CN111533937A - Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof - Google Patents

Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof Download PDF

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CN111533937A
CN111533937A CN202010486189.5A CN202010486189A CN111533937A CN 111533937 A CN111533937 A CN 111533937A CN 202010486189 A CN202010486189 A CN 202010486189A CN 111533937 A CN111533937 A CN 111533937A
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graphene oxide
modified graphene
acid
exchange membrane
proton exchange
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李发勇
陈骏佳
高旭华
谢东
李圆
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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Abstract

The invention discloses a modified graphene oxide/Nafion composite proton exchange membrane and a preparation method and application thereof.A ATRP initiator is introduced on the surface of graphene oxide, and then a monomer containing an acidic group and a basic group is graft polymerized on the surface of the graphene oxide through ATRP reaction in sequence to obtain acid-base block copolymer modified graphene oxide; uniformly mixing the dispersion liquid of the acid-base block copolymer modified graphene oxide with a Nafion solution, and preparing the modified graphene oxide/Nafion composite proton exchange membrane by a solution casting method. According to the invention, a novel proton transfer site formed by an acid-base group at a Nafion-graphene oxide interface is utilized to construct a continuous proton transfer channel, so that the proton conductivity of the proton exchange membrane in a high-temperature and low-humidity environment can be improved, and the graphene oxide with a two-dimensional nano layered structure can block the diffusion of methanol molecules and reduce the methanol permeability of the proton exchange membrane.

Description

Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof
Technical Field
The invention relates to a fuel cell proton exchange membrane and a preparation method thereof, in particular to a modified graphene oxide/Nafion composite proton exchange membrane and a preparation method and application thereof.
Background
Along with increasingly outstanding energy and environmental problems, Proton Exchange Membrane Fuel Cells (PEMFC) become a hotspot of new energy research due to the advantages of high efficiency, green and environmental protection, and are an important component for realizing sustainable development, energy conservation, emission reduction and high-efficiency utilization of resources. The Proton Exchange Membrane (PEM) is the core component of the PEMFC, and directly determines the energy conversion efficiency and the service life of the PEMFC, wherein the proton conductivity and the methanol barrier performance are two key performance indexes of the proton exchange membrane. At present, the research and application is mostly carried out on a perfluorosulfonic acid membrane represented by Nafion, but the Nafion membrane has two key scientific problems in practical application: firstly, the water loss of the Nafion membrane is serious under the conditions of high temperature and low humidity, and the proton conductivity is obviously reduced because an ion cluster network proton transfer channel formed by sulfonic acid groups and water molecules through dynamic hydrogen bonds collapses; and secondly, when the Nafion membrane is used in a Direct Methanol Fuel Cell (DMFC), fuel methanol permeates seriously, methanol molecules easily pass through an ion cluster network along with water molecules and penetrate to a cathode, so that not only is fuel wasted, but also the normal reaction of the cathode is interfered, and the efficiency of the DMFC is obviously reduced. In addition, methanol molecules follow a dissolution-diffusion mechanism in the membrane, the dissolution is mainly determined by the structural characteristics of the membrane surface, the diffusion is determined by the internal microstructure of the membrane, and the proton conduction generally adopts a hopping mechanism and a carrying mechanism, which require proton transfer channels, proper proton carriers and water content in the membrane. Therefore, the regulation and the optimization of the microstructure of the proton exchange membrane are the key points for realizing the proton conduction and the alcohol resistance enhancement of the Nafion membrane, and have important significance for developing the PEM with high proton conductivity, low fuel permeability and high stability.
Graphene Oxide (GO) is an ultrathin two-dimensional material, and has good dispersibility in water but cannot be well dispersed in a non-polar solvent due to oxygen-containing functional groups on the surface of the graphene oxide. Covalent modification of GO can improve its dispersibility in a variety of solvents while also enhancing its compatibility in the polymer matrix. The block polymer can form a multifunctional nano structure through self-assembly, which attracts wide attention, so that different monomers can be initiated to graft the block copolymer on the GO surface through atom transfer radical polymerization. The Nafion proton exchange membrane is an acidic polymer, and on one hand, acidic functional groups (such as-SO) can be firstly introduced on the surface of GO3H) The polymer can improve the compatibility of GO and a Nafion matrix, and can increase the content of acidic functional groups in the membrane to promote proton conductivity, on the other hand, an alkali group (imidazole) -containing polymer is introduced, and acid-base block copolymer grafted graphene oxide (FGO) is introduced into the Nafion matrix, the FGO and Nafion can form an acid-base synergistic effect to construct a new efficient proton transfer channel, the two-dimensional structure of the graphene oxide can effectively regulate and control the channel size, the diffusion process of methanol molecules is blocked, and the proton conductivity and the alcohol blocking performance of the Nafion membrane under the conditions of high temperature and low humidity can be effectively improved.
