CN113097550A - Nafion composite membrane for high-temperature low-humidity proton exchange membrane fuel cell and preparation and application thereof - Google Patents
Nafion composite membrane for high-temperature low-humidity proton exchange membrane fuel cell and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
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- 238000001291 vacuum drying Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
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- 238000010438 heat treatment Methods 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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Images
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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Abstract
The invention belongs to the field of proton exchange membranes of fuel cells, and discloses a Nafion composite membrane for a high-temperature low-humidity proton exchange membrane fuel cell, and preparation and application thereof. The preparation method of the composite membrane comprises the following steps: firstly, adopting diazo salt addition reaction and atom transfer radical polymerization technology to graft a copolymer containing azole groups and hydrophilic groups on the surface of graphene to prepare copolymer grafted graphene, and then compounding the copolymer grafted graphene with Nafion to obtain the composite membrane. The azole group on the surface of the copolymer and the sulfonic acid group in the Nafion matrix can form a high-efficiency continuous proton transfer channel at a Nafion-graphene interface, the hydrophilic group can improve the water retention performance of the Nafion membrane, and the graphene with a two-dimensional layered structure can block the diffusion of methanol molecules, so that the common key scientific problems of proton conductivity reduction and high methanol fuel permeation under the high-temperature and low-humidity conditions of the Nafion proton exchange membrane can be solved.
Description
Technical Field
The invention belongs to the field of proton exchange membranes of fuel cells, and particularly relates to a Nafion composite membrane for a high-temperature low-humidity proton exchange membrane fuel cell, and preparation and application thereof.
Background
The fuel cell has the outstanding characteristics of high efficiency, zero pollution, zero emission and the like as a novel power generation device, plays an increasingly important role in the energy field, promotes the energy to be low-carbonized and clean, and is the field which solves the energy problem most effectively and has the most development prospect. Among them, Proton Exchange Membrane Fuel Cells (PEMFCs) are considered to be the most promising next-generation clean energy due to their advantages such as high specific power, fast start-up, and simple structure, and are the hot spots for new energy research. 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 thereof. 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 Nafion membrane has larger dependence on water content, the water loss 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. Therefore, the development of a PEM with high proton conductivity and low methanol fuel permeability is of great significance for the scale-up application of PEMFCs.
The method has become a new way for constructing a high-efficiency transfer channel by grafting a polymer containing proton conducting groups and Nafion on the surface of an inorganic material, but the research on strengthening the proton conducting and alcohol blocking performance of a Nafion membrane by grafting the polymer containing proton conducting groups on the surface by taking graphene as a filling material has not been reported yet. The research on the preparation of the Nafion composite membrane by introducing azole groups and hydrophilic groups on the surface of graphene through diazonium salt addition reaction and atom transfer radical polymerization reaction and compounding with Nafion is not carried out.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a Nafion composite membrane for a high-temperature low-humidity proton exchange membrane fuel cell.
The invention also aims to provide the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell prepared by the method.
The invention further aims to provide application of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell.
The purpose of the invention is realized by the following scheme:
a preparation method of a Nafion composite membrane for a high-temperature low-humidity proton exchange membrane fuel cell comprises the following steps:
(1) reducing graphene oxide to obtain graphene, and grafting an Atom Transfer Radical Polymerization (ATRP) initiator to the surface of the graphene through a diazonium salt addition reaction to obtain ATRP initiator graft modified graphene;
(2) carrying out graft polymerization on an azole group and a hydrophilic group on the surface of graphene through ATRP reaction to obtain copolymer grafted graphene containing the azole group and the hydrophilic group;
(3) uniformly mixing the dispersion liquid of the copolymer grafted graphene containing azole groups and hydrophilic groups with a Nafion solution, and preparing the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell by adopting a solution casting method.
The method for grafting an Atom Transfer Radical Polymerization (ATRP) initiator to the surface of graphene through a diazonium salt addition reaction described in step (1) is: dispersing the reduced graphene in water, and then adding 4-aminophenylethanol and isoamyl nitrite for reaction to obtain hydroxyl modified graphene; and then reacting the hydroxyl modified graphene with an Atom Transfer Radical Polymerization (ATRP) initiator under the action of a nitrogen atmosphere and a catalyst to obtain the ATRP initiator graft modified graphene.
In order to disperse the graphene in the water in the step (1), a dispersant, such as sodium dodecyl sulfate, may be further added thereto to improve the dispersibility of the graphene in the water.
