrane, a preparation method and application thereof. The preparation method is simple, efficient and environment-friendly, the liquid-phase components are locked in the electrolyte after cross-linking polymerization, and the lithium ion conductive electrolyte has the function of quickly conducting lithium ions. The prepared asymmetric electrolyte consists of a gel polyelectrolyte layer supported by a network structure and a composite electrolyte thin layer enriched with inorganic particles on one side. The gel polymer layer can realize flexible contact with the positive electrode side, and the composite electrolyte thin layer enriched with inorganic particles is expected to inhibit dendritic growth in the lithium negative electrode cycle process.

Description

Asymmetric composite solid electrolyte membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an asymmetric composite solid electrolyte membrane and a preparation method and application thereof.
Background
In recent years, polymer solid electrolytes have attracted much attention in the field of solid-state batteries because of their good processability and good interfacial compatibility with electrodes. Among them, gel polymer electrolytes show great application prospects due to their high ionic conductance. The introduction of the in-situ polymerization technology further simplifies the preparation process of the gel electrolyte and reduces the use of polluting organic solvents. However, the gel polymer electrolyte cannot inhibit the growth of dendrites during battery cycling due to its limited mechanical properties, which would cause a serious safety problem for a solid-state battery using lithium metal as a negative electrode.
Therefore, the development of a high-safety, high-energy density solid-state lithium metal battery is urgently needed. It is well known that inorganic particles represented by inorganic electrolytes generally have high mechanical strength, and thus can effectively suppress dendritic growth in lithium metal batteries. Therefore, the introduction of inorganic particles into the gel electrolyte is one of the strategies to improve the safety of the battery. In the invention, inorganic particles are introduced into one side of an electrolyte by utilizing the enrichment effect of a membrane with a net structure on the particles, and then the inorganic particles are cured in situ, so that the asymmetric composite solid electrolyte membrane is designed.
Disclosure of Invention
The invention provides a preparation method of an asymmetric composite solid electrolyte membrane.
The invention firstly mixes the cross linker, lithium salt, solvent and inorganic particles to form uniform precursor solution, then drops the precursor solution on the supporting membrane with net structure, because of the filtering action of the membrane with net structure, the inorganic particles can be enriched on one side of the membrane, and the rest solution can pass through and fully infiltrate the membrane with net structure, after cross linking polymerization by the cross linker, an asymmetric composite solid electrolyte membrane is formed, which is composed of a gel electrolyte layer supported by net structure and a composite electrolyte thin layer enriched with inorganic particles on one side. In a solid-state battery, the gel layer can achieve flexible contact with the positive electrode side, and the thin layer of the composite electrolyte rich in inorganic particles is expected to inhibit dendritic growth during the lithium negative electrode cycle.
A method for preparing an asymmetric composite solid electrolyte membrane, comprising the steps of:
(1) adding a cross-linking agent and lithium salt into a solvent, and stirring to obtain a uniform solution;
(2) and (2) adding inorganic particles into the uniform solution obtained in the step (1), fully stirring, and finally adding an initiator into the solution, and uniformly stirring to obtain a mixed solution.
(3) And (3) dropwise adding the electrolyte precursor mixed solution obtained in the step (2) on a support membrane with a net structure, concentrating inorganic particles on one side of the net structure through the filtering action of the net structure, polymerizing a cross-linking agent in the solution under the action of ultraviolet light or heating, and fully curing to form the asymmetric composite solid electrolyte membrane.
The invention utilizes the filtering action of the net-shaped structure membrane to enrich inorganic particles on one side of the net, and then the asymmetric composite solid electrolyte membrane is formed after the inorganic particles are crosslinked and solidified in a precursor solution by a crosslinking agent.
The preparation method comprises the steps of dissolving a cross-linking agent and lithium salt in a solvent, adding inorganic particles, fully stirring, adding an initiator, stirring to obtain a uniform mixed solution, dripping the mixed solution on a supporting membrane with a net structure, enriching the inorganic particles on one side through the filtering action of a net, enabling the rest solution to penetrate through and infiltrate the membrane, and finally curing under the irradiation of an ultraviolet lamp or under the heating condition to form the asymmetric composite solid electrolyte membrane.