In Journal of Membrane Science,531(2017),47-58, "Acid-base branched graphene oxide to enhance the proton conductivity of the composite Membrane" Acid-base branched graphene oxide to polymer electrolyte Membrane "is grafted with Acid (phosphate group) base (imidazole group) block copolymer on the surface of graphene oxide by surface atom transfer radical polymerization, and then the Acid-base branched graphene oxide is compounded with sulfonated polyether ether ketone and chitosan to improve the proton conductivity of the composite Membrane.
In conclusion, the acid-base block polymer modified graphene oxide has been applied to the preparation of composite proton exchange membranes, but it has not been found that monomers containing acidic groups (sulfonic acid) and basic groups (imidazole) are sequentially graft-polymerized onto the surface of graphene oxide through an ATRP reaction, and the acid-base block polymer modified graphene oxide/Nafion composite proton exchange membrane is prepared by compounding with Nafion, so that the proton conductivity and alcohol resistance of the Nafion membrane are enhanced, and the common problem that the proton conductivity and methanol permeability of the Nafion membrane are mutually restricted and cannot be improved simultaneously is solved.
Disclosure of Invention
The invention provides a modified graphene oxide/Nafion composite proton exchange membrane and a preparation method and application thereof to solve the defects.
The purpose of the invention is realized by the following technical scheme: a modified graphene oxide/Nafion composite proton exchange membrane is prepared by the following preparation method, wherein the preparation method comprises the following steps:
(1) introducing an ATRP initiator on the surface of graphene oxide to obtain GO-Br;
(2) sequentially carrying out graft polymerization on monomers containing acidic groups and basic groups on the GO-Br surface obtained in the step (1) through ATRP reaction to obtain acid-base block copolymer modified graphene oxide;
(3) uniformly mixing the acid-base block copolymer modified graphene oxide dispersion liquid with a Nafion solution, and preparing the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane by a solution casting method.
The method for introducing the ATRP initiator into the surface of the graphene oxide in the step (1) comprises the following steps: ultrasonically dispersing graphene oxide into an absolute ethyl alcohol/N-Dimethylformamide (DMF) mixed solvent, adding ammonia water, stirring for 2 hours at 40 ℃, dropwise adding an ethanol solution of (3-aminopropyl) triethoxysilane (APTES) for reaction to prepare aminated modified graphene oxide (GO-NH)2) Then GO-NH2Ultrasonically dispersing into tetrahydrofuran, using triethylamine as a catalyst, carrying out amide reaction with α -bromine isobutyryl bromide at 0 ℃ in a nitrogen atmosphere, and then carrying out graphite oxideIntroducing ATRP initiator to the alkene to obtain GO-Br.
The method for preparing the acid-base block copolymer modified graphene oxide in the step (2) comprises the following steps: ultrasonically dispersing the GO-Br obtained in the step (1) into a deionized water/alcohol-added mixed solvent, adding a monomer containing an acidic group, reacting for 48 hours under the action of a catalyst and a nitrogen atmosphere to obtain a polymer modified graphene oxide containing the acidic group, dispersing the polymer modified graphene oxide into a water/ethanol solution, adding a monomer containing an alkaline group, and reacting for 48 hours under the action of a catalyst and a nitrogen atmosphere to obtain an acid-base block copolymer modified graphene oxide.
Further, the acid group-containing monomer used in the step (2) is 3-sulfopropyl methacrylate potassium Salt (SPMA), and the basic group-containing monomer used is 1-Vinyl Imidazole (VI); the catalyst used was 2,2' -bipyridine/cuprous bromide.