The mass ratio of the graphene to the 4-aminophenylethanol to the isoamyl nitrite in the step (1) is 1: 4-8: 2-6;
the step (1) of adding 4-aminophenylethanol and isoamylnitrite for reaction refers to a step of reacting for 12-24 hours at 60-100 ℃, and the method further comprises a purification step after the reaction is finished, and specifically comprises the following steps: and cooling the obtained reaction liquid to room temperature, filtering, washing by sequentially adopting deionized water, absolute ethyl alcohol and acetone, and drying in vacuum to obtain the hydroxyl modified graphene (rGO-OH).
The Atom Transfer Radical Polymerization (ATRP) initiator in the step (1) is one of alpha-bromoisobutyryl bromide, 2-bromopropionyl bromide, 2-bromon-butyryl bromide and bromoacetyl bromide, and is preferably alpha-bromoisobutyryl bromide;
the mass ratio of the hydroxyl modified graphene to an Atom Transfer Radical Polymerization (ATRP) initiator in the step (1) is 1: 10-20;
the catalyst in the step (1) is triethylamine, and the dosage of the catalyst is a catalytic amount.
The reaction in the nitrogen atmosphere and under the action of the catalyst in the step (1) refers to a reaction at room temperature for 24-48 hours.
In the step (1), after the hydroxyl modified graphene and the ATRP initiator react in a nitrogen atmosphere and under the action of a catalyst, a purification step is also included, which specifically comprises the following steps: and filtering the obtained reaction solution, sequentially washing with deionized water, absolute ethyl alcohol and acetone, and drying in vacuum to obtain the purified ATRP initiator graft modified graphene.
The method for graft polymerization of an azole group and a hydrophilic group on the surface of graphene by ATRP reaction described in step (2) is as follows: mixing ATRP initiator graft modified graphene, monomer containing azole group and monomer containing hydrophilic group, and then adding catalyst in nitrogen atmosphere to react to obtain copolymer graft graphene containing azole group and hydrophilic group.
In the step (2), the monomer containing azole groups is 1-vinylimidazole or 2-methyl-1-vinylimidazole; the monomer containing the hydrophilic group is polyethylene glycol methyl ether methacrylate.
In the step (2), the dosage of the monomer containing azole group and the monomer containing hydrophilic group satisfies the following conditions: the molar ratio of the azole group to the hydrophilic group is 10: 1-1: 1; the mass ratio of the ATRP initiator grafted modified graphene to the monomer containing azole groups is 1: 10-20;
the catalyst in the step (2) is 2,2' -bipyridyl/cuprous bromide, and the dosage of the catalyst is a catalytic amount.
The reaction in the step (2) is carried out at room temperature for 24-48 h.
The copolymer grafted graphene containing azole groups and hydrophilic groups in the step (2) has the following structure:
wherein R is1is-H or-CH3。
The step (3) specifically comprises the following steps: dispersing copolymer grafted graphene containing azole groups and hydrophilic groups into a DMF solution, mixing the copolymer grafted graphene with the DMF solution of Nafion to obtain a uniform membrane casting solution, casting to form a membrane, drying in vacuum, and finally treating with hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1mol/L) in sequence to obtain the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell.
In the step (3), the mass ratio of the Nafion to the copolymer grafted graphene is 100: 0.5-2.
The treatment in the step (3) is soaking treatment at 80 ℃ for 1 h.
The Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell is prepared by the method.
The Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell is applied to the preparation of a methanol fuel cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, a copolymer containing an imidazole group and a hydrophilic polyethylene glycol group is introduced on the surface of graphene through a diazo addition reaction and ATRP, and is doped into a Nafion matrix, wherein the imidazole group has proton transfer capability at high temperature, and can form an acid-base pair with a sulfonic acid group of Nafion to be used as a jump site with a low energy barrier to quickly transfer protons, so that the proton conductivity of the Nafion composite membrane at high temperature is enhanced; the introduction of the hydrophilic polyethylene glycol group improves the water retention performance of the Nafion composite membrane of the membrane, optimizes the water environment of a proton transfer channel of the membrane, provides a proper physical microenvironment for proton transfer, and promotes the proton conductivity of the Nafion membrane under low humidity.
2. The copolymer grafted graphene containing imidazole groups and hydrophilic polyethylene glycol groups prepared by the method can improve the dispersibility of the graphene in a Nafion matrix, and the two-dimensional layered structure of the graphene can effectively regulate and control the channel size, prevent the diffusion of methanol molecules and strengthen the alcohol-blocking characteristic of the membrane.