In the step (1), the amount of the added cross-linking agent is 10-50% of the mass of the solvent, and the amount of the added lithium salt is 5-50% of the mass of the solvent.
The cross-linking agent is one or more (more than two, including two) of polyacrylate (polyethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, etc.) and polycarbonate (poly (carbon ethylene ester, poly (butyl carbonate), etc.).
The lithium salt is one or more (more than two, including two) of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium difluorophosphate, lithium bis (trifluoromethylsulfonyl) imide or lithium trifluoromethanesulfonate.
The solvent is one or more (more than two) of triethyl phosphate, trimethyl phosphate, fluoroethylene carbonate, diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethylene carbonate, 1, 3-dioxolane and 1, 2-dimethoxyethane.
In the step (2), stirring for 0.5-4h (preferably 2h) until the particles are uniformly dispersed in the solution.
The initiator is further added to the solution and stirred for 5 to 20 minutes (more preferably 10 minutes).
Wherein, the added inorganic particles account for 5 to 50 percent (preferably 10 percent) of the mass of the solvent, and the added initiator accounts for 0.5 to 3 percent (most preferably 1.5 percent) of the mass of the cross-linking agent.
The inorganic particles are one or more (two or more) of inorganic electrolytes (garnet type fast ion conductors, perovskite type fast ion conductors, sodium super-ion conductor type electrolytes, sulfur-series solid electrolytes and the like), metal organic framework materials and oxide particles (titanium dioxide, silicon dioxide, aluminum oxide and the like).
The asymmetric composite solid electrolyte membrane consists of a gel electrolyte layer supported by a network structure and a composite electrolyte thin layer enriched with inorganic particles on one side.
Conditions of polymerization: polymerizing for 10-30min (preferably 15min) under the irradiation of an ultraviolet lamp or polymerizing for 1-3 h at 60-80 ℃, preferably polymerizing for 2h at 70 ℃.
The asymmetric composite solid electrolyte membrane is used as a solid electrolyte in the preparation of a solid battery.
A solid-state battery consists of a positive electrode, an electrolyte and a negative electrode, wherein the electrolyte adopts the asymmetric composite solid-state electrolyte membrane, and the positive electrode is one of lithium iron phosphate, lithium cobaltate, ternary materials, lithium sulfide and sulfur; the negative electrode is a metal lithium sheet, silicon-based or carbon-based negative electrode. The specific assembly method is as follows: firstly, placing the support film with the net structure on a positive electrode, then dropwise adding an electrolyte precursor, then placing a negative electrode, and finally carrying out in-situ curing to obtain the solid-state battery. The gel electrolyte layer supported by the network structure in the solid-state battery is assembled to the anode, and the inorganic particle-enriched composite electrolyte thin layer with good mechanical property is assembled to the cathode. I.e. the asymmetric composite solid electrolyte membrane is arranged between said positive and negative electrodes. The gel polymer layer can realize flexible contact with the positive electrode side, and the composite electrolyte thin layer enriched with inorganic particles is expected to inhibit dendritic growth in the lithium negative electrode cycle process.
The obtained asymmetric composite solid electrolyte membrane is assembled into a stainless steel blocking battery for testing, and the testing frequency is 10-2-106Hz, the ionic conductivity of the electrolyte was tested in an environment of 25 ℃.
The obtained asymmetric composite solid electrolyte membrane is assembled into a lithium cobaltate full cell to be tested, so that the performance of the lithium cobaltate full cell is tested.
Compared with the prior art, the invention has the following advantages:
the invention provides a preparation method of an asymmetric composite electrolyte, which comprises the steps of mixing a cross-linking agent, lithium salt, a solvent and inorganic particles to form a uniform precursor solution, then dropwise adding the precursor solution onto a supporting membrane with a net structure, wherein the inorganic particles can be enriched on one side of the membrane due to the filtering action of the membrane with the net structure, the rest solution can penetrate through and fully infiltrate the membrane with the net structure, and an asymmetric composite solid electrolyte membrane is formed after cross-linking polymerization by the cross-linking agent and consists of a gel electrolyte layer supported by the net structure and a composite electrolyte thin layer enriched with the inorganic particles on one side. The preparation method is simple, efficient and environment-friendly, the liquid-phase components are locked in the electrolyte after cross-linking polymerization, and the lithium ion conductive electrolyte has the function of quickly conducting lithium ions. The gel polymer layer can realize flexible contact with the positive electrode side, and the composite electrolyte thin layer enriched with inorganic particles is expected to inhibit dendritic growth in the lithium negative electrode cycle process. The asymmetric composite solid electrolyte membrane is applied to a solid battery, so that the rapid lithium ion conduction in the battery can be ensured, and the long-term stability of the battery in the circulating process can be improved.
