CN111261914B - Graphene oxide polymer composite proton exchange membrane and preparation method and application thereof - Google Patents
Graphene oxide polymer composite proton exchange membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a graphene oxide polymer composite proton exchange membrane, a preparation method and application thereof. The composite proton exchange membrane comprises graphene oxide and polymer resin; the graphene oxide is modified by adenosine triphosphate, and the mass percentage of the graphene oxide in the composite proton exchange membrane is 0.1-15%; the mass percentage of the polymer resin in the composite proton exchange membrane is 85-99.9%. According to the invention, orderly distributed graphene oxide in the composite proton exchange membrane constructs a proton transmission channel with long-range continuity, and strong interaction is generated between phosphoric acid groups and sulfonic acid groups in the graphene oxide channel, so that abundant proton transmission sites are provided for the composite proton exchange membrane, and the improvement of proton transmission performance is promoted; the graphene oxide has a layered arrangement structure, effectively serves as a barrier layer of methanol molecules, delays the permeation rate of fuel, and improves the selectivity of the proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a graphene oxide/polymer resin composite proton exchange membrane, a preparation method and application thereof.
Background
A Direct Methanol Fuel Cell (DMFC) is a novel energy conversion device for directly converting chemical energy of methanol into electric energy, and has the advantages of high energy density, fast start, low pollution, compact design, and the like, and is receiving a great deal of attention. Proton Exchange Membranes (PEM) are the core components of membrane electrodes in DMFCs and function primarily to isolate fuel from oxidant, to isolate electrons, to conduct protons specifically, and to directly determine the operating performance of the cell. Currently, the most widely commercialized proton exchange membrane is the perfluorosulfonic acid proton exchange membrane, which is most commonly known as Nafion membrane; nafion membranes exhibit good performance to some extent, but in high temperature environments, proton conductivity and mechanical stability of Nafion membranes can drop dramatically, especially concentration diffusion and electromigration diffusion selectivity of methanol and water are low, which can lead to severe methanol fuel permeation, greatly limiting the operating performance and operating life of fuel cells, which can greatly limit the scale-up applications of fuel cells.
Oxidized graphene(GO) is the oxidation state of graphene, and the surface is rich in functional groups such as hydroxyl, carboxyl and the like; compared with graphene, GO has better hydrophilicity and biocompatibility. The functional groups on the surface of GO can be used as proton donors and acceptors, are excellent proton conductor materials, and the method for introducing the functional groups into a proton exchange membrane to improve the membrane performance is widely focused by researchers. In the prior art, nafion/GO-Nafion nano composite proton exchange membrane is mainly prepared by a knife coating method, and in the composite proton exchange membrane, the interfacial compatibility of GO nano sheets and perfluorinated sulfonic acid matrixes is obviously improved due to the introduction of Nafion molecular chains; in addition, sulfonic acid groups in the matrix are aggregated on the surface of GO to form proton channels, and single cell performance simulation of the composite membrane shows that the maximum energy density of the composite membrane can reach 886mW cm –2 . However, the GO composite proton exchange membrane prepared by the conventional knife coating method is randomly dispersed and arranged in the composite membrane, so that an ordered proton transmission channel cannot be constructed, and the further improvement of the proton transmission capacity of the proton exchange membrane is limited to a certain extent; furthermore, such a random arrangement does not provide good methanol barrier properties.
Disclosure of Invention
The invention aims to provide a graphene oxide polymer composite proton exchange membrane, a preparation method and application thereof, and solves the problems that the proton conductivity of the composite proton exchange membrane in the prior art is required to be further improved and the methanol barrier performance is poor.
In order to solve the technical problems, the technical scheme of the invention is realized as follows:
in one aspect, a graphene oxide polymer composite proton exchange membrane of the present invention comprises graphene oxide and a polymer resin; the graphene oxide is modified by adenosine triphosphate, and the mass percentage of the graphene oxide in the composite proton exchange membrane is 0.1-15%; the mass percentage of the polymer resin in the composite proton exchange membrane is 85-99.9%.
The composite proton exchange membrane comprises graphene oxide and polymer resin, wherein the graphene oxide is oxidized graphene modified by adenosine triphosphate, the two-dimensional composite proton exchange membrane is of an ordered lamellar distribution structure in the composite proton exchange membrane, the ordered distribution of the oxidized graphene modified by adenosine triphosphate enables the structure of tightly combined graphene oxide and polymer resin to have long-range continuity, and strong interaction is generated between phosphoric acid groups and sulfonic acid groups in a channel of the oxidized graphene modified by adenosine triphosphate, so that rich proton transfer sites are provided for the composite proton exchange membrane, the cooperative reinforcement of proton transfer carriers is realized, the proton transfer energy barrier is reduced, and a high-efficiency proton transfer channel is formed, so that the improvement of the proton transfer performance of the composite membrane is promoted. The layered arrangement structure of the graphene oxide in the composite proton exchange membrane can effectively serve as a barrier layer of methanol molecules, so that the permeation rate of methanol is delayed, and the selectivity of the proton exchange membrane is improved.
