CN113078343A - MOF (metal organic framework) based laminated composite proton exchange membrane as well as preparation method and application thereof - Google Patents
MOF (metal organic framework) based laminated composite proton exchange membrane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fuel cells, and particularly discloses a preparation method of an MOF (metal organic framework) base laminated composite proton exchange membrane, which comprises the following steps: 1) preparing MOF nanosheets; 2) preparing a MOF nanosheet layered membrane from the MOF nanosheets prepared in the step 1); 3) and introducing a polymer into the MOF nanosheet layered membrane to obtain the MOF-based layered composite proton exchange membrane. The MOF-based laminated composite proton exchange membrane prepared by the invention has excellent proton conductivity under the condition of low humidity.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a Metal Organic Framework (MOF) based laminated composite proton exchange membrane, and a preparation method and application thereof.
Background
The hydrogen fuel cell is a novel power generation device which directly converts chemical energy into electric energy and has the characteristics of high efficiency, high energy density, low pollution and the like; when pure hydrogen is used as the fuel, the product is water. Proton exchange membrane (Proton Ex)change Membrane, PEM) is the heart of the cell, and its proton conductivity determines cell performance and structural stability determines cell life. PEMs developed at present are basically polymeric membranes, represented by perfluorosulfonic acid polymeric membranes Nafion. The Nafion membrane has a unique bicontinuous phase structure under saturated humidity, and a continuous sulfonic acid ion channel can conduct protons at high speed (10 to 10)-1S·cm-1). However, membrane ion channels are highly water dependent. At low humidity, the ion channels shrink and even collapse, and the membrane conductivity decays by more than three orders of magnitude. Therefore, the design and controlled preparation of high conductivity PEMs at low humidity is an important task in the fields of membrane technology and energy.
In recent years, the use of Metal Organic Framework (MOF) materials for proton conduction has received increasing attention. The MOFs have the characteristics of easily adjustable structure, high specific surface area, high porosity and the like, so that guest molecules can be effectively distributed in the MOFs, and the MOFs comprise various small molecules (such as imidazole, triazole and the like) and high molecular chain segments (such as PEO, ssDNA and the like), and are an ideal porous platform for constructing multifunctional materials. However, in the process of using MOFs as electrolyte material, there is still an important challenge how to prepare crystalline material such as MOFs into film. The traditional method is to directly compress the MOFs powder into tablets or directly react to prepare the film through direct growth or a secondary growth method assisted by seed crystals. However, the proton transfer process of the MOFs membrane prepared by the methods is limited by the bulk crystal phase and the grain boundary, and the proton conduction capability of the membrane is weak (10)-7～10-3S·cm-1). The incorporation of MOFs particles into polymer matrices to prepare Mixed Matrix Membranes (MMMs) is another common film-forming method. However, the MOFs are easy to agglomerate in the film, the compatibility with the common interface between the MOFs and the polymer is poor, a continuous hydrogen bond network cannot be formed, and the rapid transfer of protons is not facilitated.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a MOF-based layered composite proton exchange membrane having excellent proton conductivity under low humidity conditions, and a preparation method and application thereof.
The invention provides a preparation method of an MOF (metal-organic framework) base laminated composite proton exchange membrane, which comprises the following steps of:
1) preparing MOF nanosheets;
2) preparing a MOF nanosheet layered membrane from the MOF nanosheets prepared in the step 1);
3) and introducing a polymer into the MOF nanosheet layered membrane to obtain the MOF-based layered composite proton exchange membrane.
According to the invention, the MOF nanosheets can be prepared using methods conventional in the art. Preferably, step 1) comprises: dissolving a ligand and a metal salt in a reaction solvent, adding a catalyst, reacting to form a colloidal suspension, carrying out ultrasonic treatment on the colloidal suspension, separating, washing and drying to obtain the MOF nanosheet.
In the present invention, the metal salt may be at least one selected from a transition metal salt and a lanthanide metal salt. Preferably, the metal salt is cobalt chloride hexahydrate (CoCl)2·6H2O) and nickel chloride hexahydrate (NiCl)2·6H2O), the molar ratio of cobalt chloride hexahydrate and nickel chloride hexahydrate being from 1: 2 to 2: 1, preferably 1: 1.
According to the present invention, the ligand may be at least one of an aromatic carboxylic acid and a nitrogen-containing heterocyclic compound. Preferably, the ligand is terephthalic acid, 4' -biphenyldicarboxylic acid or p-terphenyl-4, 4 "dicarboxylic acid.
In the present invention, the molar ratio of the metal salt to the ligand may be 1: 9 to 9: 1, preferably 1: 1.
According to the present invention, the reaction solvent comprises a first solvent, water and ethanol, and the first solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-diethylformamide, tetrahydrofuran, pyrrolidone, and dimethylsulfoxide. Preferably, the first solvent is N, N-Dimethylformamide (DMF). The volume ratio of the first solvent, water and ethanol may be 20-10: 1, preferably 16: 1.
Preferably, the catalyst is triethylamine.
In the invention, the ligand and the metal salt are dissolved in the reaction solvent by firstly dissolving the ligand in the reaction solvent and adding the catalyst, and then dissolving the metal salt in the reaction solvent, and the method specifically comprises the following steps: adding the ligand into the reaction solvent under stirring, then adding the catalyst, adding the metal salt after the ligand is completely dissolved, and continuously stirring for reaction for 0.5-1h to obtain uniform colloidal suspension.