Drawings
FIG. 1 is a schematic view of the structure of an asymmetric composite solid electrolyte membrane in example 1;
FIG. 2 is a scanning electron micrograph of an asymmetric composite solid electrolyte membrane according to example 1;
fig. 3 is an impedance map of a clogged cell assembled from an asymmetric composite solid electrolyte membrane in example 1, in fig. 3, the abscissa is the real part of the impedance Nyquist diagram, and the ordinate is the imaginary part of the impedance Nyquist diagram;
fig. 4 is a graph showing cycle performance of a lithium cobaltate solid state lithium battery assembled with an asymmetric composite solid state electrolyte membrane and a gel electrolyte in application example 1 and application example 4, in fig. 4, the abscissa is the number of cycles and the ordinate is the discharge capacity.
Detailed Description
The present invention will be described in detail below with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) 0.1g of lithium salt (LiDFOB) and 0.2g of polyethylene glycol diacrylate (PEGDA, average molecular weight 600, avadin) as a crosslinking agent were added to 1.0g of a solvent of ethylene carbonate/dimethyl carbonate (EC/DMC, mixed in a volume ratio of 1: 1), and sufficiently stirred to obtain a uniform solution.
(2) To the homogeneous solution obtained by the previous stirring, 0.1g of LLZTO nanoparticles was added and stirred for 2 hours, and then 0.003g of thermal initiator AIBN (1.5% of PEGDA) was added and stirred for 10 minutes to obtain a homogeneous solution.
(3) And (3) taking a dry cellulose membrane, dropwise adding the uniform solution obtained in the previous step on the cellulose membrane, and then transferring the cellulose membrane into an oven to polymerize for 2 hours at 70 ℃ to obtain the asymmetric composite solid electrolyte membrane with the LLZTO nanoparticles enriched on one side of the cellulose membrane.
The structure and morphology of the asymmetric composite solid electrolyte membrane prepared in this example are shown in fig. 1 and 2, respectively.
The results of the impedance test of the stainless steel-made plugged cell assembled with the asymmetric composite solid electrolyte membrane prepared in this example are shown in FIG. 3, and the ionic conductivity calculated is 1.25X 10–3S cm–1.
Example 2
(1) 0.05g of lithium salt (LiDFOB) and 0.3g of polyethylene glycol diacrylate (PEGDA, average molecular weight 600, avadin) as a crosslinking agent were added to 1.0g of a solvent of ethylene carbonate/dimethyl carbonate (EC/DMC, mixed in a volume ratio of 1: 1), and sufficiently stirred to obtain a uniform solution.
(2) To the homogeneous solution obtained by the previous stirring, 0.2g of LLZTO nanoparticles was added and stirred for 2 hours, and then 0.0045g of thermal initiator AIBN (1.5% of PEGDA) was added and stirred for 10 minutes to obtain a homogeneous solution.
(3) And (3) taking a dry cellulose membrane, dropwise adding the uniform solution obtained in the previous step on the cellulose membrane, and then transferring the cellulose membrane into an oven to polymerize for 2 hours at 70 ℃ to obtain the asymmetric composite solid electrolyte membrane with the LLZTO nanoparticles enriched on one side of the cellulose membrane.
The ion conductivity of the asymmetric composite solid electrolyte membrane prepared in this example was 1.12X 10–3S cm–1.
Example 3
(1) 0.15g of lithium salt (LiDFOB) and 0.3g of crosslinking agent ethoxylated trimethylolpropane triacrylate (ETPTA, average molecular weight 692, avadin) were added to 1.0g of ethylene carbonate/dimethyl carbonate (EC/DMC, mixed in a volume ratio of 1: 1) solvent, and sufficiently stirred to obtain a uniform solution.
