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Side chain sulfonated polyimide/perfluorosulfonic acid composite membrane, preparation method and application thereof

A sulfonated polyimide, perfluorosulfonic acid technology, applied in the direction of separator/film/diaphragm/spacer element, electrochemical generator, fuel cell, etc., can solve the problem of not particularly effectively improving the sulfonated polyamide The chemical stability of imine membrane, unfavorable composite membrane uniformity and high mechanical properties, and the chemical stability of composite membrane are not easy to achieve the effect of excellent mechanical properties and proton selection properties, excellent hydrolytic stability, chemical stability and dimensional stability.

Active Publication Date: 2018-08-21
湖南德沃普电气股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, inorganic fillers have the following three defects: (1) Inorganic substances and sulfonated polyimides have strong incompatibility, which makes it difficult for inorganic substances to be incorporated into composite membranes in large quantities, thus making the chemical composition of composite membranes difficult. The stability is not easy to be greatly improved; (2) It is difficult for the inorganic matter to distribute uniformly in the sulfonated polyimide membrane, and it is easy to agglomerate, which is not conducive to the uniformity and high mechanical properties of the composite membrane; (3) The blockage of the inorganic matter The effect will reduce the proton conductivity of the composite membrane, which is not conducive to the high voltage efficiency of the battery
In addition, researchers also tried to introduce organic substances (such as polyvinyl alcohol, chitosan, etc.) into sulfonated polyimide membranes, but the introduction of these organic substances did not effectively improve the chemical stability

Method used

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  • Side chain sulfonated polyimide/perfluorosulfonic acid composite membrane, preparation method and application thereof
  • Side chain sulfonated polyimide/perfluorosulfonic acid composite membrane, preparation method and application thereof
  • Side chain sulfonated polyimide/perfluorosulfonic acid composite membrane, preparation method and application thereof

Examples

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Comparison scheme
Effect test

Embodiment 1

[0048] A side-chain type sulfonated polyimide / perfluorosulfonic acid composite membrane of the present invention has a thickness of 45 μm, and the side-chain type sulfonated polyimide polymer and perfluorosulfonic acid polymer are polymerized The mass ratio of substance is 1.0:0.01, and the chemical structural formula of described side chain type sulfonated polyimide polymer is as follows:

[0049]

[0050] The preparation method of the side chain type sulfonated polyimide / perfluorosulfonic acid composite membrane comprises the following steps:

[0051] (1) Under the protection of argon, put 2.0mmol 2,2'-disulfonic acid benzidine, 55.0mL m-cresol and 1.3mL triethylamine into a 250mL three-port round bottom with a serpentine condenser In the flask, stir until the solid is dissolved; then add 4.0mmol 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2.0mmol 2,2-bis(3-amino-4-hydroxy Phenyl)hexafluoropropane, stirred until the solid was dissolved; finally added 8.0mmol 1...

Embodiment 2

[0065] A side-chain type sulfonated polyimide / perfluorosulfonic acid composite membrane of the present invention has a thickness of 55 μm, and the side-chain type sulfonated polyimide polymer and perfluorosulfonic acid polymer are polymerized The mass ratio of substance is 1.0:0.01, and the chemical structural formula of described side chain type sulfonated polyimide polymer is as follows:

[0066]

[0067] The preparation method of the side chain type sulfonated polyimide / perfluorosulfonic acid composite membrane comprises the following steps:

[0068] (1) Under the protection of argon, put 4.0mmol 2,2'-disulfonic acid benzidine, 110.0mL m-cresol and 2.6mL triethylamine into a 500mL three-port round bottom with a serpentine condenser In the flask, stir until the solid is dissolved; then add 8.0mmol 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 4.0mmol 2,2-bis(3-amino-4-hydroxy Phenyl)hexafluoropropane, stirred until the solid was dissolved; finally added 16.0mmol...

Embodiment 3

[0072] A side-chain type sulfonated polyimide / perfluorosulfonic acid composite membrane of the present invention has a thickness of 35 μm, and the side-chain type sulfonated polyimide polymer and perfluorosulfonic acid polymer are polymerized The mass ratio of substance is 1.0:0.01, and the chemical structural formula of described side chain type sulfonated polyimide polymer is as follows:

[0073]

[0074] The preparation method of the side chain type sulfonated polyimide / perfluorosulfonic acid composite membrane comprises the following steps:

[0075] (1) Under the protection of argon, put 3.0mmol 2,2'-disulfonic acid benzidine, 85.0mL m-cresol and 2.0mL triethylamine into a 250mL three-port round bottom with a serpentine condenser In the flask, stir until the solid is dissolved; then add 6.0mmol 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 3.0mmol 2,2-bis(3-amino-4-hydroxy Phenyl)hexafluoropropane, stirred until the solid was dissolved; finally added 12.0mmol ...

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Abstract

The invention discloses a side chain sulfonated polyimide / perfluorosulfonic acid composite membrane. The composite membrane comprises a side chain sulfonated polyimide macromoleclar polymer and a perfluorosulfonic acid macromoleclar polymer in a mass ratio of 1.0:0.05-0.25. The composite membrane not only has excellent hydrolysis stability, chemical stability and dimensional stability, but also has excellent mechanical properties and proton selectivity. The invention also provides a preparation method of the side chain sulfonated polyimide / perfluorosulfonic acid composite membrane characterized by simple process and easy operation. The invention also provides application of the composite membrane in all vanadium flow batteries, and the composite membrane has good application prospects in the field of all vanadium flow batteries, and can make batteries show excellent battery efficiency and charge-discharge cycle stability when used as a diaphragm.

Description

technical field [0001] The invention belongs to the field of battery diaphragms, and in particular relates to a side-chain type sulfonated polyimide / perfluorosulfonic acid composite membrane and its preparation method and application. Background technique [0002] Energy shortage has become a serious problem that all countries in the world have to face. The contradiction between power supply and demand caused by energy shortage has become one of the bottlenecks restricting the sustainable development of my country's economy and improving people's living standards. The utilization of renewable energy has become the basic national policy of my country's energy development. However, the renewable energy power generation process has obvious discontinuity and instability, and is easily affected by factors such as power generation time, day and night, and season. Therefore, equipped with efficient large-scale power storage devices is an important means to solve the unsteady charac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M2/14H01M2/16H01M8/18H01M50/403H01M50/411
CPCH01M8/188H01M50/403H01M50/409Y02E60/50Y02E60/10
Inventor 刘素琴李劲超魏达刘祖社刘杰
Owner 湖南德沃普电气股份有限公司
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