The film thickness of the composite proton exchange membrane is 57-225 mu m, and the methanol permeability coefficient is 1.23-3.31X10 - 7 cm 2 s -1 The barrier property to small molecules such as methanol is obviously improved compared with that of a perfluorosulfonic acid proton exchange membrane-Nafion membrane; the proton conductivity of the composite proton exchange membrane of the invention is 0.143-0.305S cm under the environment of 80 ℃ and 100% relative humidity -1 The proton conductivity of the composite proton exchange membrane of the invention is 0.065-0.195S cm under the environment of 140 ℃ and 50% relative humidity -1 The method comprises the steps of carrying out a first treatment on the surface of the Therefore, the composite proton exchange membrane still shows extremely high proton conductivity at 140 ℃ and 50% RH high temperature and low humidity environment, which is improved by 2.03-6.09 times compared with the perfluorosulfonic acid proton exchange membrane-Nafion membrane. The selectivity of the composite proton exchange membrane is 2.06-4.15X10 5 S·s·cm -3 Compared with a perfluorinated sulfonic acid proton exchange membrane, namely a Nafion membrane, the method has obvious improvement.
As a preferred embodiment, the mass ratio of adenosine triphosphate to graphene oxide in the graphene oxide is 1:40-40:1. The graphene oxide is the adenosine triphosphate modified graphene oxide, and the channel of the graphene oxide is filled with the phosphoric acid group and the sulfonic acid group, so that the connection performance of the graphene oxide and the polymer resin is improved. Adenosine triphosphate is also called Adenosine Triphosphate (ATP) and is the most direct energy source in organisms, and is formed by connecting adenine, ribose and three phosphate groups, and a large number of phosphate groups are introduced into a proton exchange membrane by an ATP immobilization method, so that the high-performance proton exchange membrane is prepared.
As a preferred embodiment, the size of the plate diameter of the graphene oxide is 0.1-3 mu m, and the thickness of the graphene oxide is 0.5-2.5nm. According to the preparation method, nanoscale graphene oxide is preferably adopted, the nano graphene oxide sheet modified by adenosine triphosphate is selected, the adenosine triphosphate is filled in a nano channel of the graphene oxide, the combination force of a phosphoric acid group and a sulfonic acid group in the nano channel is strong, and the interface effect between the graphene oxide and a polymer matrix is enhanced; the two-dimensional nano sheets are in an ordered sheet layer distribution structure in the composite proton exchange membrane, and the ordered distributed nano graphene oxide nano sheets enable the interconnected graphene oxide and polymer resin nano structures to have long-range continuity on the nano scale, so that the proton transfer path is favorably optimized, and the proton transfer efficiency is improved; the tight nano-scale lamellar structure can effectively serve as a barrier layer of methanol molecules, so that the permeation rate of fuel is delayed, and the selectivity of the proton exchange membrane is improved.
As a preferred embodiment, the polymer resin is any one of perfluorosulfonic acid resin, sulfonated polyether ketone resin, sulfonated polysulfone resin, sulfonated polyimide resin, sulfonated polystyrene resin, and sulfonated polybenzoxazole resin. The polymer resin of the invention selects the polymer with sulfonic acid groups, the sulfonic acid polymer has excellent ion exchange capacity, and the sulfonic acid groups in the molecular chain interact with the surface of graphene oxide and phosphoric acid groups in the channel to form rich hydrogen bond structures, thereby constructing a proton transmission channel with long-range continuity in the composite membrane; the polymer resin has excellent polar solvent solubility, can be prepared into a homogeneous and stable film-forming solution with graphene oxide, and has sulfonic acid groups introduced into a molecular structure, so that the excellent proton conductivity of the composite film is ensured.
In another aspect, the preparation method of the graphene oxide polymer composite proton exchange membrane provided by the invention comprises the following steps: 1) Taking graphene oxide, dispersing the graphene oxide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in a phosphate buffer solution according to a mass ratio of 1:1-6:8-20, and performing an activation reaction for 0.1-3h to obtain a dispersion solution; 2) Adding adenosine triphosphate into the dispersion solution obtained in the step 1), wherein the mass ratio of the adenosine triphosphate to the graphene oxide is 1:40-40:1, and continuously reacting for 1-6h at 20-50 ℃, filtering, washing and drying to obtain ATP@GO powder; 3) Dissolving polymer resin in a polar solvent to obtain a polymer resin solution; dissolving the ATP@GO powder obtained in the step 2) in a polar solvent to obtain an ATP@GO solution; mixing a polymer resin solution and an ATP@GO solution to obtain a mixed solution, wherein the ATP@GO powder accounts for 0.1-15% of the mass of the polymer resin in the mixed solution; 4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution obtained in the step 3) on a high-temperature film-forming substrate layer by layer, wherein the spraying speed is 0.01-0.3mL min -1 Spraying liquid for 0.2-5h, electrostatic voltage for 0.5-3KV, and heating the substrate to 50-90 ℃ to obtain a composite film; 5) And (3) drying and acidifying the composite membrane obtained in the step (4) to obtain the composite proton exchange membrane.
