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ZIF@CNT modified polymer hybrid proton exchange membrane and preparation method thereof

A proton exchange membrane and polymer technology, applied in the field of polymer hybrid proton exchange membrane and its preparation, can solve the problems of no significant increase in proton conductivity, low absolute value, poor mechanical strength, etc., and achieve a good industrial production basis, The effect of low production cost and easy mass production

Active Publication Date: 2017-05-31
FUDAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For example, "Materials Chemistry A" (Journal of Materials Chemistry A 2015 (3) 15838-15842 ) reported that a ZIF-8@GO modified proton exchange membrane was prepared by doping ZIF-8@GO in Nafion. At 120°C and 40% RH, the proton conductivity reaches 0.28 S / cm, but under high humidity conditions, the proton conductivity does not increase significantly
"ACS Applied Materials and Surfaces" (ACS Applied Materials and Interfaces 2016, 8(35), 23015–23021) reported that polyvinyl phosphate-modified hollow ZIF-8 was directly calendered into a film, which was heated at 140 °C under anhydrous conditions. The proton conductivity is 3.2 (±0.12)×10-3 S / cm, which is significantly improved compared with the pure polyvinyl phosphate membrane. However, as a proton exchange membrane mainly made of inorganic materials, its mechanical strength is poor. shorter lifespan
"Membrane Science" (Journal of Membrane Science 2016, 499, 156-163) reported that ZIF-8 was compounded into a PVA / PAMPS composite membrane matrix, and the membrane had a proton conductivity of 0.134 at 100% humidity and 80°C. S / cm, compared with pure PVA / PAMPS, the proton conductivity has been greatly improved, but the absolute value is low, far lower than some commonly used commercial proton exchange membranes

Method used

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  • ZIF@CNT modified polymer hybrid proton exchange membrane and preparation method thereof
  • ZIF@CNT modified polymer hybrid proton exchange membrane and preparation method thereof
  • ZIF@CNT modified polymer hybrid proton exchange membrane and preparation method thereof

Examples

Experimental program
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Embodiment 1

[0021] 1. Ultrasonic dispersion of 120mg CNT-COOH in 30 mL of methanol, then weighed 0.2971 g of zinc nitrate hexahydrate and 0.6568 g of 2-methylimidazole were dissolved in 15 mL of methanol, and then poured them into the above CNT-CCOH dispersion solution, and transferred to a 100 mL polytetrafluoroethylene liner, covered the lid and put it into the reaction kettle to seal it tightly, and then placed it in a constant temperature oven at 90 °C for 10 h, and the reaction product was separated by centrifugation. First, it was washed continuously with fresh methanol solvent, and the product was centrifuged and finally placed in an oven at 50 °C for 6 h to obtain ZIF@CNT composite particles.

[0022] 2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form a SPEEK solution, add 0.5 wt% ZIF@CNT to the above polymer solution, and sonicate for 3h To disperse evenly; carefully pour the dispersion into a mold and quickly place it in an oven at ...

Embodiment 2

[0025] 1. Ultrasonic dispersion of 120mg CNT-COOH in 30 mL of methanol, then weighed 0.2971 g of zinc nitrate hexahydrate and 0.6568 g of 2-methylimidazole were dissolved in 15 mL of methanol, and then poured them into the above CNT-CCOH dispersion solution, and transferred to a 100 mL polytetrafluoroethylene liner, covered the lid and put it into the reaction kettle to seal it tightly, and then placed it in a constant temperature oven at 90 °C for 10 h, and the reaction product was separated by centrifugation. First, it was washed continuously with fresh methanol solvent, and the product was centrifuged and finally placed in an oven at 50 °C for 6 h to obtain ZIF@CNT composite particles.

[0026]2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form a SPEEK solution, add 1 wt% ZIF@CNT to the above polymer solution, and sonicate for 3h To disperse evenly; carefully pour the dispersion into a mold and quickly place it in an oven at 60°...

Embodiment 3

[0028] 1. Ultrasonic dispersion of 120mg CNT-COOH in 30 mL of methanol, then weighed 0.2971 g of zinc nitrate hexahydrate and 0.6568 g of 2-methylimidazole were dissolved in 15 mL of methanol, and then poured them into the above CNT-CCOH dispersion solution, and transferred to a 100 mL polytetrafluoroethylene liner, covered the lid and put it into the reaction kettle to seal it tightly, and then placed it in a constant temperature oven at 90 °C for 10 h, and the reaction product was separated by centrifugation. First, it was washed continuously with fresh methanol solvent, and the product was centrifuged and finally placed in an oven at 50 °C for 6 h to obtain ZIF@CNT composite particles.

[0029] 2. Take 200 mg of SPEEK (sulfonation degree 62%), add 3mL N,N-dimethylformamide, dissolve to form a SPEEK solution, add 1.5wt% ZIF@CNT to the above polymer solution, and sonicate for 3h To disperse evenly; carefully pour the dispersion into a mold and quickly place it in an oven at 6...

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Abstract

The invention belongs to the technical field of membranes, and particularly discloses a zeolite imidazate skeleton coated carbon nanotube composite material modified polymer hybrid proton exchange membrane and a preparation method thereof. Composite particles (ZIF@CNT) of a zeolite imidazate skeleton (ZIF) fully-coated carbon nano tube (CNT) are firstly prepared and are uniformly dispersed in a polymer base body, the proton conduction rate of the prepared ZIF@CNT modified polymer hybrid proton exchange membrane, compared with a relatively pure polymer proton exchange membrane, is obviously improved, and is also higher than that of a CNT modified polymer hybrid proton exchange membrane. Besides, through strong mutual effect between imidazole and polymer in ZIF@CNT, the fuel obstructing capacity of the hybrid proton exchange membrane is further improved. Therefore, the ZIF@CNT modified polymer hybrid proton exchange membrane has higher selectivity. The method disclosed by the invention is simple in operation process, mild in operation condition, relatively low in production cost and easy for batch and large-scale production, and has a wide application prospect.

Description

technical field [0001] The invention belongs to the field of membrane technology, and in particular relates to a polymer hybrid proton exchange membrane modified by a zeolite imidazolate framework and a carbon nanotube composite (ZIF@CNT) and a preparation method thereof. Background technique [0002] Fuel cells (FC) have excellent properties such as high energy conversion rate, no pollution, wide range of fuel sources, and low noise, and have gradually become one of the most competitive alternative power sources for internal combustion engines. Direct methanol fuel cells (DMFCs), the sixth generation of FCs, have attracted extensive academic and industrial attention with the additional advantages of mild operating conditions, high energy density, long lifetime, and no need for fuel pretreatment devices. Proton exchange membrane (PEM) is one of the core components of DMFC, and optimizing its performance plays a vital role in the development of high-performance DMFC. On the ...

Claims

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Application Information

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IPC IPC(8): C08J5/22C08K9/10C08K7/24C08K3/04C08L61/16H01M8/0239H01M8/0243
CPCC08J5/2262C08J2361/16C08K3/04C08K7/24C08K9/10C08K2201/011C08L2203/16C08L2203/20H01M8/0239H01M8/0243C08L61/16Y02E60/50Y02P70/50
Inventor 孙华圳汤蓓蓓武培怡
Owner FUDAN UNIV
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