The acid-base block copolymer modified graphene oxide prepared in the step (2) has the following structure:
Figure BDA0002519159640000031
wherein R is
Figure BDA0002519159640000032
The method for preparing the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane in the step (3) comprises the following steps: ultrasonically dispersing the acid-base block copolymer modified graphene oxide into a DMF (dimethyl formamide) solution, mixing the acid-base block copolymer modified graphene oxide with the DMF solution of Nafion, obtaining a uniform membrane casting solution under the alternate action of ultrasound and stirring, casting the membrane into a membrane, performing vacuum drying, and finally sequentially treating with hydrogen peroxide, deionized water and a sulfuric acid solution to obtain the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane.
In the step (3), the mass ratio of Nafion to acid-base block copolymer modified graphene oxide is 100: 0.5-2.
The acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane is used for preparing a methanol fuel cell.
The invention has the following beneficial effects:
1. according to the invention, an acid-base block copolymer is grafted on the surface of graphene oxide through atom transfer radical polymerization, and is compounded with Nafion to prepare an acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane, a continuous proton transfer channel is constructed by utilizing acid-base groups on the surface of graphene oxide and novel proton transfer sites formed by acid-base groups of Nafion at the interface of Nafion-graphene oxide, and the proton conductivity of the Nafion proton exchange membrane is efficiently enhanced under the conditions of high temperature and low humidity.
2. According to the invention, the free volume characteristic of a polymer is regulated and controlled through the interaction of a Nafion-graphene oxide interface, the channel size can be effectively regulated and controlled by utilizing a two-dimensional layered structure of graphene oxide, the diffusion process of methanol molecules is blocked, and the alcohol blocking performance of a Nafion proton exchange membrane is enhanced.
3. The acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane prepared by the invention can solve the common key scientific problem that the proton conductivity and the methanol permeability of the Nafion proton exchange membrane are restricted and cannot be improved simultaneously, so that the Nafion membrane has important significance in the commercial application and popularization of proton exchange membrane fuel cells.
Drawings
Fig. 1 is an FTIR spectrum of graphene oxide (a), aminated modified graphene oxide (b), ATRP initiator grafted graphene oxide (c), acid group-containing polymer grafted graphene oxide (d), and acid-base block copolymer modified graphene oxide (e) prepared according to the present invention.
Fig. 2 is an SEM image of a pure Nafion membrane (a) and an acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane (b) prepared by the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1
0.5g of Graphene Oxide (GO) prepared by a Hummers method is dispersed to 200mL of ethanol and N, N-dimethyl formyl in 30 minutes by ultrasonicAdding 40mL of ammonia water into an amine (DMF) mixed solvent (volume ratio is 1:1), stirring for 2 hours at 40 ℃, dissolving 2.2mL of (3-aminopropyl) triethoxysilane (APTES) into 100mL of ethanol solution, dropwise adding into the GO dispersion liquid, continuously stirring and reacting overnight at 40 ℃ after dropwise adding is finished, cooling to room temperature, centrifuging, washing with absolute ethyl alcohol and acetone in sequence, and drying in vacuum to obtain amino modified graphene oxide (GO-NH)2). 0.5g of GO-NH2Dispersing into 40mL of DMF by ultrasonic treatment for 30 minutes, adding 5mL of triethylamine, cooling to 0 ℃, slowly dropwise adding α -bromine isobutyryl bromide 1.74 mL/30 mL of DMF solution under the nitrogen atmosphere, reacting for 36 hours at room temperature after dropwise adding, filtering, washing with DMF, absolute ethyl alcohol and acetone in sequence, and drying in vacuum to obtain the ATRP initiator grafted graphene oxide (GO-Br).
Dispersing 0.1g of GO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2) by ultrasonic dispersion, adding 3.2g of 3-sulfopropyl methacrylic acid potassium Salt (SPMA), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, immersing the product into 1M sulfuric acid solution, standing overnight, washing with deionized water to be neutral, and performing freeze drying to obtain the acid group-containing polymer grafted graphene oxide. Ultrasonically dispersing the obtained acid group-containing polymer grafted graphene oxide into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.24g of 1-Vinyl Imidazole (VI), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the acid-base block copolymer modified graphene oxide.
