WO2023197787A1 - Conductive polyaniline/graphene oxide-modified nafion composite proton exchange membrane and use thereof - Google Patents
Conductive polyaniline/graphene oxide-modified nafion composite proton exchange membrane and use thereof Download PDFInfo
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- WO2023197787A1 WO2023197787A1 PCT/CN2023/080289 CN2023080289W WO2023197787A1 WO 2023197787 A1 WO2023197787 A1 WO 2023197787A1 CN 2023080289 W CN2023080289 W CN 2023080289W WO 2023197787 A1 WO2023197787 A1 WO 2023197787A1
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- conductive polyaniline
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 229920000557 Nafion® Polymers 0.000 title claims abstract description 90
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 8
- 239000005457 ice water Substances 0.000 claims abstract description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the invention relates to a fuel cell proton exchange membrane and a preparation method thereof, in particular to a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane and its application.
- the proton exchange membrane is a key component of the proton exchange membrane fuel cell (PEMFC). It can effectively utilize hydrogen as an environmentally friendly energy source to generate electricity. Its proton conductivity directly determines the battery performance.
- PEM perfluorosulfonic acid resin
- Nafion perfluorosulfonic acid resin
- water and temperature have a significant impact on the proton conductivity of the Nafion membrane. Under high temperature and water shortage conditions, the proton transport capability declines, resulting in a significant decrease in the proton conductivity.
- Graphene has many excellent physical and chemical properties due to its unique two-dimensional layered structure, such as: High strength, high electron mobility, high specific surface area and high thermal conductivity, etc. These excellent properties make graphene have good application prospects in the fields of energy storage, sensors and composite materials.
- the hydrophobic nature of graphene makes it difficult to disperse in water and commonly used organic solvents, which severely limits its application.
- Graphene oxide has various hydrophilic groups, which can inherit the excellent properties of graphene while improving its dispersion in the Nafion matrix. J.
- the technical problem to be solved by the present invention is: in order to solve the problem of relatively poor selectivity of the Nafion membrane in the prior art and at the same time enhance the proton conductivity, the present invention provides a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane and applications.
- the invention provides a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane.
- the Nafion composite proton exchange membrane is prepared by the following method:
- graphene oxide (graphene oxide is prepared by the Hummers method) is ultrasonically dispersed into hydrochloric acid, then polyvinylpyrrolidone is added under ice-water bath conditions, and stirred for 10 to 40 minutes after addition, so that the temperature of the resulting solution is 0°C;
- the stirring time is 30 to 35 minutes. During the stirring process, keep the solution temperature at 0°C, then add conductive polyaniline and continue stirring the reaction. The reaction time is 3 to 6 hours;
- reaction product is filtered, washed, and vacuum dried after washing to obtain a conductive polyaniline/graphene oxide composite material
- the conductive polyaniline/graphene oxide composite material obtained in step a is ultrasonically dispersed into the isopropyl alcohol aqueous solution, and then the perfluorosulfonic acid resin Nafion is added to continue ultrasonic dispersion.
- the dispersion time is 30 to 40 minutes;
- the mass volume ratio between the graphene oxide and hydrochloric acid added in step a is 1g:80 ⁇ 120mL; the concentration of the hydrochloric acid is 1mol/L.
- the mass ratio of the graphene oxide and polyvinylpyrrolidone added in step a is 18 to 23:1 (preferably 20:1 ).
- the mass ratio of the graphene oxide and ammonium persulfate added in step a is 1.8 to 2.3:1 (preferably 2:1) ;
- the mass ratio added between the graphene oxide and the conductive polyaniline is 1.8-2.3: 2.7-3.2 (preferably 2:3).
- step a When vacuum drying is described in, the vacuum degree is 133Pa, the drying temperature is 60°C, and the drying time is 20 to 30 hours.
- the mass ratio between the conductive polyaniline/graphene oxide composite material and the isopropyl alcohol aqueous solution in step b is 1:69 ⁇ 70;
- the isopropyl alcohol aqueous solution is mixed with isopropyl alcohol and water according to a mass ratio of 2:1.
- the mass ratio between the perfluorosulfonic acid resin Nafion and the conductive polyaniline/graphene oxide composite material in step b is 100: 1 ⁇ 2.
- the mass ratio of the graphene oxide and cuprous bromide added in step b is 6 to 10:1 (preferably 8:1). 1), the mass/volume ratio added between the copper bromide and concentrated sulfuric acid is 1g:100 ⁇ 150mL; the volume ratio added between the concentrated sulfuric acid and hydrogen peroxide is 1:1 ⁇ 2 (Preferably 1:1).
- conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane it is transferred to a hydrothermal reactor for reaction as described in step b, and the reaction is carried out in a 200-220°C oven for 4-8 hours; the vacuum When drying, the vacuum degree is 133Pa and the drying time is 10 to 16 hours.
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane prepared by the invention is used in methanol fuel cells.
- the graphene oxide loaded on the Nafion membrane has various hydrophilic groups (-NH 2 , -OH, -SO 3 H) that have good compatibility with the polymer membrane, and can Improve the water retention performance of Nafion membrane.
- the nanocomposite film can still retain a certain amount of moisture.
- These hot molecules have high enough diffusion capabilities to ensure that the Nafion composite film has good proton conductivity.
- the groups on the surface of conductive polyaniline can combine with the Nafion membrane to form a conductive network, which enhances the proton conductivity of the composite membrane. Enhanced proton conductivity.
- graphene oxide has various hydrophilic groups, which can not only inherit the excellent properties of graphene, but also improve its dispersion in the Nafion matrix.
- the size of polyaniline can be controlled by adjusting the temperature, thereby effectively regulating the channel size of the Nafion composite proton exchange membrane, avoiding the diffusion of methanol molecules, thereby improving the alcohol-blocking performance of the Nafion membrane.
