A kind of carbon nanotube doped basic anion exchange composite membrane and its preparation method and application

A basic anion, carbon nanotube technology, applied in anion exchange, ion exchange, chemical instruments and methods, etc., can solve the problems of complex preparation process, poor membrane stability, unfavorable environmental protection, etc., and achieves simple preparation method, film-forming property Good, easy-to-operate effect

Inactive Publication Date: 2016-01-20
DONGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In recent years, various new quaternary ammonium polymers have been reported, such as PES-C, PPESK, PEI, PVDF and FEP [J.Wang, J.Wang, S.Li, S.Zhang, J.Membr. Sci.368(2011)246;L.Li,Y.Wang,J.Membr.Sci.262(2005)1;J.Fang,P.K.Shen,J.Membr.Sci.285(2006)317;G.Wang , Y.Weng, D.Chu, D.Xie, R.Chen, J.Membr.Sci.326(2009) 4.], but the preparation of these quaternary ammonium base polymers often go through chloromethylation, quaternary There are three steps from amination to alkalization, the preparation process is complex, and the price is high, especially when it involves highly toxic or even strong carcinogenic chloromethyl methyl ether and trimethylamine reagents, which is not conducive to environmental protection [J.F.Zhou, M .Unlu, J.A.Vega, P.A.Kohl, J.PowerSources190(2009)285;Y.Wu,C.Wu,J.R.Varcoec,S.D.Poyntonc,T.Xu,Y.Fu,J.PowerSources,195(2010)3069;Y .Xiong, Q.L.Liu, Q.H.Zeng, J.PowerSources, 193(2009)541; G.Wang, Y.Weng, D.Chu, D.Xie, R.Chen, J.Membr.Sci, 326(2009)4 ]
At the same time, nucleophilic attack or Hoffman elimination reaction is prone to occur in high temperature and high concentration alkaline solution, resulting in poor membrane stability

Method used

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  • A kind of carbon nanotube doped basic anion exchange composite membrane and its preparation method and application
  • A kind of carbon nanotube doped basic anion exchange composite membrane and its preparation method and application
  • A kind of carbon nanotube doped basic anion exchange composite membrane and its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0029] Dissolve 30g of PVA powder in 300ml of deionized water, heat and stir at 90°C until a transparent and homogeneous solution is prepared to obtain a 10% PVA stock solution; prepare a uniform PDDA solution according to the mass ratio of PVA to PDDA = 1:0.5; press PVA and PDDA 1wt% of the total amount was stirred and ultrasonicated respectively to prepare uniform mixed solutions of unmodified multi-walled carbon nanotubes MWCNTs, hydroxyl-modified multi-walled carbon nanotubes MWCNTs-OH, and carboxyl-modified multi-walled carbon nanotubes MWCNTs-COOH; the above solutions Mix and stir for 24 hours to obtain a uniform mixed solution, cast the mixed solution into a plastic disc, and dry naturally to form a film. The film was peeled off and placed in an oven for heat treatment at 150°C for 1 hour, and then immersed in 10% (volume percent) glutaraldehyde (GA, 25wt.%) acetone (≥99.5wt.%) containing a small amount (2% mass percent) of HCl. %) solution and stirred for 1 h, the memb...

Embodiment 2

[0032]Dissolve 30g of PVA powder in 300ml of deionized water, heat and stir at 90°C until a transparent and homogeneous solution is prepared to obtain a 10% PVA stock solution; prepare a uniform PDDA solution according to the mass ratio of PVA to PDDA = 1:0.5; press PVA and PDDA 0wt.%, 0.5wt.%, 1wt.%, 2wt.%, 3wt.% of the total amount were stirred separately and ultrasonically prepared to prepare uniform mixed solutions with different hydroxyl-modified multi-walled carbon nanotubes MWCNTs-OH doping content; mix the above The solution was cast into a plastic disc and dried naturally to form a film. Peel off the film and place it in an oven for heat treatment at 150°C for 1 hour, then soak in 5% (volume percent) glutaraldehyde (GA, 25wt.%) acetone (≥99.5wt.%) containing a small amount of HCl (0.2%, mass percent) .%) solution and stirred for 1 h, the membrane was taken out, immersed in deionized water to fully wash, and then stored in deionized water to obtain a modified quaternar...

Embodiment 3

[0035] The prepared PVA / 50%PDDA / MWCNTs-OH - The power generation performance of composite membrane prepared membrane electrode (MEA) was carried out on GE / FC1-100 fuel cell activation system. Both cathode and anode use Johnson Matthey's commercial 40% Pt / C catalyst with a Pt loading of 0.5 mg / cm 2 . The hot pressing condition of membrane electrode MEA is 6MPa-60℃-6min, and the effective active area of ​​membrane electrode MEA is 4cm 2 . The anode fuel is hydrogen with a flow rate of 100mL / min; the cathode is oxygen with a flow rate of 70mL / min. Power generation tests were performed at room temperature and 40°C respectively, and the results are as follows image 3 shown.

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Abstract

The invention relates to a carbon-nanotube-doped type basic anion exchange composite membrane, and a preparation method and application thereof. The composite membrane comprises: oxygen group-containing water-soluble polyvinyl alcohol PVA and a quaternary ammonium group-containing water-soluble polymer with a mass ratio of 1:0.5-1, and carbon nanotube accounting for 0.5-3 wt% of the above two components. The preparation method comprises: dissolving oxygen group-containing water-soluble polyvinyl alcohol in deionized water, heating to 90 DEG C and stirring into a transparent homogeneous solution; respectively dissolving the quaternary ammonium group-containing water-soluble polymer and carbon nanotube in deionized water, mixing the above three solutions to obtain a homogeneous solution, drying to form a membrane and further to obtain a polymer membrane; performing crosslinking processing on the polymer membrane, and finally performing ion exchange to obtain the composite membrane. The composite membrane is applicable to fuel cells, metal-air cells, chlor-alkali industry and wastewater processing. The composite membrane provided by the invention has relatively high hydroxide ion conductivity and excellent stability and endurance, is simple in production, good in membrane forming ability, low in cost, green and environment friendly.

Description

technical field [0001] The invention belongs to the field of ion-exchange composite membrane and its preparation and application, in particular to a carbon nanotube-doped alkaline anion-exchange composite membrane and its preparation method and application. Background technique [0002] Polymer Electrolyte Membrane Fuel Cells (PEMFCs) have become a research hotspot because of their advantages of fast start-up and fast response to load changes. Among them, the ion exchange membrane is an important part of PEMFCs, and its conductivity and stability have great influence on the power generation performance of fuel cells. It plays a vital role. There are many kinds of ion exchange membranes for PEMFCs, which can be divided into proton exchange membranes (PEMs) and alkaline anion exchange membranes (AAEMs) according to the different conduction ions, such as commercial proton exchange membranes produced by DuPont in the United States , are widely used in proton exchange membrane ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J41/14C08J5/22H01M8/10H01M8/02
CPCY02E60/50Y02P70/50
Inventor 乔锦丽张璟宋菲菲高颖
Owner DONGHUA UNIV
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