Dispersing acid-base block copolymer modified graphene oxide 2.5mg into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic treatment for 4h, dissolving 0.5g of Nafion into 8mL of DMF, mixing the two solutions, performing ultrasonic treatment for 30 min and stirring for 30 min, circulating for four times to obtain a uniform casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 h, heating to 120 ℃ and drying for 12 h, and finally performing treatment sequentially by hydrogen peroxide (3%), deionized water and sulfuric acid solution (1M) at 80 ℃ to obtain 0.5 wt% acid-base embedded solutionThe segmented copolymer modified graphene oxide/Nafion composite proton exchange membrane. The water absorption rate of the proton exchange membrane at room temperature is 30.7 percent; the proton conductivity at 80 ℃ and a relative humidity of 40% is 0.011S cm-1。
Example 2
Dispersing 0.5g of Graphene Oxide (GO) prepared by a Hummers method into 200mL of ethanol and N, N-Dimethylformamide (DMF) mixed solvent (volume ratio is 1:1) after ultrasonic treatment for 30 minutes, adding 40mL of ammonia water, stirring at 40 ℃ for 2 hours, dissolving 2.2mL of (3-aminopropyl) triethoxysilane (APTES) into 100mL of ethanol solution, dropwise adding into the GO dispersion liquid, continuously stirring at 40 ℃ after dropwise adding is finished, reacting overnight, cooling to room temperature, centrifuging, washing with absolute ethanol and acetone in sequence, and vacuum drying to obtain amino modified graphene oxide (GO-NH)2). 0.5g of GO-NH2Dispersing into 40mL of DMF by ultrasonic treatment for 30 minutes, adding 5mL of triethylamine, cooling to 0 ℃, slowly dropwise adding α -bromine isobutyryl bromide 1.74 mL/30 mL of DMF solution under the nitrogen atmosphere, reacting for 36 hours at room temperature after dropwise adding, filtering, washing with DMF, absolute ethyl alcohol and acetone in sequence, and drying in vacuum to obtain the ATRP initiator grafted graphene oxide (GO-Br).
Dispersing 0.1g of GO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2) by ultrasonic dispersion, adding 3.2g of 3-sulfopropyl methacrylic acid potassium Salt (SPMA), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, immersing the product into 1M sulfuric acid solution, standing overnight, washing with deionized water to be neutral, and performing freeze drying to obtain the acid group-containing polymer grafted graphene oxide. Ultrasonically dispersing the obtained acid group-containing polymer grafted graphene oxide into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.24g of 1-Vinyl Imidazole (VI), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the acid-base block copolymer modified graphene oxide.
Modifying graphene oxide with acid-base block copolymerDispersing 5mg of ultrasonic wave into 2mL of N, N-Dimethylformamide (DMF) for 4h, dissolving 0.5g of Nafion into 8mL of DMF, mixing the two solutions, performing ultrasonic wave for 30 min and stirring for 30 min, circulating for four times to obtain a uniform membrane casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 h, heating to 120 ℃, drying for 12 h, and finally sequentially performing treatment on hydrogen peroxide (3%), deionized water and sulfuric acid solution (1M) at 80 ℃ to obtain the 1 wt% acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane. The water absorption of the proton exchange membrane at room temperature is 34.5 percent; proton conductivity at 80 ℃ and 40% relative humidity of 0.029S cm-1。
Example 3
Dispersing 0.5g of Graphene Oxide (GO) prepared by a Hummers method into 200mL of ethanol and N, N-Dimethylformamide (DMF) mixed solvent (volume ratio is 1:1) after ultrasonic treatment for 30 minutes, adding 40mL of ammonia water, stirring at 40 ℃ for 2 hours, dissolving 2.2mL of (3-aminopropyl) triethoxysilane (APTES) into 100mL of ethanol solution, dropwise adding into the GO dispersion liquid, continuously stirring at 40 ℃ after dropwise adding is finished, reacting overnight, cooling to room temperature, centrifuging, washing with absolute ethanol and acetone in sequence, and vacuum drying to obtain amino modified graphene oxide (GO-NH)2). 0.5g of GO-NH2Dispersing into 40mL of DMF by ultrasonic treatment for 30 minutes, adding 5mL of triethylamine, cooling to 0 ℃, slowly dropwise adding α -bromine isobutyryl bromide 1.74 mL/30 mL of DMF solution under the nitrogen atmosphere, reacting for 36 hours at room temperature after dropwise adding, filtering, washing with DMF, absolute ethyl alcohol and acetone in sequence, and drying in vacuum to obtain the ATRP initiator grafted graphene oxide (GO-Br).