(2) 0.1g of LLZTO nanoparticles was added to the homogeneous solution obtained by the previous stirring step, and stirred for 2 hours, and then 0.0045g of thermal initiator AIBN (1.5% of ETPTA) was added and stirred for 10 minutes to obtain a homogeneous solution.
(3) And (3) taking a dry cellulose membrane, dropwise adding the uniform solution obtained in the previous step on the cellulose membrane, and then transferring the cellulose membrane into an oven to polymerize for 2 hours at 70 ℃ to obtain the asymmetric composite solid electrolyte membrane with the LLZTO nanoparticles enriched on one side of the cellulose membrane.
The ion conductivity of the asymmetric composite solid electrolyte membrane prepared in this example was 1.15X 10–3S cm–1.
Comparative example 1
(1) 0.1g of lithium salt (LiDFOB) and 0.2g of polyethylene glycol diacrylate (PEGDA, average molecular weight 600, avadin) as a crosslinking agent were added to 1.0g of a solvent of ethylene carbonate/dimethyl carbonate (EC/DMC, mixed in a volume ratio of 1: 1), and sufficiently stirred to obtain a uniform solution.
(2) To the homogeneous solution obtained by the previous stirring step, 0.003g of thermal initiator AIBN (1.5% based on PEGDA) was added and stirred for another 10 minutes to obtain a homogeneous solution.
(3) Taking a piece of dry cellulose membrane, dropwise adding the uniform solution obtained in the previous step on the cellulose membrane, and then transferring the cellulose membrane into an oven to polymerize for 2 hours at 70 ℃ to obtain the gel electrolyte.
The ionic conductivity of the gel electrolyte membrane prepared in this example was 1.27X 10–3S cm–1.
Application example 1
The asymmetric composite solid electrolyte membrane prepared in example 1 was assembled into a solid lithium battery by the following method:
0.8g of lithium cobaltate positive electrode active material, 0.1g of carbon nano tube (conductive agent) and 0.1g of polyvinylidene fluoride (binder) are fully ground, dissolved in 3mL of N-methyl pyrrolidone and fully stirred for 4 hours to obtain uniform slurry. And (3) coating the uniform slurry on an aluminum foil current collector, and performing vacuum drying at 60 ℃ for 12h to obtain the positive plate.
The prepared lithium cobaltate pole piece is used as a positive pole, the metal lithium piece is used as a negative pole, the asymmetric composite solid electrolyte membrane prepared in the example is used as an electrolyte, and the CR2025 button cell is assembled, wherein the assembly process of the cell is completed in a glove box which is filled with argon and has the water oxygen content of less than 0.1 ppm. The specific assembly method is as follows: the membrane with the net structure is placed on the anode, then the electrolyte precursor is dripped upwards, the cathode is placed, and finally the solid-state battery can be obtained by in-situ solidification. The solid-state battery is characterized in that a gel polyelectrolyte layer supported by a net structure is assembled to a positive electrode, and a composite electrolyte thin layer with good mechanical property and rich in inorganic particles is assembled to a negative electrode.
And carrying out constant-current charge-discharge test on the obtained lithium cobaltate solid-state battery on an electrochemical workstation, wherein the charge-discharge interval is 3-4.3V, and the current density is 0.2C.
In this application example, the cycle performance of a lithium cobalt oxide battery assembled from the asymmetric composite solid electrolyte membrane prepared in example 1 is shown in fig. 4, and the capacity retention rate after 100 cycles is 95%.
Application example 2
The constant current charge-discharge cycle stability of the lithium cobaltate cell assembled from the asymmetric composite solid electrolyte membrane prepared in example 2 was tested by the same method for assembling the solid lithium cell and the constant current charge-discharge cycle stability test method as in application example 1.
The results show that the lithium cobalt oxide battery assembled by the asymmetric composite solid electrolyte membrane prepared in example 2 has good cycle stability, and the capacity retention rate is 90% after 100 cycles.
Application example 3
The constant current charge-discharge cycle stability of the lithium cobaltate cell assembled from the asymmetric composite solid electrolyte membrane prepared in example 3 was tested by the same assembly method of the solid lithium cell and the constant current charge-discharge cycle stability test method as in application example 1.