Firstly, carrying out surface modification on graphene oxide by using adenosine triphosphate to modify the graphene oxide, and then preparing a two-dimensional ATP@GO/polymer resin composite proton exchange membrane by using the graphene oxide modified by the adenosine triphosphate; graphene oxide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are dispersed in a phosphate buffer solution under the action of ultrasound, the pH value of the phosphate buffer solution is usually 6-8, the continuous reaction after adenosine triphosphate is added is also carried out under the action of ultrasound, the obtained composite membrane is dried under the action of ultrasound, the acidification process is to protonate the composite membrane, and the protonation process is carried out by adopting the concentration of 1-2mol L -1 Acidifying with dilute sulfuric acid for 6-24 hr. The invention has simple film forming process and good safetyThe method is environment-friendly, has no special requirement on equipment, can be widely used for accurate preparation of proton exchange membranes and effective regulation and control of structures thereof, is easy to realize large-scale production, and has wide application prospect.
As a preferred embodiment, in the step 1), the mass ratio of graphene oxide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is 1:2-4:6-12; preferably, in the step 1), the reaction time is 0.5 to 2 hours. According to the invention, graphene oxide is firstly activated in two solvents of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, a carboxyl group in the graphene oxide is activated, and a carboxyl ammonia reaction is catalyzed, so that carboxyl on GO and amino in ATP are subjected to a carboxyl ammonia reaction, and ATP is immobilized on the GO surface; the reaction time was controlled to sufficiently activate the carboxyl group.
As a preferred embodiment, in the step 2), the mass ratio of adenosine triphosphate to graphene oxide is 1:1-10:1; preferably, in the step 2), the ambient temperature is 20-40 ℃; preferably, in the step 2), the reaction time is continued for 2 to 4 hours. According to the invention, the graphene oxide is modified by adopting the adenosine triphosphate, the mass ratio of the adenosine triphosphate to the graphene oxide is controlled, if the mass ratio of ATP to GO is small, the ATP amount finally immobilized on the GO surface is small, the number of functional groups on the functionalized GO surface is limited, and the effect of a nano channel in the composite membrane is reduced; in contrast, if the ATP immobilization amount is excessive, repeated accumulation of ATP on the surface of GO is triggered, the water storage structure of GO in the composite membrane is destroyed, and the interaction between GO and a polymer matrix is affected; the invention controls the proper reaction temperature to make the reaction fully proceed; the present invention controls the proper reaction time, which is at least 2 hours above to ensure the above process due to the slower progress of the synthesis reaction.
As a preferred embodiment, in the step 4), the spraying speed is 0.05-0.25mL min -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, in the step 4), the spraying time is 0.5-2h; preferably, in the step 4), the electrostatic voltage is 0.8-2KV; preferably, in the step 4), the temperature of the heated substrate is 60 DEG C-80 ℃. The invention adopts the electrostatic spraying technology to carry out self-assembly, accurately controls the electrostatic layer-by-layer self-assembly process, can realize the accurate preparation of the composite film, and can control the size of the finally formed composite film through liquid spraying time, liquid spraying speed and the like; in addition, the spraying technology has stroke control, i.e. the needle head can move repeatedly to control the film forming size.
As a preferred embodiment, the mass percentage of the polymer resin in the mixed solution of the step 3) is 1-25%; preferably, the concentration of the polymer resin in the mixed solution of the step 3) is 2-5%; preferably, in the step 3), the polar solvent is any one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, acetone, water, ethanol, methanol, propanol, isopropanol, ethylene glycol or glycerol. According to the invention, the mass percentage of the polymer resin in the mixed solution influences the connection structure strength of the polymer resin and the graphene oxide modified by the adenosine triphosphate, and if the mass percentage of the polymer resin in the mixed solution is too high, the solution viscosity is excessively high, so that two defects are caused: (1) graphene oxide dispersion is not uniform; (2) polymer spraying is not easy to realize; because the polymer resin is easier to disperse in the polar solvent, and simultaneously, the ATP@GO powder can be well dispersed in the polar solvent, the reaction of the polymer resin and the ATP@GO is facilitated to be promoted, and the reaction is enabled to be full.