- the conductive polyaniline/graphene oxide-modified Nafion composite proton exchange membrane prepared by the present invention can solve the problem of the decline of proton transmission capacity under high temperature and water shortage conditions, which will lead to a significant decrease in proton conductivity and the relative selectivity of the Nafion membrane between protons.
- the common key scientific problem that leads to the penetration of methanol molecules shows good prospects for the commercial application and promotion of Nafion proton exchange membranes in fuel cells.
- Figure 1 is an SEM image of the 2wt% PANI/GO@Nafion composite proton exchange membrane prepared in Example 5 of the present invention.
- the perfluorosulfonic acid resin (Nafion) used in the following examples is produced by DuPont Company of the United States.
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
- the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
- the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
- the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
- the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
- the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention the Nafion
- the detailed preparation method of the composite proton exchange membrane is as follows:
- the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
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Abstract
The present invention discloses a conductive polyaniline/graphene oxide-modified Nafion composite proton exchange membrane and the use thereof. The conductive polyaniline/graphene oxide-modified Nafion composite proton exchange membrane is obtained by first dispersing graphene oxide into hydrochloric acid, adding polyvinylpyrrolidone thereto in an ice-water bath, and stirring same to make the temperature of the resulting solution be 0°C; then adding ammonium persulfate thereto, continuing to stir same, then adding conductive polyaniline, and stirring same for a reaction; performing a treatment after the reaction so as to obtain a conductive polyaniline/graphene oxide composite material; dispersing the resulting composite material into an aqueous isopropanol solution, then adding a Nafion resin, continuing to disperse same, adding cuprous bromide, hydrogen peroxide and sulfuric acid after dispersion, and then carrying out a hydrothermal reaction; and sequentially subjecting the resulting product to washing, casting into a film and vacuum drying to obtain the conductive polyaniline/graphene oxide-modified Nafion composite proton exchange membrane. The product obtained in the present invention can effectively solve the problem of relatively poor selectivity of a Nafion membrane in the prior art; moreover, the proton conduction capability thereof is enhanced.
Description
本发明涉及一种燃料电池质子交换膜及其制备方法，具体涉及一种导电聚苯胺/氧化石墨烯修饰Nafion复合质子交换膜及其应用。The invention relates to a fuel cell proton exchange membrane and a preparation method thereof, in particular to a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane and its application.
质子交换膜(PEM)是质子交换膜燃料电池(PEMFC)的关键组成部分，它可以有效地利用氢作为一种环境友好的能源来发电，其质子传导率直接决定着电池性能。目前，最常见的PEM是全氟磺酸树脂(PFSA)膜，在商业上称为Nafion，主要是因其具有优异的质子导电性、化学与电化学稳定性以及耐久性，从而受到了广泛的关注。然而，水和温度对Nafion膜的质子电导率有显著影响，在高温缺水状态下，质子传输能力衰退进而导致质子电导率明显降低。另外，Nafion膜在质子间的选择性相对较差导致其他离子或小分子迁移，最终整个电化学能源系统出现问题。Nafion膜直接应用于甲醇燃料电池(DMFC)中时，燃料甲醇渗透严重，甲醇分子通过氢键与水分子结合，结合后一起通过离子簇网络穿透到阴极，对阴极正常反应造成干扰，导致DMFC效率显著下降。J.Polymer Chemistry,3(2012)，1373-1383，“Developments of highly proton-conductive sulfonated polymers for proton exchange membrane fuel cells”中提出，目前的研究主要分为两类，一类是设计和合成新型聚电解质制备聚电解质，另一类是用有机或无机添加剂对现有的聚电解质进行改性。The proton exchange membrane (PEM) is a key component of the proton exchange membrane fuel cell (PEMFC). It can effectively utilize hydrogen as an environmentally friendly energy source to generate electricity. Its proton conductivity directly determines the battery performance. Currently, the most common PEM is perfluorosulfonic acid resin (PFSA) membrane, commercially known as Nafion, which is widely used due to its excellent proton conductivity, chemical and electrochemical stability, and durability. focus on. However, water and temperature have a significant impact on the proton conductivity of the Nafion membrane. Under high temperature and water shortage conditions, the proton transport capability declines, resulting in a significant decrease in the proton conductivity. In addition, the relatively poor selectivity of the Nafion membrane between protons leads to the migration of other ions or small molecules, and eventually problems occur in the entire electrochemical energy system. When the Nafion membrane is directly used in a methanol fuel cell (DMFC), the fuel methanol penetrates seriously. The methanol molecules combine with water molecules through hydrogen bonds. After the combination, they penetrate into the cathode through the ion cluster network, causing interference to the normal reaction of the cathode and causing DMFC Efficiency drops significantly. J. Polymer Chemistry, 3 (2012), 1373-1383, "Developments of highly proton-conductive sulfonated polymers for proton exchange membrane fuel cells" proposed that current research is mainly divided into two categories. One is the design and synthesis of new polymers. Electrolytes are used to prepare polyelectrolytes, and the other is to modify existing polyelectrolytes with organic or inorganic additives.
