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A kind of preparation method of metal organic framework modified nanofiber proton exchange membrane

A metal-organic framework and proton exchange membrane technology, applied in fiber treatment, nanotechnology, nanotechnology, etc., can solve problems such as reducing effective proton conduction sites, limiting the overall performance of proton exchange membranes, and affecting the stability of fiber matrix, etc., to achieve Reduce the permeability of methanol, the preparation method is simple and easy, and the effect of good proton conductivity

Active Publication Date: 2022-07-15
TIANJIN POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the complexity of chemical bonding, the limitation of the loading capacity of MOFs, and the fact that MOFs are mostly encapsulated in fibers, it affects the stability of the fiber matrix and reduces the effective proton conduction sites, thereby limiting the overall performance of the proton exchange membrane.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Sulfonated polyethersulfone (SPES) was added to N,N-dimethylformamide (DMF) and stirred to prepare an electrospinning solution with a concentration of 30 wt%; SPES was mixed with proton conductor UIO-66-NH 2 Blended into DMF with a concentration of 15 wt% SPES, UIO-66-NH 2 It accounts for 10wt% of SPES, and stirs evenly to obtain electrostatic spray solution. The two solutions were transferred to the syringe respectively, and synchronous electrospinning / electrospraying was performed, wherein the electrospinning parameters were set as: voltage 25kV, feeding speed 0.8mL / h, receiving distance 20cm; electrostatic spray parameters were: voltage 30kV, The feed rate was 0.6 mL / h, and the receiving distance was 15 cm. The collected composite membrane was heated for 15 min in a DMF steam atmosphere, and then hot-pressed at 110 °C and 10 MPa for 5 min to finally obtain UIO-66-NH 2 Modified SPES nanofiber proton exchange membrane.

Embodiment 2

[0019] Sulfonated polyaryletherketone (SPPEK) was added to N,N-dimethylacetamide (DMAc) and stirred to prepare an electrospinning solution with a concentration of 35 wt%; SPPEK was mixed with proton conductor MIL-101-NH 2 -SO 3 H was blended into DMAc with a concentration of 10 wt% SPPEK, UIO-66-NH 2 -SO 3 H accounted for 15 wt% of SPPEK, and the electrostatic spray solution was obtained by stirring uniformly. The two solutions were transferred to the syringe respectively, and synchronous electrospinning / electrospraying was carried out. The electrospinning parameters were set as: voltage 30kV, feeding speed 1.2mL / h, receiving distance 20cm; electrostatic spray parameters were: voltage 30kV, The feed rate was 0.8 mL / h, and the receiving distance was 18 cm. The collected composite membrane was heated for 10 min in a DMAc vapor atmosphere, and then hot-pressed for 8 min at 120 °C and 12 MPa to finally obtain UIO-66-NH 2 -SO 3 Modified SPPEK nanofiber proton exchange membrane...

Embodiment 3

[0021] First, the solvent of the perfluorosulfonic acid (Nafion) solution was evaporated to dryness by rotary evaporation, and then it was added to N,N-dimethylformamide (DMF) to prepare an electrospinning solution with a concentration of 25 wt%; Nafion was mixed with The proton conductor ZIF-8 was blended into DMF, wherein the Nafion solution was 12wt%, ZIF-8 accounted for 8wt% of Nafion, and the electrostatic spray solution was obtained by stirring uniformly. The two solutions were transferred into syringes, and synchronous electrospinning / electrospraying were performed. The electrospinning parameters were set as: voltage 20kV, feeding speed 0.6mL / h, receiving distance 18cm; electrostatic spray parameters were: voltage 28kV, The feed rate was 0.3 mL / h, and the receiving distance was 13 cm. The collected composite membrane was heated for 5 min in a DMF steam atmosphere, and then hot-pressed at 80 °C and 10 MPa for 5 min to finally obtain a ZIF-8 modified Nafion fiber proton e...

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PUM

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Abstract

The present invention provides a method for preparing a metal-organic framework-modified nanofiber proton exchange membrane. The method realizes the uniform distribution of metal-organic framework among proton-conducting polymer nanofibers through synchronous electrospinning / electrostatic spraying technology, and is processed by solvent steam and heat. After pressure treatment, the polymer nanofibers and the polymer layer coated on the surface of the metal-organic framework are melted and cross-linked to form a dense metal-organic framework modified nanofiber proton exchange membrane. In the present invention, the proton-conducting polymer nanofibers are cross-linked and interconnected to form a continuous proton transfer channel, and the metal-organic framework proton conductor is tightly anchored therein, providing a more sufficient and effective transfer site for the proton carrier, so that the composite membrane has excellent proton Conductivity. In addition, the presence of metal-organic frameworks between nanofibers hinders the passage of methanol to a certain extent, which greatly reduces the methanol permeability of the composite membranes. The preparation method is simple and easy to implement, has strong applicability, and is easier to realize large-scale production operations.

Description

technical field [0001] The invention belongs to the field of fuel cells, in particular to a preparation method of a metal-organic framework modified nanofiber proton exchange membrane. Background technique [0002] As one of the important components of proton exchange membrane fuel cell (PEMFC), proton exchange membrane directly affects the performance of fuel cell. Perfluorosulfonic acid (Nafion) membranes are the most widely used proton exchange membranes due to their stable proton conductivity. However, Nafion membrane has shortcomings such as high methanol permeability and poor mechanical stability during long-term operation, and the high cost of Nafion membrane hinders its commercial development. At present, research on new high-performance proton membrane materials mainly focuses on the development of new proton-conducting polymers with alternative chemical backbones and proton-conducting groups, such as sulfonated polyaryl ethers, polyimides, and polyphenylenes. , p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M8/1088H01M8/1046D04H3/147D04H3/033D01D5/00B82Y30/00
CPCH01M8/1088H01M8/1046D01D5/003D01D5/0092D04H3/033D04H3/147B82Y30/00Y02P70/50
Inventor 程博闻王利媛康卫民王航邓南平闫静鞠敬鸽
Owner TIANJIN POLYTECHNIC UNIV