In yet another aspect, the invention provides the use of a graphene oxide polymer composite proton exchange membrane for assembling a fuel cell. The composite proton exchange membrane is used for a fuel cell, wherein the graphene oxide modified by the adenosine triphosphate can effectively serve as a barrier layer of methanol molecules, fuel and oxidant are isolated, electrons are isolated, protons are specifically conducted, the permeation rate of the fuel is delayed, the selectivity of the proton exchange membrane is improved, and the performance of the fuel cell is improved.
Compared with the prior art, the invention has the beneficial effects that: the composite proton exchange membrane is a two-dimensional composite proton exchange membrane, the graphene oxide modified by the adenosine triphosphate is in an ordered lamellar distribution structure in the composite proton exchange membrane, the structure of the tightly combined graphene oxide and polymer resin is provided with long-range continuity by the sequentially distributed graphene oxide modified by the adenosine triphosphate, and strong interaction is generated between phosphoric acid groups and sulfonic acid groups in a graphene oxide channel modified by the adenosine triphosphate, so that rich proton transfer sites are provided for the composite proton exchange membrane, the cooperative reinforcement of a proton transfer carrier is realized, the proton transfer energy barrier is reduced, and a high-efficiency proton transfer channel is formed, thereby promoting the improvement of the proton conductivity of the composite membrane; in addition, the layered arrangement structure of the graphene oxide in the composite proton exchange membrane can effectively serve as a barrier layer of methanol molecules, so that the permeation rate of fuel is delayed, and the selectivity of the proton exchange membrane is improved. The composite proton exchange membrane has simple film forming process, is safe and environment-friendly, can be widely used for accurate preparation of the proton exchange membrane and effective regulation and control of the structure of the proton exchange membrane, is easy to realize large-scale production, and has wide application prospect. The composite proton exchange membrane can be used for assembling fuel cells, has obviously improved barrier property to small molecules such as methanol and the like compared with a perfluorosulfonic acid proton exchange membrane-Nafion membrane, still shows extremely high proton conduction performance in a high-temperature low-humidity environment with 140 ℃ and 50% RH, and has obviously improved selectivity compared with the perfluorosulfonic acid proton exchange membrane-Nafion membrane by 2.03-6.09 times compared with the perfluorosulfonic acid proton exchange membrane-Nafion membrane.
Drawings
FIG. 1 is a transmission electron micrograph of ATP@GO nanoplatelets obtained according to an embodiment of the invention;
FIG. 2 is an infrared spectrum of ATP@GO nanoplatelets and untreated GO obtained in accordance with an embodiment of the present invention;
FIG. 3 is a photograph of a scanning electron microscope of a cross section of a composite proton exchange membrane according to an embodiment of the present invention;
wherein, in fig. 2: 1-untreated GO;2-ATP@GO nano-sheets.
Detailed Description
The following description of the present invention will be made more complete and clear in view of some embodiments of the present invention, and it is evident that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention discloses a preparation method of a graphene oxide polymer composite proton exchange membrane, which comprises the following steps:
1) Taking Graphene Oxide (GO), ultrasonically dispersing 10mg of graphene oxide, 34.5mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 103.6mg of N-hydroxysuccinimide in a phosphate buffer solution with a pH value of 6.86, and performing an activation reaction for 1h to obtain a dispersion solution;
2) Taking Adenosine Triphosphate (ATP), adding 50mg of adenosine triphosphate into the dispersion solution, and continuing ultrasonic reaction for 3 hours at 20 ℃; finally, repeatedly centrifuging, washing with absolute ethyl alcohol and deionized water, and drying in a vacuum oven to obtain ATP@GO powder;
3) Dissolving 20mg of the ATP@GO powder into 20mL of absolute ethyl alcohol to obtain an ATP@GO solution; then, taking 20mL of perfluorinated sulfonic acid resin-perfluorinated sulfonic acid Nafion solution with the mass concentration of 5%, adding ATP@GO solution into the perfluorinated sulfonic acid Nafion solution, carrying out ultrasonic treatment and blending to obtain a mixed solution, wherein the mass percentage of ATP@GO powder in the mixed solution and Nafion polymer resin is 2%;
4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution layer by layer on a high-temperature film forming substrate, wherein the spraying speed is 0.08mL min -1 The spraying time is 5h, the electrostatic voltage is 0.5KV, the path of the spraying needle head travel is 3X 3cm, and the temperature of the heated substrate is 70 ℃ to obtain a composite film;
5) Placing the above composite membrane in a 90 deg.C oven, heat treating for 2 hr, and soaking in 1M H 2 SO 4 Soaking in the solution for 6 hours to fully protonate the composite membrane, thus obtaining the composite proton exchange membrane.