石墨烯因其独特二维层状结构，从而具有诸多优异的物理化学性质，例如：
高强度、高电子迁移率、高比表面积和高的热导率等。这些优异的性能使得石墨烯在能量存储、传感器以及复合材料等领域具有较好的应用前景。但是，石墨烯的疏水特性使其很难分散于水及常用的有机溶剂中，由此严重限制了其应用。氧化石墨烯具有各种亲水基团，能够继承石墨烯的优良性质的同时改善其在Nafion基体中的分散性。J.Journal of Membrane Science，514(2016)，86-94，“Nanohybrids of graphene oxide chemically-bonded with Nafion:Preparation and application for proton exchange membrane fuel cells”一文中，通过Nafion上的C-F基团与GO的C＝C基团之间的原子转移自由基加成反应(ATRA)，制备了GO/Nafion复合材料。相比纯Nafion膜、GO-Nafion复合膜可使质子电导率提高1.6倍。然而，该方法对Nafion膜选择性相对较差的问题没有实质性改善。Graphene has many excellent physical and chemical properties due to its unique two-dimensional layered structure, such as: High strength, high electron mobility, high specific surface area and high thermal conductivity, etc. These excellent properties make graphene have good application prospects in the fields of energy storage, sensors and composite materials. However, the hydrophobic nature of graphene makes it difficult to disperse in water and commonly used organic solvents, which severely limits its application. Graphene oxide has various hydrophilic groups, which can inherit the excellent properties of graphene while improving its dispersion in the Nafion matrix. J. Journal of Membrane Science, 514 (2016), 86-94, in the article "Nanohybrids of graphene oxide chemically-bonded with Nafion: Preparation and application for proton exchange membrane fuel cells", the CF group on Nafion interacts with GO GO/Nafion composites were prepared through atom transfer radical addition reaction (ATRA) between C=C groups. Compared with pure Nafion membrane, GO-Nafion composite membrane can increase proton conductivity by 1.6 times. However, this method does not substantially improve the problem of relatively poor selectivity of Nafion membranes.
三、发明内容：3. Contents of the invention:
本发明要解决的技术问题是：为了解决现有技术中Nafion膜选择性相对较差的问题，同时强化质子传导能力，本发明提供了一种导电聚苯胺/氧化石墨烯修饰Nafion复合质子交换膜及应用。The technical problem to be solved by the present invention is: in order to solve the problem of relatively poor selectivity of the Nafion membrane in the prior art and at the same time enhance the proton conductivity, the present invention provides a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane and applications.
为了解决上述问题，本发明采取的技术方案是：In order to solve the above problems, the technical solution adopted by the present invention is:
本发明提供一种导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion复合质子交换膜是通过以下方法制备所得：The invention provides a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane. The Nafion composite proton exchange membrane is prepared by the following method:
a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将(氧化石墨烯是采用Hummers方法制备得到)氧化石墨烯超声分散至盐酸中，接着在冰水浴条件下加入聚乙烯吡咯烷酮，加入后搅拌10～40min，使其所得溶液温度为0℃；First, graphene oxide (graphene oxide is prepared by the Hummers method) is ultrasonically dispersed into hydrochloric acid, then polyvinylpyrrolidone is added under ice-water bath conditions, and stirred for 10 to 40 minutes after addition, so that the temperature of the resulting solution is 0°C;
然后在所得溶液中加入过硫酸铵继续进行搅拌，搅拌时间为30～35min，在
搅拌过程中，使溶液温度始终保持为0℃，接着加入导电聚苯胺继续搅拌反应，反应时间为3～6h；Then add ammonium persulfate to the resulting solution and continue stirring. The stirring time is 30 to 35 minutes. During the stirring process, keep the solution temperature at 0°C, then add conductive polyaniline and continue stirring the reaction. The reaction time is 3 to 6 hours;
反应后，将反应产物依次进行过滤、洗涤，洗涤后进行真空干燥，得到导电聚苯胺/氧化石墨烯复合材料复合材料；After the reaction, the reaction product is filtered, washed, and vacuum dried after washing to obtain a conductive polyaniline/graphene oxide composite material;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料超声分散至异丙醇水溶液中，然后加入全氟磺酸树脂Nafion继续超声分散，分散时间为30～40min；The conductive polyaniline/graphene oxide composite material obtained in step a is ultrasonically dispersed into the isopropyl alcohol aqueous solution, and then the perfluorosulfonic acid resin Nafion is added to continue ultrasonic dispersion. The dispersion time is 30 to 40 minutes;
超声分散后，在所得溶液中加入溴化亚铜、浓硫酸(质量分数98％)和过氧化氢(浓度为5％)，然后转移至水热反应釜中进行反应；反应后，将所得产物采用(60℃)去离子水进行洗涤，所得铸膜液浇铸成膜，接着进行真空干燥，得到导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add copper bromide, concentrated sulfuric acid (mass fraction 98%) and hydrogen peroxide (concentration 5%) to the resulting solution, and then transfer it to a hydrothermal reactor for reaction; after the reaction, the resulting product Use (60°C) deionized water for washing, and the resulting casting liquid is cast into a film, and then dried in a vacuum to obtain a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane.
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤a中所述氧化石墨烯与盐酸二者之间加入的质量体积比为1g：80～120mL；所述盐酸的浓度为1mol/L。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass volume ratio between the graphene oxide and hydrochloric acid added in step a is 1g:80~120mL; the concentration of the hydrochloric acid is 1mol/L.
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤a中所述氧化石墨烯与聚乙烯吡咯烷酮二者之间加入的质量比为18～23：1(优选为20：1)。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass ratio of the graphene oxide and polyvinylpyrrolidone added in step a is 18 to 23:1 (preferably 20:1 ).
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤a中所述氧化石墨烯与过硫酸铵二者之间加入的质量比1.8～2.3：1(优选为2：1)；所述氧化石墨烯与导电聚苯胺二者之间加入的质量比1.8～2.3：2.7～3.2(优选为2：3)。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass ratio of the graphene oxide and ammonium persulfate added in step a is 1.8 to 2.3:1 (preferably 2:1) ; The mass ratio added between the graphene oxide and the conductive polyaniline is 1.8-2.3: 2.7-3.2 (preferably 2:3).
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤a
中所述真空干燥时，真空度为133Pa、干燥温度为60℃、干燥时间为20～30h。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, step a When vacuum drying is described in, the vacuum degree is 133Pa, the drying temperature is 60°C, and the drying time is 20 to 30 hours.
