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Modified metal organic framework (MOF) compound material, preparation method, proton exchange membrane and application thereof

A metal organic framework, proton exchange membrane technology, applied in the field of proton exchange membrane, preparation method, modified MOF material, can solve the problem of low membrane selectivity, affecting the service life of vanadium redox flow battery, proton exchange membrane proton conductivity and It is difficult to improve the performance of vanadium ion resistance at the same time, so as to achieve the effect of high proton conductivity and low vanadium ion permeability

Pending Publication Date: 2021-11-26
NORTH CHINA ELECTRIC POWER UNIV (BAODING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, the permeation of fuel greatly affects the service life of vanadium redox flow batteries, and the proton conductivity and vanadium ion resistance of proton exchange membranes are usually difficult to improve at the same time, and the selectivity of the membrane is very low.

Method used

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  • Modified metal organic framework (MOF) compound material, preparation method, proton exchange membrane and application thereof
  • Modified metal organic framework (MOF) compound material, preparation method, proton exchange membrane and application thereof
  • Modified metal organic framework (MOF) compound material, preparation method, proton exchange membrane and application thereof

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preparation example Construction

[0046] According to one aspect of the present invention, a kind of preparation method of modified MOF material is provided, comprising the following steps:

[0047] Provide a mixed solution containing MOF, monomer and initiator;

[0048] removing the air in the pores of the MOF in the mixed solution, and

[0049] In-situ free radical polymerization of the monomers in the mixed solution;

[0050] Wherein, the monomer contains a sulfonate group, and the window size of the MOF is smaller than (Such as figure 1 middle is the window size).

[0051] In the present invention, monomers, initiators and MOFs are prepared into a mixed solution. In the mixed solution, monomers and initiators exist in MOF pores. After removing the air in MOF pores, the monomers present in MOF pores Under the action of the initiator, the in-situ radical polymerization reaction occurs, and the monomers are polymerized into polymers in the pores of the MOF. The polymer shuttles and connects in the con...

Embodiment 1

[0082] Dissolve 1.0 g of sodium p-styrenesulfonate in N,N-dimethylformamide / water (12mL, 10:2v:v) solution, and then add azobisisobutyronitrile (mass of sodium p-styrenesulfonate 3%) was added to the aforementioned dispersion. After that, 0.7g of UiO-66 was added to the sodium p-styrenesulfonate-azobisisobutyronitrile solution, and N 2 , and then vacuumed for 10 minutes, repeated three times to remove the oxygen in the pores of the MOF. The aforementioned dispersion was stirred in an 80° C. oil bath under a nitrogen atmosphere for 5 days. After the product is collected, soak it in N,N-dimethylformamide for a period of time to remove unreacted sodium p-styrene sulfonate and unfixed polyvinylbenzene sulfonate, and collect the product after drying. The resulting modified MOF material has a size of about 50 nm.

[0083] Disperse the above-mentioned modified MOF evenly in deionized water to make a dispersion liquid, dissolve sulfonated polyether ether ketone in N,N-dimethylaceta...

Embodiment 2

[0085] Dissolve 1.0 g of sodium p-styrenesulfonate in N,N-dimethylformamide / water (12mL, 10:2v:v) solution, and then add azobisisobutyronitrile (mass of sodium p-styrenesulfonate 3%) was added to the aforementioned dispersion. Then take 0.7g of UiO-66-NH 2 Add it into the sodium p-styrenesulfonate-azobisisobutyrocyanide solution. After stirring evenly, nitrogen gas is introduced, and then vacuumed for 10 minutes. Repeat three times to remove the oxygen in the pores of the MOF. The aforementioned dispersion was stirred in an 80° C. oil bath under a nitrogen atmosphere for 5 days. After collecting the product, soak it in N,N-dimethylformamide for a period of time to remove unreacted sodium p-styrene sulfonate and unfixed polyvinylbenzene sulfonate, and dry it to collect the product.

[0086] The film-forming process of the proton exchange membrane is the same as in Example 1, except that the modified MOF used is replaced by the modified MOF prepared in Example 2.

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Abstract

The invention relates to the technical field of flow batteries, in particular to a modified metal organic framework compound material, a preparation method, a proton exchange membrane and application thereof. The preparation method of the modified MOF material comprises the following steps: providing a mixed solution containing MOF, a monomer and an initiator; and removing air in MOF holes in the mixed solution, and carrying out in-situ free radical polymerization on monomers in the mixed solution, wherein the monomer contains a sulfonate group. The window of the MOF is smaller than that of a proton exchange membrane prepared from the modified MOF material, and the modified MOF material has high proton conductivity and low vanadium ion permeability and can be used for a flow battery.

Description

technical field [0001] The present application relates to the technical field of liquid flow batteries, in particular to a modified MOF material, a preparation method, a proton exchange membrane and applications thereof. Background technique [0002] The proton exchange membrane is the core component of the all-vanadium redox flow battery, but the hydrocarbon-based proton exchange membrane has limited its development because of its low proton conductivity. An ideal proton exchange membrane should have 0.1S cm in water -1 around the proton conductivity. Increasing the degree of sulfonation can increase the proton conductivity of the proton exchange membrane, but too high a degree of sulfonation usually leads to a decrease in the mechanical properties of the proton exchange membrane. [0003] Compared with perfluorosulfonic acid membranes such as Nafion, to achieve the same proton conductivity, hydrocarbon-based proton exchange membranes generally require a higher degree of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F112/14C08F120/58C08L25/18C08L33/24C08L87/00C08J5/22H01M8/1004H01M8/1032H01M8/1072H01M8/18C08L61/16
CPCC08F112/14C08F120/58C08L25/18C08L33/24C08J5/2275H01M8/1032H01M8/1072H01M8/1004H01M8/188C08J2361/16C08J2425/18C08J2433/24C08J2487/00C08L87/00Y02E60/50
Inventor 何少剑翟绍雄路忠睿林俊
Owner NORTH CHINA ELECTRIC POWER UNIV (BAODING)
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