The atp@go powder obtained in this example is scanned on a transmission electron microscope of model H7650 manufactured by HITACHI corporation, and as can be seen from fig. 1, the atp@go powder obtained in the invention has an obvious single-layer lamellar structure, and after ATP loading treatment, the morphological structure of GO is not damaged obviously.
The ATP@GO powder obtained in the embodiment, namely ATP@GO nano sheets, and raw material Graphene Oxide (GO), namely untreated GO, are respectively placed on a Nicolet iS50 type infrared spectrum analyzer manufactured by Siemens Feishmania technology company for infrared spectrum (FTIR) analysis, and as can be seen from figure 2, GO iS 3269cm -1 ，1728cm -1 And 1633cm -1 Characteristic peaks appear at the positions, and the three characteristic peaks respectively correspond to an O-H telescopic vibration peak in hydroxyl and carboxyl, a C=O telescopic vibration peak in carboxyl and an sp2 hybridized C=C telescopic vibration peak on GO carbocycle; after introducing ATP into GO, the obtained ATP@GO powder is 3269cm -1 The extension vibration peak of O-H in hydroxyl and carboxyl is shown at 1728cm -1 The peak intensity of C=O in the carboxyl group is obviously reduced and is 1633cm -1 The vicinity shows a strong peak more pronounced than GO, because the positions of c=o and c=c stretching vibration peaks in the generated amide bond are closer, and the peak intensity is obviously improved at the position affected by the positions, so that the peaks are superimposed peaks of c=o and c=c stretching vibration peaks. Furthermore, the ATP@GO powder was at 1372 and 1097cm, respectively -1 There are also two new peaks, caused by the stretching vibrations of p=o and P-O, respectively. The above results indicate that ATP molecules have been successfully introduced into the surface of GO.
The section of the composite proton exchange membrane obtained in this example is scanned on a scanning electron microscope of model S4800 manufactured by Hitachi, and as can be seen from FIG. 3, the prepared composite membrane is compact and defect-free, the ATP@GO two-dimensional nano sheets are in a remarkable sheet-shaped stacking arrangement structure, and are uniformly dispersed in a matrix and tightly combined with a Nafion matrix, no obvious phase separation exists, so that the compact composite membrane can be prepared by the electrostatic layer-by-layer self-assembly method.
Example two
The preparation method of the graphene oxide polymer composite proton exchange membrane comprises the following steps:
1) Taking Graphene Oxide (GO), dispersing 10mg of graphene oxide, 10mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 80mg of N-hydroxysuccinimide in a phosphate buffer solution by ultrasonic, and performing an activation reaction for 3 hours to obtain a dispersion solution;
2) Taking Adenosine Triphosphate (ATP), adding 400mg of adenosine triphosphate into the dispersion solution obtained in the step 1), continuously reacting for 4 hours at the temperature of 30 ℃, filtering, washing and drying to obtain ATP@GO powder;
3) Dissolving 5g of polymer resin, namely sulfonated polyether sulfone, in 20mL of N, N-dimethylformamide to obtain a polymer resin solution; dissolving 5mg of the ATP@GO powder in 20mL of N, N-dimethylformamide to obtain an ATP@GO solution; mixing a polymer resin solution and an ATP@GO solution, and carrying out sufficient ultrasonic blending to obtain a mixed solution, wherein the mass percentage of ATP@GO powder and Nafion polymer resin in the mixed solution is 0.1%;
4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution obtained in the step 3) on a high-temperature film forming substrate layer by layer, wherein the spraying speed is 0.01mL min -1 Spraying liquid for 2h, wherein the electrostatic voltage is 1.5KV, and the temperature of a heating substrate is50 ℃ to obtain the composite proton exchange membrane;
5) Placing the above composite membrane in an oven at 80deg.C, heat treating for 1 hr, and soaking in 2M H 2 SO 4 Soaking in the solution for 4 hours to fully protonate the composite membrane, thus obtaining the composite proton exchange membrane.
Example III
The preparation method of the graphene oxide polymer composite proton exchange membrane comprises the following steps:
1) Taking Graphene Oxide (GO), dispersing 10mg of graphene oxide, 60mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide in a phosphate buffer solution by ultrasonic, and performing an activation reaction for 1h to obtain a dispersion solution;
2) Taking Adenosine Triphosphate (ATP), adding 200mg of adenosine triphosphate into the dispersion solution obtained in the step 1), continuously reacting for 1h at 50 ℃, filtering, washing and drying to obtain ATP@GO powder;
3) Taking 1g of polymer resin, namely sulfonated polybenzoxazole, and dissolving the polymer resin into 20mL of dimethyl sulfoxide to obtain a polymer resin solution; dissolving 150mg of the ATP@GO powder in 40mL of dimethyl sulfoxide to obtain an ATP@GO solution; mixing a polymer resin solution and an ATP@GO solution, and carrying out sufficient ultrasonic blending to obtain a mixed solution, wherein the mass percentage of ATP@GO powder and Nafion polymer resin in the mixed solution is 15%;
4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution obtained in the step 3) on a high-temperature film forming substrate layer by layer, wherein the spraying speed is 0.3mL min -1 The spraying time is 2h, the electrostatic voltage is 3KV, the temperature of the heated substrate is 90 ℃, and the composite proton exchange membrane is obtained.