Drawings
FIG. 1 is a proton transfer diagram of a Nafion composite membrane prepared by the invention.
Fig. 2 is an SEM image of the Nafion composite membrane prepared in example 2 of the present invention.
FIG. 3 shows the water absorption rates of Nafion composite membranes with different mass fractions of copolymer grafted graphene at 25 ℃ and 60 ℃.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reagents used in the examples are commercially available without specific reference.
Example 1
Dispersing 0.5g of Graphene Oxide (GO) into 250mL of deionized water by ultrasonic for 30 minutes, adding 10g of ascorbic acid, heating to 60 ℃, stirring for 4 hours, cooling to room temperature, filtering, washing with deionized water for three times, adding 0.5g of the obtained product graphene and sodium dodecyl sulfate into 250mL of deionized water, performing ultrasonic for 30 minutes, adding 2g of 4-aminophenylethanol and 1.5mL of isoamyl nitrite, reacting overnight at 80 ℃, finally cooling to room temperature, filtering, washing with deionized water, anhydrous ethanol and acetone in sequence, and performing vacuum drying to obtain hydroxyl modified graphene (rGO-OH). Adding 0.2g of rGO-OH into 40mL of tetrahydrofuran, adding 2mL of triethylamine, introducing nitrogen for 10 minutes, cooling to 0 ℃, slowly dropwise adding a solution of 1.2mL of alpha-bromoisobutyryl bromide/10 mL of tetrahydrofuran, continuing to react for 24 hours at room temperature after dropwise adding is finished, finally filtering, sequentially adopting deionization, absolute ethyl alcohol and acetone for washing, vacuum drying, and vacuum drying to obtain the ATRP initiator grafted modified graphene (rGO-Br).
Ultrasonically dispersing 0.1g of rGO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.2g of 1-vinyl imidazole and 0.8g of methoxypolyethylene glycol methacrylate (Mn-300), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide in a nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the copolymer grafted graphene (F-rGO) containing imidazolyl groups and hydrophilic groups.
Dispersing 2.5mg of copolymer grafted graphene containing imidazolyl group and hydrophilic group into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic wave for 4h, dissolving 0.5g of Nafion into 8mL of DMF, mixing the two solutions, and performing ultrasonic wave for 30 minutes and stirring for 3 minutesAnd circulating for four times to obtain a uniform membrane casting solution 0 minute, casting to form a membrane, vacuum drying at 80 ℃ for 12 hours, heating to 120 ℃, drying for 12 hours, and finally soaking in hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) at 80 ℃ for 1 hour to obtain the 0.5 wt% functionalized graphene/Nafion nano composite proton exchange membrane. The proton conductivity of the Nafion composite membrane is 5.7mS cm at 80 ℃ and 40 percent of relative humidity-1The methanol permeability is 5.2X 10-7cm2s-1。
Example 2
Dispersing 0.5g of Graphene Oxide (GO) into 250mL of deionized water by ultrasonic for 30 minutes, adding 10g of ascorbic acid, heating to 60 ℃, stirring for 4 hours, cooling to room temperature, filtering, washing with deionized water for three times, adding the obtained product and 0.5g of sodium dodecyl sulfate into 250mL of deionized water, performing ultrasonic for 30 minutes, adding 2g of 4-aminophenylethanol and 1.5mL of isoamyl nitrite, reacting overnight at 80 ℃, finally cooling to room temperature, filtering, washing with deionized water, anhydrous ethanol and acetone in sequence, and performing vacuum drying to obtain the hydroxyl modified graphene (rGO-OH). Adding 0.2g of rGO-OH into 40mL of tetrahydrofuran, adding 2mL of triethylamine, introducing nitrogen for 10 minutes, cooling to 0 ℃, slowly dropwise adding a solution of 1.2mL of alpha-bromoisobutyryl bromide/10 mL of tetrahydrofuran, continuing to react for 24 hours at room temperature after dropwise adding is finished, finally filtering, sequentially adopting deionization, absolute ethyl alcohol and acetone for washing, vacuum drying, and vacuum drying to obtain the ATRP initiator grafted modified graphene (rGO-Br).
Ultrasonically dispersing 0.1g of rGO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.2g of 1-vinyl imidazole and 0.8g of methoxypolyethylene glycol methacrylate (Mn-300), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide in a nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the copolymer grafted graphene (F-rGO) containing imidazolyl groups and hydrophilic groups.