Dispersing 0.1g of GO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2) by ultrasonic dispersion, adding 3.2g of 3-sulfopropyl methacrylic acid potassium Salt (SPMA), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, immersing the product into 1M sulfuric acid solution, standing overnight, washing with deionized water to be neutral, and performing freeze drying to obtain the acid group-containing polymer grafted graphene oxide. Ultrasonically dispersing the obtained acid group-containing polymer grafted graphene oxide into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.24g of 1-Vinyl Imidazole (VI), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the acid-base block copolymer modified graphene oxide.
Dispersing 7.5mg of acid-base block copolymer modified graphene oxide into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic treatment for 4h, dissolving 0.5g of Nafion into 8mL of DMF, mixing the two solutions, performing ultrasonic treatment for 30 min and stirring for 30 min, circulating for four times to obtain a uniform membrane casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 h, heating to 120 ℃ and drying for 12 h, and finally sequentially performing treatment on hydrogen peroxide (3%), deionized water and sulfuric acid solution (1M) at 80 ℃ to obtain the 1.5 wt% acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane. The water absorption of the proton exchange membrane at room temperature is 34.9%; proton conductivity at 80 ℃ and 40% relative humidity of 0.032S cm-1。
Example 4
Dispersing 0.5g of Graphene Oxide (GO) prepared by a Hummers method into 200mL of ethanol and N, N-Dimethylformamide (DMF) mixed solvent (volume ratio is 1:1) after ultrasonic treatment for 30 minutes, adding 40mL of ammonia water, stirring at 40 ℃ for 2 hours, dissolving 2.2mL of (3-aminopropyl) triethoxysilane (APTES) into 100mL of ethanol solution, dropwise adding into the GO dispersion liquid, continuously stirring at 40 ℃ after dropwise adding is finished, reacting overnight, cooling to room temperature, centrifuging, washing with absolute ethanol and acetone in sequence, and vacuum drying to obtain amino modified graphene oxide (GO-NH)2). 0.5g of GO-NH2Dispersing into 40mL of DMF by ultrasonic treatment for 30 minutes, adding 5mL of triethylamine, cooling to 0 ℃, slowly dropwise adding α -bromine isobutyryl bromide 1.74 mL/30 mL of DMF solution under the nitrogen atmosphere, reacting for 36 hours at room temperature after dropwise adding, filtering, washing with DMF, absolute ethyl alcohol and acetone in sequence, and drying in vacuum to obtain the ATRP initiator grafted graphene oxide (GO-Br).
Dispersing 0.1g of GO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2) by ultrasonic dispersion, adding 3.2g of 3-sulfopropyl methacrylic acid potassium Salt (SPMA), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, immersing the product into 1M sulfuric acid solution, standing overnight, washing with deionized water to be neutral, and performing freeze drying to obtain the acid group-containing polymer grafted graphene oxide. Ultrasonically dispersing the obtained acid group-containing polymer grafted graphene oxide into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.24g of 1-Vinyl Imidazole (VI), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide under the nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the acid-base block copolymer modified graphene oxide.
Dispersing 10mg of acid-base block copolymer modified graphene oxide into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic treatment for 4h, dissolving 0.5g of Nafion into 8mL of DMF, mixing the two solutions, performing ultrasonic treatment for 30 min and stirring for 30 min, circulating for four times to obtain a uniform casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 h, heating to 120 ℃ and drying for 12 h, and finally sequentially performing treatment at 80 ℃ by using hydrogen peroxide (3%), deionized water and sulfuric acid solution (1M) to obtain the 2 wt% acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane. The water absorption of the proton exchange membrane at room temperature is 34.8 percent; proton conductivity at 80 ℃ and 40% relative humidity was 0.033S cm-1。
Comparative example
And (2) casting a Nafion solution to form a membrane, drying the membrane for 12 hours in vacuum at 80 ℃, heating the membrane to 120 ℃, drying the membrane for 12 hours, and finally treating the membrane at 80 ℃ by hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) in sequence to obtain the pure Nafion proton exchange membrane. The water absorption rate of the proton exchange membrane at room temperature is 24.5 percent; proton conductivity at 80 ℃ and 40% relative humidity of 0.003S cm-1。
As shown in fig. 1, FTIR spectra of Graphene oxide (a), aminated modified Graphene oxide (b), hydroxyl-modified ATRP initiator graft-modified Graphene (Graphene-Br) (c), acid group-containing polymer graft Graphene oxide (d), and acid-base block copolymer modified Graphene oxide (e) obtained in the steps of the preparation method of the present invention.