5) Placing the above composite membrane in oven at 60deg.C, heat treating for 6 hr, and soaking in 2M H 2 SO 4 Soaking in the solution for 4 hours to fully protonate the composite membrane, thus obtaining the composite proton exchange membrane.
Example IV
The preparation method of the graphene oxide polymer composite proton exchange membrane comprises the following steps:
1) Taking Graphene Oxide (GO), dispersing 10mg of graphene oxide, 40mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 120mg of N-hydroxysuccinimide in a phosphate buffer solution with a pH value of 6.86 in an ultrasonic manner, and carrying out an activation reaction for 0.1h to obtain a dispersion solution;
2) Taking Adenosine Triphosphate (ATP), adding 0.25mg of adenosine triphosphate into the dispersion solution obtained in the step 1), continuously reacting for 6 hours at the temperature of 30 ℃, filtering, washing and drying to obtain ATP@GO powder;
3) Dissolving 5g of polymer resin-sulfonated polyether ether ketone in 20mL of N, N-dimethylacetamide to obtain a polymer resin solution; dissolving 250mg of the ATP@GO powder in 50mL of N, N-dimethylacetamide to obtain an ATP@GO solution; mixing a polymer resin solution and an ATP@GO solution, and carrying out sufficient ultrasonic blending to obtain a mixed solution, wherein the mass percentage of ATP@GO powder and Nafion polymer resin in the mixed solution is 5%;
4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution obtained in the step 3) on a high-temperature film forming substrate layer by layer, wherein the spraying speed is 0.1mL min -1 Spraying liquid for 0.2h, wherein the electrostatic voltage is 1KV, and the temperature of a heating substrate is 80 ℃ to obtain the composite proton exchange membrane;
5) Placing the above composite membrane in oven at 70deg.C, heat treating for 3 hr, and soaking in 1M H 2 SO 4 Soaking in the solution for 24 hours to fully protonate the composite membrane, thus obtaining the composite proton exchange membrane.
Comparative example one
A method for preparing a perfluorosulfonic acid membrane, comprising the steps of:
1) Adding 20mL of absolute ethyl alcohol into Naifon solution of perfluorinated sulfonic acid with the same volume and the mass concentration of 5%, and fully and uniformly dispersing by ultrasonic to obtain a mixed solution;
2) Adopting an electrostatic layer-by-layer self-assembly technology, and utilizing an electrostatic spraying instrument to self-assemble the mixed solution layer-by-layer on a high-temperature film-forming substrate, wherein the spraying speed is 0.15mL min -1 Spraying liquid for 2 hours, wherein the electrostatic voltage is 1KV, and the temperature of a heated substrate is 70 ℃ to obtain a composite film;
3) Placing the above composite membrane in a 90 deg.C oven, heat treating for 2 hr, and soaking in 1M H 2 SO 4 Soaking in the solution for 6 hours to fully protonate the composite membrane, thus obtaining the perfluorosulfonic acid proton exchange membrane.
Comparative example two
The preparation method of the graphene oxide polymer composite proton exchange membrane comprises the following steps:
1) Dissolving the 10mg pure GO powder in 20mL absolute ethyl alcohol to obtain GO solution; then, taking 20mL of perfluorinated sulfonic acid resin-perfluorinated sulfonic acid Nafion solution with the mass concentration of 5%, adding the GO solution into the perfluorinated sulfonic acid Nafion solution, carrying out ultrasonic mixing to obtain a mixed solution, wherein the mass percentage of the GO powder and Nafion polymer resin in the mixed solution is 1%;
2) Adopting an electrostatic layer-by-layer self-assembly technology, utilizing an electrostatic spraying instrument to self-assemble the mixed solution layer-by-layer on a high-temperature film-forming substrate, and spraying liquidThe speed is 0.15mL min -1 Spraying liquid for 2 hours, wherein the electrostatic voltage is 1KV, and the temperature of a heated substrate is 70 ℃ to obtain a composite film;
3) Placing the above composite membrane in a 90 deg.C oven, heat treating for 2 hr, and soaking in 1M H 2 SO 4 Soaking in the solution for 6h to fully protonate the composite membrane to obtain the contrast composite proton exchange membrane.