Dispersing 5mg of copolymer grafted graphene containing imidazolyl group and hydrophilic group 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 minutes and stirring for 30 minutes, circulating for four times to obtain a uniform membrane casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 hours, heating to 120 ℃, drying for 12 hours, and finally performing soaking treatment for 1 hour at 80 ℃ by using hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) respectively to obtain the 1 wt% functionalized graphene/Nafion nano composite proton exchange membrane. The proton conductivity of the Nafion composite membrane is 7.0mS cm at 80 ℃ and 40% of relative humidity-1The methanol permeability is 2.6X 10-7cm2s-1。
Example 3
Dispersing 0.5g of Graphene Oxide (GO) into 250mL of deionized water by ultrasonic for 30 minutes, adding 10g of ascorbic acid, heating to 60 ℃, stirring for 4 hours, cooling to room temperature, filtering, washing with deionized water for three times, adding the obtained product and 0.5g of sodium dodecyl sulfate into 250mL of deionized water, performing ultrasonic for 30 minutes, adding 2g of 4-aminophenylethanol and 1.5mL of isoamyl nitrite, reacting overnight at 80 ℃, finally cooling to room temperature, filtering, washing with deionized water, anhydrous ethanol and acetone in sequence, and performing vacuum drying to obtain the hydroxyl modified graphene (rGO-OH). Adding 0.2g of rGO-OH into 40mL of tetrahydrofuran, adding 2mL of triethylamine, introducing nitrogen for 10 minutes, cooling to 0 ℃, slowly dropwise adding a solution of 1.2mL of alpha-bromoisobutyryl bromide/10 mL of tetrahydrofuran, continuing to react for 24 hours at room temperature after dropwise adding is finished, finally filtering, sequentially adopting deionization, absolute ethyl alcohol and acetone for washing, vacuum drying, and vacuum drying to obtain the ATRP initiator grafted modified graphene (rGO-Br).
Ultrasonically dispersing 0.1g of rGO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.2g of 1-vinyl imidazole and 0.8g of methoxypolyethylene glycol methacrylate (Mn-300), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide in a nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the copolymer grafted graphene (F-rGO) containing imidazolyl groups and hydrophilic groups.
7.5mg of copolymer grafted graphene containing imidazolyl group and hydrophilic group is dispersed into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic treatment for 4h, 0.5g of Nafion is dissolved into 8mL of DMF, and the solution is stirredAnd mixing the two solutions, performing ultrasonic treatment for 30 minutes and stirring for 30 minutes, circulating for four times to obtain a uniform membrane casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 hours, heating to 120 ℃, drying for 12 hours, and finally performing soaking treatment for 1 hour at 80 ℃ by using hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) respectively to obtain the 1.5 wt% functionalized graphene/Nafion nano composite proton exchange membrane. The proton conductivity of the Nafion composite membrane is 6.8mS cm at 80 ℃ and 40 percent of relative humidity-1The methanol permeability is 2.3X 10-7cm2s-1。
Example 4
Dispersing 0.5g of Graphene Oxide (GO) into 250mL of deionized water by ultrasonic for 30 minutes, adding 10g of ascorbic acid, heating to 60 ℃, stirring for 4 hours, cooling to room temperature, filtering, washing with deionized water for three times, adding the obtained product and 0.5g of sodium dodecyl sulfate into 250mL of deionized water, performing ultrasonic for 30 minutes, adding 2g of 4-aminophenylethanol and 1.5mL of isoamyl nitrite, reacting overnight at 80 ℃, finally cooling to room temperature, filtering, washing with deionized water, anhydrous ethanol and acetone in sequence, and performing vacuum drying to obtain the hydroxyl modified graphene (rGO-OH). Adding 0.2g of rGO-OH into 40mL of tetrahydrofuran, adding 2mL of triethylamine, introducing nitrogen for 10 minutes, cooling to 0 ℃, slowly dropwise adding a solution of 1.2mL of alpha-bromoisobutyryl bromide/10 mL of tetrahydrofuran, continuing to react for 24 hours at room temperature after dropwise adding is finished, finally filtering, sequentially adopting deionization, absolute ethyl alcohol and acetone for washing, vacuum drying, and vacuum drying to obtain the ATRP initiator grafted modified graphene (rGO-Br).
