Composite solid electrolyte membrane based on metal-organic framework material as well as preparation method and application of composite solid electrolyte membrane

A technology of solid electrolyte membrane and organic framework, which is applied in the direction of composite electrolyte, electrolyte battery manufacturing, non-aqueous electrolyte battery, etc. It can solve the problems of low conduction efficiency, limited high-voltage electrochemical stability, and insufficient ionic conductivity of solid electrolytes, etc. , to improve ionic conductivity, solve the problem of poor electrochemical stability at high voltage and easy control

Active Publication Date: 2021-08-06
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The Cu(BDC)MOF in the composite solid electrolyte membrane only provides active sites to absorb free lithium ions, and serves as a conduction path for lithium ions for lithium ion transmission, but does not produce cross-linking and polymerization with polymers, only physically mixed Form exists, so that there is an obvious physical interface between the polymer and the MOF, and the conduction efficiency of lithium ions between the MOF particles and the interface between the MOF and the polymer is not high, so there is still insufficient ionic conductivity of the solid electrolyte, and the high-voltage battery Problems with limited chemical stability

Method used

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  • Composite solid electrolyte membrane based on metal-organic framework material as well as preparation method and application of composite solid electrolyte membrane
  • Composite solid electrolyte membrane based on metal-organic framework material as well as preparation method and application of composite solid electrolyte membrane
  • Composite solid electrolyte membrane based on metal-organic framework material as well as preparation method and application of composite solid electrolyte membrane

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Experimental program
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Embodiment 1

[0044] A composite solid electrolyte membrane based on a metal-organic framework material comprising:

[0045] A polymer network formed by cross-linking polymerization of polyethylene oxide (PEO) and metal-organic framework (MOF) modified by toluene diisocyanate (TDI); lithium salt dispersed in the polymer network.

[0046]Among them, toluene diisocyanate is used as an intermediate, and the two ends are respectively connected with metal-organic framework materials and polyethylene oxide to form a network structure.

[0047] Preferably, the cross-linked polymerization mode of the polymer network structure is represented by a structural formula, as follows:

[0048]

[0049] Wherein said B and A, B and C are connected by a C-O chemical bond;

[0050] Wherein, A represents a metal-organic framework material group, B represents a toluene diisocyanate group, and C represents a polyethylene oxide group, and their respective structural formulas are as follows:

[0051] A:

[...

Embodiment 2

[0063] The preparation method of the metal-organic framework material (TDI-MOF) modified by toluene diisocyanate comprises the following steps:

[0064] (1) 8mmol Cu(NO 3 ) 2 and 4 mmol of 2,5-dihydroxyterephthalic acid were dissolved in 80 ml of a mixed liquid of N,N-dimethylformamide and absolute ethanol at a volume ratio of 20:1. Then the mixed liquid was heated at 80 °C overnight, the powder was obtained by centrifugation and washed with DMF, and finally the product was vacuum-dried at 150 °C overnight to obtain Cu-MOF-74 material.

[0065] (2) In a glove box filled with argon, disperse TDI and Cu-MOF-74 materials in toluene solvent at a mass ratio of 3:1, MOF is 10% of the solvent mass; heat and stir the mixture at 50 °C 6h, a crosslinking reaction occurs to obtain a metal-organic framework (TDI-MOF) modified with toluene diisocyanate and washed and dried;

[0066] The obtained toluene diisocyanate modified metal-organic framework (TDI-MOF) was characterized. SEM imag...

Embodiment 3

[0068] A preparation method for a solid electrolyte membrane at room temperature, comprising the following steps:

[0069] (1) In a glove box filled with argon, the TDI-MOF material prepared in Example 2 and LiTFSI lithium salt were dissolved in anhydrous acetonitrile, and ultrasonically dispersed to obtain the first slurry;

[0070] (2) Add polyethylene oxide to the first slurry obtained in step (1), and heat and stir at 50° C. for 5 hours to cause a crosslinking reaction between the TDI-MOF material and PEO to obtain a second slurry.

[0071] (3) The second slurry obtained in step (2) was poured onto a polytetrafluoroethylene template, and dried at 50° C. for 12 hours to obtain a treated PEO-TDI-MOF / LiTFSI composite solid electrolyte membrane.

[0072] Among them, the amount of lithium salt added is according to n(EO) / n(Li + )=20, the TDI-MOF material accounts for 2.5% of the mass of the composite solid electrolyte membrane.

[0073] The above-mentioned composite solid ele...

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Abstract

The invention discloses a composite solid electrolyte membrane based on a metal-organic framework material as well as a preparation method and application of the composite solid electrolyte membrane. The composite solid electrolyte membrane comprises a polymer network and lithium salt, wherein the polymer network is formed by polymerizing polyoxyethylene (PEO) and a metal-organic framework material (MOF) modified by toluene diisocynate (TDI), and the lithium salt is dispersed in the polymer network. According to the composite solid electrolyte membrane based on the metal-organic framework material as well as the preparation method and application of the composite solid electrolyte membrane of the invention, the toluene diisocynate is used as an intermediate, so that the MOF and the PEO are connected through chemical bonds, the ionic conductivity of lithium ions can be greatly enhanced, meanwhile, oxygenolysis of hydroxyl groups of the PEO under high voltage can be avoided, and the high-voltage electrochemical stability is remarkably improved. The preparation method is simple, easy to control, low in cost and easy to industrialize, and has a bright application prospect in the fields of high-specific-energy solid-state battery systems and flexible electronic energy storage devices.

Description

technical field [0001] The invention relates to the technical field of solid electrolyte materials, in particular to a composite solid electrolyte membrane based on a metal-organic framework material and its preparation method and application. Background technique [0002] Due to environmental problems such as the depletion of fossil fuels and global warming, the development of green, environmentally friendly and sustainable new energy materials and technologies has become an important strategic issue for countries all over the world. Lithium-ion batteries have been widely used in mobile phones, electric vehicles and other fields, but the frequent safety accidents such as fire, combustion and explosion caused by the leakage of flammable organic electrolyte limit the further application of lithium-ion batteries. At the same time, with social development and scientific and technological progress, people's demand for energy is increasing, and the energy density of the existing ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0565H01M10/058H01M10/0525C08G83/00
CPCH01M10/0565H01M10/058H01M10/0525C08G83/008H01M2300/0088Y02P70/50Y02E60/10
Inventor 欧星罗弼白笑宇张佳峰张宝
Owner CENT SOUTH UNIV
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