The results show that the lithium cobalt oxide battery assembled by the asymmetric composite solid electrolyte membrane prepared in example 3 has good cycle stability, and the capacity retention rate is 92% after 100 cycles.
Application example 4
The lithium cobaltate solid-state battery assembled with the gel electrolyte prepared in comparative example 1 was tested for constant current charge-discharge cycle stability using the same method for assembling a solid-state lithium battery and constant current charge-discharge cycle stability test method as in application example 1. The cycle stability test results of the lithium cobalt oxide battery assembled from the gel electrolyte prepared in comparative example 1 are shown in fig. 4.
As can be seen from fig. 4, the lithium cobaltate solid state lithium battery assembled using the gel electrolyte prepared in comparative example 1 exhibited a very fast capacity fade, demonstrating that the lithium cobaltate solid state lithium battery assembled using the asymmetric composite solid state electrolyte membrane prepared according to the present invention has good cycle stability.
From the above examples, the invention introduces the inorganic particle-enriched composite electrolyte thin layer on one side of the gel electrolyte by a simple method, and the inorganic particle-enriched composite electrolyte layer can effectively inhibit dendritic crystal growth in the lithium battery and also can prevent the battery short circuit caused by the penetration of the electrolyte by the dendritic crystal, so that the lithium cobaltate battery assembled by the inorganic particle-enriched composite electrolyte thin layer shows good cycle stability, which is beneficial to further improving the energy density of the existing battery system.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. A method for preparing an asymmetric composite solid electrolyte membrane, comprising the steps of:
(1) adding a cross-linking agent and lithium salt into a solvent, and stirring to obtain a uniform solution;
(2) adding inorganic particles into the uniform solution obtained in the step (1), fully stirring, and finally adding an initiator into the solution, and stirring to obtain an electrolyte precursor mixed solution;
(3) and (3) dropwise adding the electrolyte precursor mixed solution obtained in the step (2) on a support membrane with a net structure, concentrating inorganic particles on one side of the net structure through the filtering action of the net structure, polymerizing a cross-linking agent in the solution under the action of ultraviolet light or heating, and fully curing to form the asymmetric composite solid electrolyte membrane.
2. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (1), the amount of the crosslinking agent added is 10% to 50% by mass of the solvent, and the amount of the lithium salt added is 5% to 50% by mass of the solvent.
3. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (1), the crosslinking agent is one or two or more of polyacrylate and polycarbonate;
the lithium salt is one or more than two of bistrifluoromethane sulfonyl imide lithium, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium dioxalate borate, lithium oxalodifluoroborate, lithium difluorophosphate, bis (trifluoromethylsulfonyl) imide lithium or lithium trifluoromethanesulfonate;
the solvent is one or more than two of triethyl phosphate, trimethyl phosphate, fluoroethylene carbonate, diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethylene carbonate, 1, 3-dioxolane and 1, 2-dimethoxyethane.
4. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (2), the particles are sufficiently stirred for 0.5 to 4 hours until the particles are uniformly dispersed in the solution;
and adding an initiator into the solution, and stirring for 5-20 minutes.
5. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (2), the inorganic particles are added in an amount of 5% to 50% by mass based on the solvent;
the added initiator accounts for 0.5 to 3 percent of the mass of the cross-linking agent.
6. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (2), the inorganic particles are one or two or more of inorganic electrolytes, metal-organic framework materials, and oxide particles.
7. The method for producing an asymmetric composite solid electrolyte membrane according to claim 1, wherein in the step (3), the support membrane of the mesh structure is one or two or more of a cellulose membrane, a commercial separator, a polyimide membrane, and a nylon membrane.
8. The production method of an asymmetric composite solid electrolyte membrane according to claim 1, characterized in that in step (3), the conditions of polymerization: polymerizing for 10-20min under the irradiation of an ultraviolet lamp or polymerizing for 1-3 h at 60-80 ℃.
9. The asymmetric composite solid electrolyte membrane produced by the production method according to any one of claims 1 to 8, wherein the asymmetric composite solid electrolyte membrane is composed of a gel electrolyte layer supported by a network structure and an inorganic particle-rich composite electrolyte layer on one side.