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤b中所述导电聚苯胺/氧化石墨烯复合材料与异丙醇水溶液二者之间加入的质量比为1：69～70；所述异丙醇水溶液由异丙醇和水按照质量比2：1混合而成。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass ratio between the conductive polyaniline/graphene oxide composite material and the isopropyl alcohol aqueous solution in step b is 1:69~ 70; The isopropyl alcohol aqueous solution is mixed with isopropyl alcohol and water according to a mass ratio of 2:1.
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤b中所述全氟磺酸树脂Nafion与导电聚苯胺/氧化石墨烯复合材料二者之间加入的质量比为100：1～2。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass ratio between the perfluorosulfonic acid resin Nafion and the conductive polyaniline/graphene oxide composite material in step b is 100: 1～2.
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤b中所述氧化石墨烯与溴化亚铜二者之间加入的质量比为6～10：1(优选为8：1)，所述溴化亚铜与浓硫酸二者之间加入的质量体积比为1g：100～150mL；所述浓硫酸与过氧化氢二者之间加入的体积比为1：1～2(优选为1：1)。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, the mass ratio of the graphene oxide and cuprous bromide added in step b is 6 to 10:1 (preferably 8:1). 1), the mass/volume ratio added between the copper bromide and concentrated sulfuric acid is 1g:100~150mL; the volume ratio added between the concentrated sulfuric acid and hydrogen peroxide is 1:1~2 (Preferably 1:1).
根据上述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，步骤b中所述转移至水热反应釜中进行反应，是在200～220℃烘箱中进行反应4～8h；所述真空干燥时，真空度为133Pa、干燥时间为10～16h。According to the above-mentioned conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, it is transferred to a hydrothermal reactor for reaction as described in step b, and the reaction is carried out in a 200-220°C oven for 4-8 hours; the vacuum When drying, the vacuum degree is 133Pa and the drying time is 10 to 16 hours.
本发明制备所得导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜在甲醇燃料电池中的应用。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane prepared by the invention is used in methanol fuel cells.
本发明的积极有益效果：Positive beneficial effects of the present invention:
1、本发明技术方案中，负载在Nafion膜上的氧化石墨烯具有与高分子膜有良好的相容性各种亲水基团(-NH2、-OH、-SO3H)，并且能够提高Nafion膜的保水性能。在高温条件下，纳米复合膜依然能够保留一定的水分，这些热分子具有足够高的扩散能力，保证Nafion复合膜具有良好的质子导电性。导电聚苯胺表面的基团能与Nafion膜结合，形成导电网络，加强了复合膜的质子导电性，
强化了质子的传导能力。1. In the technical solution of the present invention, the graphene oxide loaded on the Nafion membrane has various hydrophilic groups (-NH 2 , -OH, -SO 3 H) that have good compatibility with the polymer membrane, and can Improve the water retention performance of Nafion membrane. Under high temperature conditions, the nanocomposite film can still retain a certain amount of moisture. These hot molecules have high enough diffusion capabilities to ensure that the Nafion composite film has good proton conductivity. The groups on the surface of conductive polyaniline can combine with the Nafion membrane to form a conductive network, which enhances the proton conductivity of the composite membrane. Enhanced proton conductivity.
2、本发明技术方案中，氧化石墨烯具有各种亲水基团，能够继承石墨烯的优良性质的同时，还能够改善其在Nafion基体中的分散性。此外，通过调节温度可控制聚苯胺的尺寸，进而有效调控Nafion复合质子交换膜的通道尺寸，避免甲醇分子的扩散，从而提高Nafion膜的阻醇性能。2. In the technical solution of the present invention, graphene oxide has various hydrophilic groups, which can not only inherit the excellent properties of graphene, but also improve its dispersion in the Nafion matrix. In addition, the size of polyaniline can be controlled by adjusting the temperature, thereby effectively regulating the channel size of the Nafion composite proton exchange membrane, avoiding the diffusion of methanol molecules, thereby improving the alcohol-blocking performance of the Nafion membrane.
3、本发明制备的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜能够解决在高温缺水状态下，质子传输能力衰退进而导致质子电导率明显降低和Nafion膜在质子间的选择性相对较差导致甲醇分子渗透的共性关键科学难题，对于Nafion质子交换膜在燃料电池上的商业化应用和推广展现了良好的前景。3. The conductive polyaniline/graphene oxide-modified Nafion composite proton exchange membrane prepared by the present invention can solve the problem of the decline of proton transmission capacity under high temperature and water shortage conditions, which will lead to a significant decrease in proton conductivity and the relative selectivity of the Nafion membrane between protons. The common key scientific problem that leads to the penetration of methanol molecules shows good prospects for the commercial application and promotion of Nafion proton exchange membranes in fuel cells.
图1本发明实施例5制备所得2wt％PANI/GO@Nafion复合质子交换膜的SEM图。Figure 1 is an SEM image of the 2wt% PANI/GO@Nafion composite proton exchange membrane prepared in Example 5 of the present invention.
以下结合实施例进一步阐述本发明，但并不限制本发明技术方案保护的范围。The present invention will be further described below with reference to the examples, but do not limit the scope of protection of the technical solution of the present invention.
以下实施例中采用的全氟磺酸树脂(Nafion)为美国杜邦公司生产。The perfluorosulfonic acid resin (Nafion) used in the following examples is produced by DuPont Company of the United States.