Ultrasonically dispersing 0.1g of rGO-Br into 20mL of methanol/deionized water mixed solvent (the mass ratio is 3:2), adding 1.2g of 1-vinyl imidazole and 0.8g of methoxypolyethylene glycol methacrylate (Mn-300), performing freeze-thaw degassing cycle for three times, adding 0.0625g of 2,2' -bipyridine and 0.0287g of cuprous bromide in a nitrogen atmosphere, reacting for 48 hours at room temperature, filtering, washing with deionized water for three times, and performing freeze drying to obtain the copolymer grafted graphene (F-rGO) containing imidazolyl groups and hydrophilic groups.
10mg of copolymer grafted graphene containing imidazolyl group and hydrophilic group is dispersed into 2mL of N, N-Dimethylformamide (DMF) by ultrasonic treatment for 4h, and 0.5g of Nafion is dissolvedAnd dissolving the solution into 8mL of DMF, mixing the two solutions, performing ultrasonic treatment for 30 minutes and stirring for 30 minutes, circulating for four times to obtain a uniform membrane casting solution, casting to form a membrane, performing vacuum drying at 80 ℃ for 12 hours, heating to 120 ℃, drying for 12 hours, and finally soaking for 1 hour at 80 ℃ by using hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) respectively to obtain the 2 wt% functionalized graphene/Nafion nano composite proton exchange membrane. The proton conductivity of the Nafion composite membrane is 6.4mS cm at 80 ℃ and 40 percent of relative humidity-1The methanol permeability is 1.8X 10-7cm2s-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 soaking the membrane for 1 hour at 80 ℃ in turn by using hydrogen peroxide (3%), deionized water and a sulfuric acid solution (1M) to obtain the pure Nafion proton exchange membrane. The Nafion membrane has a proton conductivity of 5.1mS cm at 80 ℃ and 40% relative humidity-1The methanol permeability is 10.1X 10-7cm2s-1。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a Nafion composite membrane for a high-temperature low-humidity proton exchange membrane fuel cell is characterized by comprising the following steps:
(1) reducing graphene oxide to obtain graphene, and grafting an atom transfer radical polymerization initiator to the surface of the graphene through a diazonium salt addition reaction to obtain ATRP initiator graft modified graphene;
(2) carrying out graft polymerization on an azole group and a hydrophilic group on the surface of graphene through ATRP reaction to obtain copolymer grafted graphene containing the azole group and the hydrophilic group;
(3) uniformly mixing the dispersion liquid of the copolymer grafted graphene containing azole groups and hydrophilic groups with a Nafion solution, and preparing the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell by adopting a solution casting method.
2. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 1, which is characterized in that:
the method for grafting the atom transfer radical polymerization initiator to the surface of the graphene through the diazonium salt addition reaction in the step (1) comprises the following steps: uniformly dispersing the reduced graphene in water, and then adding 4-aminophenylethanol and isoamylnitrite for reaction to obtain hydroxyl modified graphene; and then reacting the hydroxyl modified graphene with an atom transfer radical polymerization initiator under the action of a catalyst in a nitrogen atmosphere to obtain the ATRP initiator graft modified graphene.
3. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 2, characterized in that:
the mass ratio of the graphene to the 4-aminophenylethanol to the isoamyl nitrite in the step (1) is 1: 4-8: 2-6;
the step (1) of adding 4-aminophenylethanol and isoamylnitrite for reaction refers to reacting for 12-24 hours at the temperature of 60-100 ℃;
the atom transfer radical polymerization initiator in the step (1) is one of alpha-bromoisobutyryl bromide, 2-bromopropionyl bromide, 2-bromon-butyl bromide and bromoacetyl bromide;
the mass ratio of the hydroxyl modified graphene to the atom transfer radical polymerization initiator in the step (1) is 1: 10-20;
the catalyst in the step (1) is triethylamine;
the reaction in the nitrogen atmosphere and under the action of the catalyst in the step (1) refers to a reaction at room temperature for 24-48 hours.
4. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 1, which is characterized in that:
the method for graft polymerization of an azole group and a hydrophilic group on the surface of graphene by ATRP reaction described in step (2) is as follows: mixing ATRP initiator graft modified graphene, monomer containing azole group and monomer containing hydrophilic group, and then adding catalyst in nitrogen atmosphere to react to obtain copolymer graft graphene containing azole group and hydrophilic group.
5. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 4, characterized in that:
in the step (2), the monomer containing azole groups is 1-vinylimidazole or 2-methyl-1-vinylimidazole; the monomer containing the hydrophilic group is polyethylene glycol methyl ether methacrylate;
in the step (2), the dosage of the monomer containing azole group and the monomer containing hydrophilic group satisfies the following conditions: the molar ratio of the azole group to the hydrophilic group is 10: 1-1: 1; the mass ratio of the ATRP initiator grafted modified graphene to the monomer containing azole groups is 1: 10-20;
the catalyst in the step (2) is 2,2' -bipyridyl/cuprous bromide, and the dosage of the catalyst is a catalytic amount;
the reaction in the step (2) is carried out at room temperature for 24-48 h.
6. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 1, which is characterized in that:
the copolymer grafted graphene containing azole groups and hydrophilic groups in the step (2) has the following structure:
wherein R is1is-H or-CH3。
7. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 1, which is characterized in that:
the step (3) specifically comprises the following steps: dispersing copolymer grafted graphene containing azole groups and hydrophilic groups into a DMF solution, mixing the copolymer grafted graphene with the DMF solution of Nafion to obtain a uniform membrane casting solution, casting to form a membrane, drying in vacuum, and finally treating with hydrogen peroxide, deionized water and a sulfuric acid solution in sequence to obtain the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell.
8. The preparation method of the Nafion composite membrane for the high-temperature low-humidity proton exchange membrane fuel cell according to claim 1 or 7, characterized in that:
in the step (3), the mass ratio of the Nafion to the copolymer grafted graphene is 100: 0.5-2.
9. A Nafion composite membrane for a high temperature low humidity proton exchange membrane fuel cell prepared according to the method of any one of claims 1 to 8.
10. Use of a Nafion composite membrane for a high temperature low humidity proton exchange membrane fuel cell in accordance with claim 9 in the preparation of a methanol fuel cell.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935030A (en) * | 2010-08-31 | 2011-01-05 | 南京理工大学 | Functional graphene oxide for adjusting and controlling dispersibility of solvent by using organic chain segment as well as preparation method thereof |
| CN107968214A (en) * | 2017-11-09 | 2018-04-27 | 大连理工大学 | A kind of hydrophilic long pendant basic anion-exchange membrane and preparation method thereof |
| CN108598534A (en) * | 2018-05-22 | 2018-09-28 | 成都新柯力化工科技有限公司 | A kind of fuel cell humidification control water quality proton exchange and preparation method certainly |
| WO2018214843A1 (en) * | 2017-05-22 | 2018-11-29 | 大连理工大学 | Crosslinked porous membrane resulting from hydrolysis of ester group side chain and preparation method therefor |
| CN109148900A (en) * | 2018-08-15 | 2019-01-04 | 成都新柯力化工科技有限公司 | A kind of membrane electrode and preparation method improving carbon-based fuel cell catalytic activity |
| CN111533937A (en) * | 2020-06-01 | 2020-08-14 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof |
| CN111600053A (en) * | 2020-06-01 | 2020-08-28 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Functionalized graphene/Nafion composite proton exchange membrane and preparation method and application thereof |
-
2021
- 2021-04-01 CN CN202110355663.5A patent/CN113097550A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935030A (en) * | 2010-08-31 | 2011-01-05 | 南京理工大学 | Functional graphene oxide for adjusting and controlling dispersibility of solvent by using organic chain segment as well as preparation method thereof |
| WO2018214843A1 (en) * | 2017-05-22 | 2018-11-29 | 大连理工大学 | Crosslinked porous membrane resulting from hydrolysis of ester group side chain and preparation method therefor |
| CN107968214A (en) * | 2017-11-09 | 2018-04-27 | 大连理工大学 | A kind of hydrophilic long pendant basic anion-exchange membrane and preparation method thereof |
| CN108598534A (en) * | 2018-05-22 | 2018-09-28 | 成都新柯力化工科技有限公司 | A kind of fuel cell humidification control water quality proton exchange and preparation method certainly |
| CN109148900A (en) * | 2018-08-15 | 2019-01-04 | 成都新柯力化工科技有限公司 | A kind of membrane electrode and preparation method improving carbon-based fuel cell catalytic activity |
| CN111533937A (en) * | 2020-06-01 | 2020-08-14 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Modified graphene oxide/Nafion composite proton exchange membrane and preparation method and application thereof |
| CN111600053A (en) * | 2020-06-01 | 2020-08-28 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Functionalized graphene/Nafion composite proton exchange membrane and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李发勇等: ""聚甘油增塑改性聚乙烯醇复合膜性能研究"", 《塑料科技》 * |
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