The four composite proton exchange membranes obtained in examples one to four of the present invention and the perfluorosulfonic acid proton exchange membranes obtained in comparative examples one and two were subjected to performance tests, respectively, including membrane thickness, proton conductivity at 80 ℃ and 100% rh, and proton conductivity at 140 ℃ and 50% rh, wherein the membrane thickness was measured by a thickness gauge, the proton conductivity was measured according to ac impedance, and the measurement results are shown in table 1.
As can be seen from Table 1, the membrane thickness of the composite proton exchange membrane is 57-225 μm, the membrane thickness of the first comparative example is 147 μm, the membrane thickness of the second comparative example is 152 μm, the membrane thickness of the composite proton exchange membrane can be accurately regulated and controlled by a spraying process, and the composite proton exchange membrane with different thicknesses can be regulated and controlled according to actual needs, so that the use is convenient; the methanol permeability coefficient of the composite proton exchange membrane is 1.23-3.31X10 -7 cm 2 s -1 However, the methanol permeability coefficient of comparative example one was 15.59X10 -7 cm 2 s -1 The methanol permeability coefficient of comparative example II was 7.69×10 -7 cm 2 s -1 The composite proton exchange membrane has obviously improved barrier property to small molecules such as methanol and the like compared with a perfluorinated sulfonic acid proton exchange membrane, namely a Nafion membrane (namely a comparative example I) and a comparative composite proton exchange membrane (namely a comparative example II); the proton conductivity of the composite proton exchange membrane of the invention is 0.143-0.305S cm under the environment of 80 ℃ and 100% relative humidity -1 The proton conductivity of the composite proton exchange membrane of the invention is 0.065-0.195S cm under the environment of 140 ℃ and 50% relative humidity -1 The method comprises the steps of carrying out a first treatment on the surface of the However, comparative example one was conducted in an environment where the temperature was 80℃and the relative humidity was 100%Proton conductivity of 0.122S cm -1 Comparative example one proton conductivity of 0.032S cm at 140℃and 50% relative humidity -1 The method comprises the steps of carrying out a first treatment on the surface of the Comparative example two proton conductivity at 80℃and 100% relative humidity was 0.139S cm -1 Comparative example II proton conductivity at 140℃and 50% relative humidity was 0.048S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the This shows that the composite proton exchange membrane of the invention still shows extremely high proton conductivity at 140 ℃ and 50% RH high temperature and low humidity environment, which is improved by 2.03-6.09 times compared with the perfluorinated sulfonic acid proton exchange membrane, namely Nafion membrane (namely comparative example I), and is also improved by 1.35-4.06 times compared with the comparative composite proton exchange membrane (namely comparative example II). The selectivity of the composite proton exchange membrane is 2.06-4.15X10 5 S s cm -3 The method comprises the steps of carrying out a first treatment on the surface of the However, the selectivity of comparative example one was only 0.51X10 5 S s cm -3 The selectivity of comparative example II was 1.10X10 5 S s cm -3 Compared with a perfluorinated sulfonic acid proton exchange membrane, namely a Nafion membrane (namely a first comparative example) and a composite proton exchange membrane (namely a second comparative example), the method has obvious improvement. Therefore, compared with the pure Nafion membrane (i.e. the first comparative example) and the composite proton exchange membrane (i.e. the second comparative example), the proton conductivity and the methanol permeability of the composite proton exchange membrane are improved to a great extent, and particularly under the high-temperature low-humidity condition, the performance of the composite proton exchange membrane is improved more remarkably; compared with the pure Nafion membrane (i.e. the first comparative example) and the composite proton exchange membrane (i.e. the second comparative example), the selectivity of the composite proton exchange membrane is also improved to a great extent, and the selectivity of the composite proton exchange membrane is obviously improved.