实施例1：Example 1:
本发明导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion复合质子交换膜的详细制备方法如下：The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention, the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将采用Hummers方法制备得到的氧化石墨烯0.2g超声分散至20mL、1mol/L的盐酸中，超声分散时间为30min；接着在冰水浴条件下加入0.01g聚乙
烯吡咯烷酮，加入后进行搅拌30min，使其所得溶液温度为0℃；First, 0.2g of graphene oxide prepared by the Hummers method was ultrasonically dispersed into 20mL, 1mol/L hydrochloric acid, and the ultrasonic dispersion time was 30min; then 0.01g of polyethylene was added under ice-water bath conditions. After adding enpyrrolidone, stir for 30 minutes so that the temperature of the resulting solution is 0°C;
然后在所得溶液中加入0.1g过硫酸铵继续进行搅拌，搅拌时间为0.5h，在搅拌过程使溶液温度始终保持为0℃，接着加入0.3g导电聚苯胺继续搅拌反应，反应时间为4h；Then add 0.1g ammonium persulfate to the resulting solution and continue stirring. The stirring time is 0.5h. During the stirring process, the temperature of the solution is always maintained at 0°C. Then 0.3g conductive polyaniline is added to continue stirring the reaction. The reaction time is 4h;
反应后，将反应产物进行离心，所得固体采用去离子水进行洗涤(洗涤后再进行离心，如此反复操作3次)，然后将所得固体在60℃的烘箱中干燥24h，得到导电聚苯胺/氧化石墨烯复合材料；After the reaction, the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料5mg超声分散至42mL异丙醇水溶液中(异丙醇水溶液是由异丙醇和水按照质量比2:1混合而成)，然后加入0.5g全氟磺酸树脂Nafion继续超声分散30min；Ultrasonically disperse 5 mg of the conductive polyaniline/graphene oxide composite material obtained in step a into 42 mL of isopropyl alcohol aqueous solution (the isopropyl alcohol aqueous solution is a mixture of isopropyl alcohol and water at a mass ratio of 2:1), and then add 0.5 g of all Fluorosulfonic acid resin Nafion continues to be dispersed ultrasonically for 30 minutes;
超声分散后，在所得溶液中加入0.025g溴化亚铜、3mL过氧化氢(质量百分浓度5％)和3mL浓硫酸(质量百分浓度98％)，然后转移至水热反应釜中，置于烘箱中，在220℃条件下反应6h；反应后进行过滤，采用60℃的去离子水进行洗涤三次，洗涤后所得铸膜液浇铸成膜，然后进行真空干燥(所述真空干燥时，真空度为133Pa，干燥温度为70℃、干燥时间为16h)，得到1wt％导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add 0.025g cuprous bromide, 3mL hydrogen peroxide (mass percentage concentration 5%) and 3mL concentrated sulfuric acid (mass percentage concentration 98%) to the resulting solution, and then transfer it to a hydrothermal reaction kettle. Place in an oven and react at 220°C for 6 hours; filter after the reaction and wash three times with deionized water at 60°C. After washing, the resulting casting liquid is cast into a film and then vacuum dried (during the vacuum drying, The vacuum degree is 133Pa, the drying temperature is 70°C, and the drying time is 16 hours), and a 1wt% conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane is obtained.
实施例2：Example 2:
本发明导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion复合质子交换膜的详细制备方法如下：The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention, the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将采用Hummers方法制备得到的氧化石墨烯0.2g超声分散至20mL、
1mol/L的盐酸中，超声分散时间为30min；接着在冰水浴条件下加入0.01g聚乙烯吡咯烷酮，加入后进行搅拌30min，使其所得溶液温度为0℃；First, 0.2g of graphene oxide prepared by the Hummers method was ultrasonically dispersed into 20 mL. In 1 mol/L hydrochloric acid, the ultrasonic dispersion time is 30 minutes; then add 0.01g polyvinylpyrrolidone under ice water bath conditions, stir for 30 minutes after addition, so that the temperature of the resulting solution is 0°C;
然后在所得溶液中加入0.1g过硫酸铵继续进行搅拌，搅拌时间为0.5h，在搅拌过程使溶液温度始终保持为0℃，接着加入0.3g导电聚苯胺继续搅拌反应，反应时间为4h；Then add 0.1g ammonium persulfate to the resulting solution and continue stirring. The stirring time is 0.5h. During the stirring process, the temperature of the solution is always maintained at 0°C. Then 0.3g conductive polyaniline is added to continue stirring the reaction. The reaction time is 4h;
反应后，将反应产物进行离心，所得固体采用去离子水进行洗涤(洗涤后再进行离心，如此反复操作3次)，然后将所得固体在60℃的烘箱中干燥24h，得到导电聚苯胺/氧化石墨烯复合材料；After the reaction, the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料6.25mg超声分散至42mL异丙醇水溶液中(异丙醇水溶液是由异丙醇和水按照质量比2:1混合而成)，然后加入0.5g全氟磺酸树脂Nafion继续超声分散30min；Ultrasonically disperse 6.25 mg of the conductive polyaniline/graphene oxide composite obtained in step a into 42 mL of isopropyl alcohol aqueous solution (the isopropyl alcohol aqueous solution is made by mixing isopropyl alcohol and water at a mass ratio of 2:1), and then add 0.5 g Perfluorosulfonic acid resin Nafion continues to be dispersed ultrasonically for 30 minutes;
超声分散后，在所得溶液中加入0.025g溴化亚铜、3mL过氧化氢(质量百分浓度为5％)和3mL浓硫酸(质量百分浓度为98％)，然后转移至水热反应釜中，置于烘箱中，在220℃条件下反应6h；反应后进行过滤，采用60℃去离子水进行洗涤三次，洗涤后所得铸膜液浇铸成膜，然后进行真空干燥(真空干燥时，真空度为133Pa，干燥温度为70℃、干燥时间为12h)，得到1.25wt％导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add 0.025g cuprous bromide, 3mL hydrogen peroxide (mass percentage concentration: 5%) and 3mL concentrated sulfuric acid (mass percentage concentration: 98%) to the resulting solution, and then transfer to the hydrothermal reaction kettle in, placed in an oven, and reacted for 6 hours at 220°C; filtered after the reaction, washed three times with 60°C deionized water, and the cast film obtained after washing was cast into a film, and then vacuum dried (during vacuum drying, vacuum The temperature is 133Pa, the drying temperature is 70°C, and the drying time is 12h), and a 1.25wt% conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane is obtained.