FIG. 2a is an SEM image of a pure Nafion membrane of a comparative example; fig. 2b is an SEM image of the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane prepared by the present invention.

Claims (10)

1. A preparation method of a modified graphene oxide/Nafion composite proton exchange membrane is characterized by comprising the following steps:
(1) introducing an ATRP initiator on the surface of graphene oxide to obtain GO-Br;
(2) sequentially carrying out graft polymerization on monomers containing acidic groups and basic groups on the surface of GO-Br through ATRP reaction to obtain acid-base block copolymer modified graphene oxide;
(3) uniformly mixing the dispersion liquid of the acid-base block copolymer modified graphene oxide with a Nafion solution, and preparing the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane by a solution casting method.
2. The preparation method of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 1, wherein the method for introducing the ATRP initiator on the surface of the graphene oxide in the step (1) comprises the following steps: ultrasonically dispersing graphene oxide into an absolute ethyl alcohol/N-dimethylformamide mixed solvent, adding ammonia water, stirring for 2 hours at 40 ℃, dropwise adding an ethanol solution of (3-aminopropyl) triethoxysilane for reaction to prepare aminated modified graphene oxide, then ultrasonically dispersing the aminated modified graphene oxide into tetrahydrofuran, taking triethylamine as a catalyst, carrying out an amide reaction with alpha-bromoisobutyryl bromide at 0 ℃ in a nitrogen atmosphere, and introducing an ATRP initiator into the graphene oxide to obtain GO-Br.
3. The preparation method of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 1, wherein the method for preparing the acid-base block copolymer modified graphene oxide in the step (2) comprises the following steps: ultrasonically dispersing the GO-Br obtained in the step (1) into a deionized water/alcohol-added mixed solvent, adding a monomer containing an acidic group, reacting for 48 hours under the action of a catalyst and a nitrogen atmosphere to obtain a polymer modified graphene oxide containing the acidic group, dispersing the polymer modified graphene oxide into a water/ethanol solution, adding a monomer containing an alkaline group, and reacting for 48 hours under the action of a catalyst and a nitrogen atmosphere to obtain an acid-base block copolymer modified graphene oxide.
4. The method for preparing the modified graphene oxide/Nafion composite proton exchange membrane according to claim 1 or 3, wherein the acidic group-containing monomer in the step (2) is 3-sulfopropyl methacrylate potassium salt, and the basic group-containing monomer is 1-vinylimidazole.
5. The preparation method of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 3, wherein the catalyst in the step (2) is 2,2' -bipyridine/cuprous bromide.
6. The preparation method of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 1 or 3, wherein the acid-base block copolymer modified graphene oxide prepared in the step (2) has the following structure:
Figure FDA0002519159630000021
wherein R is
Figure FDA0002519159630000022
7. The preparation method of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 1, wherein the preparation method of the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane in the step (3) comprises the following steps: ultrasonically dispersing the acid-base block copolymer modified graphene oxide into a DMF (dimethyl formamide) solution, mixing the acid-base block copolymer modified graphene oxide with the DMF solution of Nafion, obtaining a uniform membrane casting solution under the alternate action of ultrasound and stirring, casting the membrane into a membrane, performing vacuum drying, and finally sequentially treating with hydrogen peroxide, deionized water and a sulfuric acid solution to obtain the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane.
8. The preparation method of the acid-base block copolymer modified graphene oxide/Nafion composite proton exchange membrane according to claim 7, wherein in the step (3), the mass ratio of Nafion to the acid-base block copolymer modified graphene oxide is 100: 0.5-2.
9. A modified graphene oxide/Nafion composite proton exchange membrane, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The use of the modified graphene oxide/Nafion composite proton exchange membrane according to claim 9, wherein the membrane is used for preparing a methanol fuel cell.
CN202010486189.5A 2020-06-01 2020-06-01 Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof Pending CN111533937A (en)

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CN114843568A (en) * 2021-02-01 2022-08-02 恒大新能源技术(深圳)有限公司 Composite proton exchange membrane, preparation method thereof and fuel cell
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