TABLE 1 Performance test results of different proton exchange membranes
Therefore, compared with the prior art, the invention has the beneficial effects that: the composite proton exchange membrane is a two-dimensional composite proton exchange membrane, the graphene oxide modified by the adenosine triphosphate is in an ordered lamellar distribution structure in the composite proton exchange membrane, the structure of the tightly combined graphene oxide and polymer resin is provided with long-range continuity by the sequentially distributed graphene oxide modified by the adenosine triphosphate, and strong interaction is generated between phosphoric acid groups and sulfonic acid groups in a graphene oxide channel modified by the adenosine triphosphate, so that rich proton transfer sites are provided for the composite proton exchange membrane, the cooperative reinforcement of a proton transfer carrier is realized, the proton transfer energy barrier is reduced, and a high-efficiency proton transfer channel is formed, thereby promoting the improvement of the proton conductivity of the composite membrane; in addition, the layered arrangement structure of the graphene oxide in the composite proton exchange membrane can effectively serve as a barrier layer of methanol molecules, so that the permeation rate of fuel is delayed, and the selectivity of the proton exchange membrane is improved. The composite proton exchange membrane has simple film forming process, is safe and environment-friendly, can be widely used for accurate preparation of the proton exchange membrane and effective regulation and control of the structure of the proton exchange membrane, is easy to realize large-scale production, and has wide application prospect. The composite proton exchange membrane can be used for assembling fuel cells, has obviously improved barrier property to small molecules such as methanol and the like compared with a perfluorosulfonic acid proton exchange membrane-Nafion membrane, still shows extremely high proton conduction performance in a high-temperature low-humidity environment with 140 ℃ and 50% RH, and has obviously improved selectivity compared with the perfluorosulfonic acid proton exchange membrane-Nafion membrane by 2.03-6.09 times compared with the perfluorosulfonic acid proton exchange membrane-Nafion membrane.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (11)
1. The preparation method of the graphene oxide polymer composite proton exchange membrane is characterized by comprising the following steps of:
1) Taking graphene oxide, wherein the size of the sheet diameter of the graphene oxide is 0.1-3 mu m, the thickness of the graphene oxide is 0.5-2.5-nm, dispersing graphene oxide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in a phosphate buffer solution according to the mass ratio of 1:1-6:8-20, and performing an activation reaction for 0.1-3h to obtain a dispersion solution;
2) Adding adenosine triphosphate into the dispersion solution obtained in the step 1), wherein the mass ratio of the adenosine triphosphate to the graphene oxide is 1:40-40:1, and continuously reacting at 20-50 ℃ for 1-6h, filtering, washing and drying to obtain ATP@GO powder;
3) Taking polymer resin, wherein the polymer resin is any one of perfluorinated sulfonic acid resin, sulfonated polyether ketone resin, sulfonated polysulfone resin, sulfonated polyimide resin, sulfonated polystyrene resin and sulfonated polybenzoxazole resin, and dissolving the polymer resin in a polar solvent to obtain a polymer resin solution; dissolving the ATP@GO powder obtained in the step 2) in a polar solvent to obtain an ATP@GO solution; mixing a polymer resin solution and an ATP@GO solution to obtain a mixed solution, wherein the ATP@GO powder accounts for 0.1-15% of the mass of the polymer resin in the mixed solution;
4) Adopting an electrostatic layer-by-layer self-assembly technology to self-assemble the mixed solution obtained in the step 3) on a high-temperature film-forming substrate layer by layer, wherein the spraying speed is 0.01-0.3mL min −1 Spraying liquid for 0.2-5h, electrostatic voltage for 0.5-3KV, and heating substrate at 50-90deg.C to obtain composite film;
5) Drying and acidifying the composite membrane obtained in the step 4) to obtain a composite proton exchange membrane;
the composite proton exchange membrane comprises polymer resin and oxidized graphene modified by adenosine triphosphate.
2. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 1, wherein the method comprises the following steps:
in the step 1), the mass ratio of graphene oxide to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to N-hydroxysuccinimide is 1:2-4:6-12.
3. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 2, wherein the method comprises the following steps:
in the step 1), the reaction time is 0.3-2 h.
4. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 1, wherein the method comprises the following steps:
in the step 2), the mass ratio of the adenosine triphosphate to the graphene oxide is 1:1-10:1.
5. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 4, wherein the method comprises the following steps:
in the step 2), the ambient temperature is 20-40 ℃, and the continuous reaction time is 2-4h.
6. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 1, wherein the method comprises the following steps:
in the step 4), the spraying speed is 0.05-0.25mL min −1 The spraying time is 0.5-2h, the electrostatic voltage is 0.8-2KV, and the temperature of the heated substrate is 60-80 ℃.
7. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 1, wherein the method comprises the following steps:
in the mixed solution of the step 3), the mass percentage of the polymer resin in the mixed solution is 1-25%.
8. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 7, wherein the method comprises the following steps:
in the mixed solution of the step 3), the mass percentage of the polymer resin in the mixed solution is 2-5%.
9. The method for preparing the graphene oxide polymer composite proton exchange membrane according to claim 1, wherein the method comprises the following steps:
in the step 3), the polar solvent is any one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetone, water, ethanol, methanol, propanol, isopropanol, ethylene glycol or glycerol.
10. The graphene oxide polymer composite proton exchange membrane is characterized in that:
the graphene oxide polymer composite proton exchange membrane is prepared according to the preparation method of the graphene oxide polymer composite proton exchange membrane in any one of claims 1-9.
11. Use of the graphene oxide polymer composite proton exchange membrane according to claim 10, characterized in that:
the composite proton exchange membrane is used for assembling a fuel cell.
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