10. The use of an asymmetric composite solid electrolyte membrane according to claim 9 in the preparation of a solid state battery comprising a positive electrode, an electrolyte, a negative electrode, said electrolyte being said asymmetric composite solid electrolyte membrane disposed between said positive and negative electrodes, said network supporting a gel electrolyte layer for the positive electrode and an inorganic particle enriched composite electrolyte layer for the negative electrode.
CN202111572790.7A 2021-12-21 2021-12-21 Asymmetric composite solid electrolyte membrane and preparation method and application thereof Pending CN114388885A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111572790.7A CN114388885A (en) 2021-12-21 2021-12-21 Asymmetric composite solid electrolyte membrane and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111572790.7A CN114388885A (en) 2021-12-21 2021-12-21 Asymmetric composite solid electrolyte membrane and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114388885A true CN114388885A (en) 2022-04-22

Family

ID=81198176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111572790.7A Pending CN114388885A (en) 2021-12-21 2021-12-21 Asymmetric composite solid electrolyte membrane and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114388885A (en)

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050042489A1 (en) * 2003-07-11 2005-02-24 Kenji Fukuta Laminate useful as a membrane-electrode assembly for fuel cells, production process therefor and a fuel cell provided with the laminate
CN1969407A (en) * 2004-07-07 2007-05-23 株式会社Lg化学 New organic/inorganic composite porous film and electrochemical device prepared thereby
CN104638296A (en) * 2015-01-23 2015-05-20 清华大学深圳研究生院 Method for preparing solid polymer electrolyte lithium ion battery
CN105591154A (en) * 2015-02-13 2016-05-18 中国科学院青岛生物能源与过程研究所 Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof
CN107078256A (en) * 2014-09-22 2017-08-18 东京应化工业株式会社 Metal secondary batteries barrier film
CN108232293A (en) * 2018-01-03 2018-06-29 清陶（昆山）能源发展有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method and its application in solid state lithium battery
CN109494390A (en) * 2018-10-30 2019-03-19 溧阳天目先导电池材料科技有限公司 A kind of modified solid electrolyte membrane and preparation method thereof and lithium battery
CN109786812A (en) * 2019-01-15 2019-05-21 北京理工大学 A kind of photo-cured solid composite electrolyte and preparation method thereof
CN110391382A (en) * 2018-04-20 2019-10-29 三星电子株式会社 Composite diaphragm, preparation method and the lithium secondary battery including it
CN110459803A (en) * 2019-08-20 2019-11-15 昆山宝创新能源科技有限公司 Composite electrolyte membrane and its preparation method and application
CN110581314A (en) * 2018-06-08 2019-12-17 郑州宇通集团有限公司 Multilayer-structure composite solid electrolyte membrane, preparation method thereof and solid battery
CN111244532A (en) * 2020-03-23 2020-06-05 上海汽车集团股份有限公司 Three-dimensional inorganic polymer composite solid electrolyte and ternary solid lithium battery
CN111378203A (en) * 2020-03-05 2020-07-07 大连理工大学 Preparation and application of rigid-flexible parallel solid electrolyte membrane
CN111463480A (en) * 2020-03-20 2020-07-28 东华大学 Filter membrane based high-performance composite solid electrolyte film and preparation method and application thereof
CN112018430A (en) * 2020-08-13 2020-12-01 浙江南都电源动力股份有限公司 Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof
CN112038693A (en) * 2020-09-11 2020-12-04 惠州亿纬锂能股份有限公司 Solid electrolyte and preparation method and application thereof
CN112838262A (en) * 2021-01-10 2021-05-25 中南大学 Preparation method of polyamide-based gel polymer electrolyte with multi-network structure

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050042489A1 (en) * 2003-07-11 2005-02-24 Kenji Fukuta Laminate useful as a membrane-electrode assembly for fuel cells, production process therefor and a fuel cell provided with the laminate
CN1969407A (en) * 2004-07-07 2007-05-23 株式会社Lg化学 New organic/inorganic composite porous film and electrochemical device prepared thereby
CN107078256A (en) * 2014-09-22 2017-08-18 东京应化工业株式会社 Metal secondary batteries barrier film
CN104638296A (en) * 2015-01-23 2015-05-20 清华大学深圳研究生院 Method for preparing solid polymer electrolyte lithium ion battery
CN105591154A (en) * 2015-02-13 2016-05-18 中国科学院青岛生物能源与过程研究所 Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof
CN108232293A (en) * 2018-01-03 2018-06-29 清陶（昆山）能源发展有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method and its application in solid state lithium battery
CN110391382A (en) * 2018-04-20 2019-10-29 三星电子株式会社 Composite diaphragm, preparation method and the lithium secondary battery including it
CN110581314A (en) * 2018-06-08 2019-12-17 郑州宇通集团有限公司 Multilayer-structure composite solid electrolyte membrane, preparation method thereof and solid battery
CN109494390A (en) * 2018-10-30 2019-03-19 溧阳天目先导电池材料科技有限公司 A kind of modified solid electrolyte membrane and preparation method thereof and lithium battery
CN109786812A (en) * 2019-01-15 2019-05-21 北京理工大学 A kind of photo-cured solid composite electrolyte and preparation method thereof
CN110459803A (en) * 2019-08-20 2019-11-15 昆山宝创新能源科技有限公司 Composite electrolyte membrane and its preparation method and application
CN111378203A (en) * 2020-03-05 2020-07-07 大连理工大学 Preparation and application of rigid-flexible parallel solid electrolyte membrane
CN111463480A (en) * 2020-03-20 2020-07-28 东华大学 Filter membrane based high-performance composite solid electrolyte film and preparation method and application thereof
CN111244532A (en) * 2020-03-23 2020-06-05 上海汽车集团股份有限公司 Three-dimensional inorganic polymer composite solid electrolyte and ternary solid lithium battery
CN112018430A (en) * 2020-08-13 2020-12-01 浙江南都电源动力股份有限公司 Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof
CN112038693A (en) * 2020-09-11 2020-12-04 惠州亿纬锂能股份有限公司 Solid electrolyte and preparation method and application thereof
CN112838262A (en) * 2021-01-10 2021-05-25 中南大学 Preparation method of polyamide-based gel polymer electrolyte with multi-network structure

Similar Documents

Publication Publication Date Title
CN110556586B (en) Polymeric organic-inorganic composite solid electrolyte and in-situ assembled all-solid-state battery
CN108493486B (en) Preparation method of in-situ polymerization solid-state battery
CN109802174A (en) A kind of preparation and its application of polycarbonate base polymer electrolyte
CN112038694B (en) Three-layer composite electrolyte with sandwich structure and preparation method and application thereof
CN111933894A (en) In-situ polymerized organic-inorganic composite solid battery
CN111697262A (en) Composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof
CN110556493B (en) Functional composite diaphragm of lithium/sodium secondary battery and preparation method thereof
CN109346767A (en) A kind of solid polymer electrolyte and its application in lithium metal battery
CN108550835B (en) Lithium iron phosphate/gel electrolyte composite positive electrode material and preparation method thereof, and solid-state lithium battery and preparation method thereof
CN105958122A (en) Three-dimensional crosslinked network polymer gel electrolyte membrane, preparation method and lithium-ion battery
CN106450327A (en) Method for improving adhesive performance of lithium battery polyvinylidene fluoride by irradiation
CN110190284B (en) Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof
CN1331935C (en) Composite microporous polymer electrolyte and its preparing method
CN110444803A (en) A kind of lithium ion battery structure of semisolid and preparation method thereof
CN107565161B (en) Cellulose-blended gel polymer electrolyte and preparation method and application thereof
CN115441048A (en) Composite electrolyte with stable gradient distribution structure, battery and preparation method
CN110957471A (en) Method for improving interfacial wettability of electrode of quasi-solid battery
CN114373986A (en) Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery
TW202320378A (en) Preparation method of all-solid composite polymer electrolyte film and all-solid lithium battery advantageous in having fast manufacturing process and excellent performance, and capable of being perfectly applied to all-solid lithium batteries with high voltage and high energy density
CN111682262B (en) Three-dimensional cross-linked network gel polymer electrolyte membrane and preparation method and application thereof
CN117219847A (en) Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery
CN114388885A (en) Asymmetric composite solid electrolyte membrane and preparation method and application thereof
CN115719859A (en) Preparation method of solid-state battery
CN115295865A (en) Preparation method of in-situ polymerization solid polymer electrolyte lithium ion battery
CN114865226A (en) Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220422