实施例3：Example 3:
本发明导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion复合质子交换膜的详细制备方法如下：The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention, the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
a、导电聚苯胺/氧化石墨烯复合材料的制备：
a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将采用Hummers方法制备得到的氧化石墨烯0.2g超声分散至20mL、1mol/L的盐酸中，超声分散时间为30min；接着在冰水浴条件下加入0.01g聚乙烯吡咯烷酮PVP，加入后进行搅拌30min，使其所得溶液温度为0℃；First, 0.2g of graphene oxide prepared by the Hummers method was ultrasonically dispersed into 20mL, 1mol/L hydrochloric acid, and the ultrasonic dispersion time was 30min; then 0.01g of polyvinylpyrrolidone PVP was added under ice-water bath conditions, and stirred for 30min after addition. , so that the temperature of the resulting solution is 0°C;
然后在所得溶液中加入0.1g过硫酸铵继续进行搅拌，搅拌时间为0.5h，在搅拌过程使溶液温度始终保持为0℃，接着加入0.3g导电聚苯胺继续搅拌反应，反应时间为4h；Then add 0.1g ammonium persulfate to the resulting solution and continue stirring. The stirring time is 0.5h. During the stirring process, the temperature of the solution is always maintained at 0°C. Then 0.3g conductive polyaniline is added to continue stirring the reaction. The reaction time is 4h;
反应后，将反应产物进行离心，所得固体采用去离子水进行洗涤(洗涤后再进行离心，如此反复操作3次)，然后将所得固体在60℃的烘箱中干燥24h，得到导电聚苯胺/氧化石墨烯复合材料；After the reaction, the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料7.5mg超声分散至42mL异丙醇水溶液中(异丙醇水溶液是由异丙醇和水按照质量比2:1混合而成)，然后加入0.5g全氟磺酸树脂Nafion继续超声分散30min；Ultrasonically disperse 7.5 mg of the conductive polyaniline/graphene oxide composite material obtained in step a into 42 mL of isopropyl alcohol aqueous solution (the isopropyl alcohol aqueous solution is made by mixing isopropyl alcohol and water at a mass ratio of 2:1), and then add 0.5 g Perfluorosulfonic acid resin Nafion continues to be dispersed ultrasonically for 30 minutes;
超声分散后，在所得溶液中加入0.025g溴化亚铜、3mL过氧化氢(质量百分浓度为5％)和3mL浓硫酸(质量百分浓度为98％)，然后转移至水热反应釜中，置于烘箱中，在220℃条件下反应6h；反应后进行过滤，采用60℃去离子水进行洗涤三次，洗涤后所得铸膜液浇铸成膜，然后进行真空干燥(真空干燥时，真空度为133Pa、干燥温度为70℃、干燥时间为12h)，得到1.5wt％导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add 0.025g cuprous bromide, 3mL hydrogen peroxide (mass percentage concentration: 5%) and 3mL concentrated sulfuric acid (mass percentage concentration: 98%) to the resulting solution, and then transfer to the hydrothermal reaction kettle in, placed in an oven, and reacted for 6 hours at 220°C; filtered after the reaction, washed three times with 60°C deionized water, and the cast film obtained after washing was cast into a film, and then vacuum dried (during vacuum drying, vacuum The temperature is 133 Pa, the drying temperature is 70°C, and the drying time is 12 hours), and a 1.5wt% conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane is obtained.
实施例4：Example 4:
本发明导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion复合质子交换膜的详细制备方法如下：
The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention, the detailed preparation method of the Nafion composite proton exchange membrane is as follows:
a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将采用Hummers方法制备得到的氧化石墨烯0.2g超声分散至20mL、1mol/L的盐酸中，超声分散时间为30min；接着在冰水浴条件下加入0.01g聚乙烯吡咯烷酮，加入后进行搅拌30min，使其所得溶液温度为0℃；First, 0.2g of graphene oxide prepared by the Hummers method was ultrasonically dispersed into 20mL, 1mol/L hydrochloric acid, and the ultrasonic dispersion time was 30min; then 0.01g of polyvinylpyrrolidone was added under ice-water bath conditions, and stirred for 30min after addition. Make the temperature of the resulting solution 0°C;
然后在所得溶液中加入0.1g过硫酸铵继续进行搅拌，搅拌时间为0.5h，在搅拌过程使溶液温度始终保持为0℃，接着加入0.3g导电聚苯胺继续搅拌反应，反应时间为4h；Then add 0.1g ammonium persulfate to the resulting solution and continue stirring. The stirring time is 0.5h. During the stirring process, the temperature of the solution is always maintained at 0°C. Then 0.3g conductive polyaniline is added to continue stirring the reaction. The reaction time is 4h;
反应后，将反应产物进行离心，所得固体采用去离子水进行洗涤(洗涤后再进行离心，如此反复操作3次)，然后将所得固体在60℃的烘箱中干燥24h，得到导电聚苯胺/氧化石墨烯复合材料；After the reaction, the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料8.75mg超声分散至42mL异丙醇水溶液中(异丙醇水溶液是由异丙醇和水按照质量比2:1混合而成)，然后加入0.5g全氟磺酸树脂Nafion继续超声分散30min；Ultrasonically disperse 8.75 mg of the conductive polyaniline/graphene oxide composite material obtained in step a into 42 mL of isopropyl alcohol aqueous solution (the isopropyl alcohol aqueous solution is made by mixing isopropyl alcohol and water at a mass ratio of 2:1), and then add 0.5 g Perfluorosulfonic acid resin Nafion continues to be dispersed ultrasonically for 30 minutes;
超声分散后，在所得溶液中加入0.025g溴化亚铜、3mL过氧化氢(质量百分浓度为5％)和3mL浓硫酸(质量百分浓度为98％)，然后转移至水热反应釜中，置于烘箱中，在220℃条件下反应6h；反应后进行过滤，采用热去离子水进行洗涤三次，洗涤后所得铸膜液浇铸成膜，然后进行真空干燥(真空干燥时，真空度为133Pa、干燥温度为70℃、干燥时间为12h)，得到1.75wt％导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add 0.025g cuprous bromide, 3mL hydrogen peroxide (mass percentage concentration: 5%) and 3mL concentrated sulfuric acid (mass percentage concentration: 98%) to the resulting solution, and then transfer to the hydrothermal reaction kettle in, placed in an oven, and reacted for 6 hours at 220°C; filtered after the reaction, washed three times with hot deionized water, and the resulting casting liquid after washing was cast into a film, and then vacuum dried (during vacuum drying, the vacuum degree (133 Pa, drying temperature of 70°C, and drying time of 12 h), a 1.75 wt% conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane was obtained.
实施例5：Example 5:
本发明导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，所述Nafion
复合质子交换膜的详细制备方法如下：The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane of the present invention, the Nafion The detailed preparation method of the composite proton exchange membrane is as follows:
a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:
首先将采用Hummers方法制备得到的氧化石墨烯0.2g超声30min分散至20mL、1mol/L的盐酸中，接着在冰水浴条件下加入0.01g聚乙烯吡咯烷酮，加入后进行搅拌30min，使其所得溶液温度为0℃；First, 0.2g of graphene oxide prepared by the Hummers method was dispersed into 20 mL, 1 mol/L hydrochloric acid by ultrasonic for 30 minutes. Then, 0.01g of polyvinylpyrrolidone was added under ice-water bath conditions. After addition, stir for 30 minutes to bring the resulting solution to temperature is 0℃;
然后在所得溶液中加入0.1g过硫酸铵继续进行搅拌，搅拌时间为0.5h，在搅拌过程使溶液温度始终保持为0℃，接着加入0.3g导电聚苯胺继续搅拌反应，反应时间为4h；Then add 0.1g ammonium persulfate to the resulting solution and continue stirring. The stirring time is 0.5h. During the stirring process, the temperature of the solution is always maintained at 0°C. Then 0.3g conductive polyaniline is added to continue stirring the reaction. The reaction time is 4h;
反应后，将反应产物进行离心，所得固体采用去离子水进行洗涤(洗涤后再进行离心，如此反复操作3次)，然后将所得固体在60℃的烘箱中干燥24h，得到导电聚苯胺/氧化石墨烯复合材料；After the reaction, the reaction product is centrifuged, and the solid obtained is washed with deionized water (centrifuge again after washing, and repeated 3 times), and then the solid obtained is dried in an oven at 60°C for 24 hours to obtain conductive polyaniline/oxidation graphene composites;
b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:
将步骤a所得导电聚苯胺/氧化石墨烯复合材料10mg超声分散至42mL异丙醇水溶液中(异丙醇水溶液是由异丙醇和水按照质量比2:1混合而成)，然后加入0.5g全氟磺酸树脂Nafion继续超声分散30min；Ultrasonically disperse 10 mg of the conductive polyaniline/graphene oxide composite material obtained in step a into 42 mL of isopropyl alcohol aqueous solution (the isopropyl alcohol aqueous solution is made by mixing isopropyl alcohol and water at a mass ratio of 2:1), and then add 0.5 g of all Fluorosulfonic acid resin Nafion continues to be dispersed ultrasonically for 30 minutes;
超声分散后，在所得溶液中加入0.025g溴化亚铜CuBr、3mL过氧化氢(质量百分浓度为5％)和3mL浓硫酸(质量百分浓度为98％)，然后转移至水热反应釜中，置于烘箱中，在220℃条件下反应6h；反应后进行过滤，采用热去离子水进行洗涤三次，洗涤后所得铸膜液浇铸成膜，然后进行真空干燥(真空干燥时，真空度为133Pa、干燥温度为70℃、干燥时间为12h)，得到2wt％导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add 0.025g copper bromide CuBr, 3mL hydrogen peroxide (mass percentage concentration: 5%) and 3mL concentrated sulfuric acid (mass percentage concentration: 98%), and then transfer to the hydrothermal reaction In the kettle, place it in an oven and react for 6 hours at 220°C; filter after the reaction and wash it three times with hot deionized water. After washing, the casting liquid obtained is cast into a film and then dried in a vacuum (during vacuum drying, vacuum The temperature is 133 Pa, the drying temperature is 70°C, and the drying time is 12 hours), and a 2wt% conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane is obtained.
本发明实施例1-5制备所得导电聚苯胺/氧化石墨烯修饰的Nafion复合质子
交换膜与纯Nafion膜在甲醇燃料电池中应用性能及其应用效果对比数据详见表1。Conductive polyaniline/graphene oxide modified Nafion composite protons prepared in Examples 1-5 of the present invention Comparative data on the application performance and application effects of exchange membranes and pure Nafion membranes in methanol fuel cells are detailed in Table 1.
表1本发明产品复合质子交换膜和纯Nafion膜相关性能及其应用效果对比
Table 1 Comparison of the relevant properties and application effects of the composite proton exchange membrane of the present invention and the pure Nafion membrane
Table 1 Comparison of the relevant properties and application effects of the composite proton exchange membrane of the present invention and the pure Nafion membrane
Claims (10)
- 一种导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于，所述Nafion复合质子交换膜是通过以下方法制备所得：A conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane, characterized in that the Nafion composite proton exchange membrane is prepared by the following method:a、导电聚苯胺/氧化石墨烯复合材料的制备：a. Preparation of conductive polyaniline/graphene oxide composite materials:首先将氧化石墨烯超声分散至盐酸中，接着在冰水浴条件下加入聚乙烯吡咯烷酮，加入后搅拌10～40min，使其所得溶液温度为0℃；First, ultrasonically disperse graphene oxide into hydrochloric acid, then add polyvinylpyrrolidone under ice-water bath conditions, stir for 10 to 40 minutes after addition, so that the temperature of the resulting solution is 0°C;然后在所得溶液中加入过硫酸铵继续进行搅拌，搅拌时间为30～35min，在搅拌过程中，使溶液温度始终保持为0℃，接着加入导电聚苯胺继续搅拌反应，反应时间为3～6h；Then add ammonium persulfate to the resulting solution and continue stirring. The stirring time is 30 to 35 minutes. During the stirring process, the temperature of the solution is always maintained at 0°C. Then conductive polyaniline is added to continue the stirring reaction. The reaction time is 3 to 6 hours;反应后，将反应产物依次进行过滤、洗涤，洗涤后进行真空干燥，得到导电聚苯胺/氧化石墨烯复合材料复合材料；After the reaction, the reaction product is filtered, washed, and vacuum dried after washing to obtain a conductive polyaniline/graphene oxide composite material;b、导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜的制备：b. Preparation of conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane:将步骤a所得导电聚苯胺/氧化石墨烯复合材料超声分散至异丙醇水溶液中，然后加入全氟磺酸树脂Nafion继续超声分散，分散时间为30～40min；The conductive polyaniline/graphene oxide composite material obtained in step a is ultrasonically dispersed into the isopropyl alcohol aqueous solution, and then the perfluorosulfonic acid resin Nafion is added to continue ultrasonic dispersion. The dispersion time is 30 to 40 minutes;超声分散后，在所得溶液中加入溴化亚铜、浓硫酸和过氧化氢，然后转移至水热反应釜中进行反应；反应后，将所得产物采用去离子水进行洗涤，所得铸膜液浇铸成膜，接着进行真空干燥，得到导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜。After ultrasonic dispersion, add copper bromide, concentrated sulfuric acid and hydrogen peroxide to the obtained solution, and then transfer it to a hydrothermal reactor for reaction; after the reaction, the obtained product is washed with deionized water, and the obtained film casting liquid is cast Film formation is followed by vacuum drying to obtain a conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤a中所述氧化石墨烯与盐酸二者之间加入的质量体积比为1g：80～120mL；所述盐酸的浓度为1mol/L。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: the mass volume ratio added between the graphene oxide and hydrochloric acid in step a is 1g:80～ 120mL; the concentration of hydrochloric acid is 1mol/L.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子 交换膜，其特征在于：步骤a中所述氧化石墨烯与聚乙烯吡咯烷酮二者之间加入的质量比为18～23：1。Conductive polyaniline/graphene oxide modified Nafion composite proton according to claim 1 The exchange membrane is characterized in that: the mass ratio of graphene oxide and polyvinylpyrrolidone added in step a is 18 to 23:1.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤a中所述氧化石墨烯与过硫酸铵二者之间加入的质量比1.8～2.3：1；所述氧化石墨烯与导电聚苯胺二者之间加入的质量比1.8～2.3：2.7～3.2。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: the mass ratio of the graphene oxide and ammonium persulfate added in step a is 1.8 to 2.3: 1; The mass ratio between the graphene oxide and the conductive polyaniline is 1.8-2.3:2.7-3.2.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤a中所述真空干燥时，真空度为133Pa、干燥温度为60℃、干燥时间为20～30h。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: during the vacuum drying in step a, the vacuum degree is 133Pa, the drying temperature is 60°C, and the drying time is 20 ~30h.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤b中所述导电聚苯胺/氧化石墨烯复合材料与异丙醇水溶液二者之间加入的质量比为1：69～70；所述异丙醇水溶液由异丙醇和水按照质量比2：1混合而成。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: the conductive polyaniline/graphene oxide composite material and the isopropyl alcohol aqueous solution in step b are added The mass ratio is 1:69-70; the isopropyl alcohol aqueous solution is mixed with isopropyl alcohol and water according to the mass ratio of 2:1.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤b中所述全氟磺酸树脂Nafion与导电聚苯胺/氧化石墨烯复合材料二者之间加入的质量比为100：1～2。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: one of the perfluorosulfonic acid resin Nafion and the conductive polyaniline/graphene oxide composite material in step b The mass ratio added is 100:1~2.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤b中所述氧化石墨烯与溴化亚铜二者之间加入的质量比为6～10：1，所述溴化亚铜与浓硫酸二者之间加入的质量体积比为1g：100～150mL；所述浓硫酸与过氧化氢二者之间加入的体积比为1：1～2。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: the mass ratio between the graphene oxide and cuprous bromide added in step b is 6~ 10:1, the mass volume ratio added between the copper bromide and concentrated sulfuric acid is 1g:100~150mL; the volume ratio added between the concentrated sulfuric acid and hydrogen peroxide is 1:1~ 2.
- 根据权利要求1所述的导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜，其特征在于：步骤b中所述转移至水热反应釜中进行反应，是在200～ 220℃烘箱中进行反应4～8h；所述真空干燥时，真空度为133Pa、干燥时间为10～16h。The conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1, characterized in that: in step b, the reaction is transferred to a hydrothermal reactor at 200 to The reaction is carried out in a 220°C oven for 4 to 8 hours; during vacuum drying, the vacuum degree is 133 Pa and the drying time is 10 to 16 hours.
- 权利要求1所述导电聚苯胺/氧化石墨烯修饰的Nafion复合质子交换膜在甲醇燃料电池中的应用。 Application of the conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane according to claim 1 in a methanol fuel cell.
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| CN110718695B (en) * | 2019-11-11 | 2021-03-26 | 北京化工大学 | Platinum-based catalytic system for formic acid fuel cell and preparation method thereof |
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| CN117238680B (en) * | 2023-11-10 | 2024-04-09 | 江西五十铃汽车有限公司 | Graphene oxide/polypyrrole composite electrode material and preparation method and application thereof |
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