In step 1) of the present invention, the ultrasonic treatment is performed in an ultrasonic machine, and the colloidal suspension is treated under a closed condition for 8-20h, preferably 16 h. The separation step is centrifugal separation, washing is washing with ethanol for 3-5 times, and drying is drying at room temperature.
In the present invention, step 2) comprises: preparing MOF nano sheets into MOF nano sheet dispersion liquid, preferably preparing MOF nano sheet ethanol dispersion liquid. And forming a film by using the MOF nanosheet dispersion liquid through suction filtration, spin coating, deposition or electrostatic atomization to obtain the MOF nanosheet layered film.
Preferably, the concentration of the MOF nanosheet dispersion is 0.1-5g/L, and more preferably 0.1 g/L.
Preferably, the MOF nanosheet dispersion is debubbled by ultrasound for 20-40min, preferably 30min, and then membrane preparation is performed. And forming a film by the MOF nanosheet dispersion liquid through a suction filtration method, wherein the suction filtration pressure is 5-10 MPa.
According to the invention, step 3) comprises: dissolving a polymer in a second solvent to prepare a polymer solution, introducing the polymer in the polymer solution into the MOF nanosheet layered membrane by a suction filtration method, and drying (drying at room temperature) to obtain the MOF-based layered composite proton exchange membrane; the pressure of the suction filtration is 5-10MPa (which can be the same as the suction filtration pressure in the preparation of the MOF nanosheet layered membrane).
Preferably, the polymer is at least one of perfluorosulfonic acid resin and derivatives thereof, sulfonated polyarylether and derivatives thereof, sulfonated polyaryletherketone and derivatives thereof, and sulfonated polyethersulfoneketone and derivatives thereof, and more preferably perfluorosulfonic acid resin (Nafion). The solvent of the polymer solution may be a solvent for forming the above-mentioned polymer into a homogeneous solution, preferably N, N-Dimethylacetamide (DMAC), and the concentration of the polymer solution is 0.1 to 20 wt%, preferably 0.25 wt%.
The second aspect of the invention provides the MOF-based laminated composite proton exchange membrane prepared by the preparation method.
The thickness of the MOF-based laminated composite proton exchange membrane prepared by the invention can be 5-200 μm, and is preferably 20 μm.
A third aspect of the invention provides the use of the MOF-based layered composite proton exchange membrane described above in a fuel cell.
The operating steps and parameters not defined in the present invention can be selected conventionally according to the prior art.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the MOF-based laminated composite proton exchange membrane prepared by the invention, MOF nano sheets with rich defect holes on the surfaces are utilized to construct a laminated membrane, so that surface pore passages of the MOF nano sheets form continuous vertical nano channels; and then introducing the polymer into the nano-channel to form a hydrogen bond network which is continuous in the vertical direction, thereby constructing a rapid proton transfer channel. Compared with commercial Nafion membranes, the transfer channel does not shrink or collapse under low humidity and has excellent proton conduction performance.
2. The preparation method of the MOF-based laminated composite proton exchange membrane has the advantages of simple operation process and mild preparation conditions, and the MOF-based laminated composite proton exchange membrane prepared by the preparation method is applied to the field of fuel cells and can effectively improve the proton conductivity of the membrane under the condition of low humidity.
Drawings
Fig. 1 is a graph comparing temperature-proton conductivity of membranes of each example and comparative example 1.
Fig. 2 is a graph comparing humidity-proton conductivity of the membranes of example 3, comparative example 1, and comparative example 2.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
A preparation method of an MOF base laminated composite proton exchange membrane comprises the following steps:
(1) firstly, 32mL of DMF, 2mL of ethanol and 2mL of water are added into a 100mL beaker; then adding 0.75mmol of terephthalic acid while stirring; then 0.8mL of triethylamine was added; after the terephthalic acid was completely dissolved, 0.375mmol of CoCl was added2·6H2O and 0.375mmol of NiCl2·6H2And O, stirring for 30min to obtain a uniform colloidal suspension. Then, the colloidal suspension was continuously sonicated under closed conditions for 16 h. And finally, centrifuging, washing for 3 times by using ethanol, and drying at room temperature to obtain A product MOF nanosheet, which is recorded as MN-A.
(2) And (3) dispersing 40mg of MN-A powder in 400mL of ethanol, and performing ultrasonic dispersion to obtain MN-A ethanol dispersion liquid. And adding the obtained MN-A ethanol dispersion liquid into A suction filtration device for suction filtration, and obtaining the MN-A layered membrane after the suction filtration is finished.
(3) And (3) adding 80mL of 0.25 wt% Nafion solution (solvent is DMAC) above the MN-A layered membrane obtained in the step (2), performing suction filtration, and drying at room temperature after the suction filtration is finished to obtain the MOF-based layered composite proton exchange membrane, wherein the membrane thickness is 20 micrometers and is recorded as MN-A @ Nafion.
Example 2
In step (1), terephthalic acid was replaced with 4,4' -biphenyldicarboxylic acid, and the remaining steps and parameters were the same as in example 1. The prepared MOF-based laminated composite proton exchange membrane is marked as MN-B @ Nafion.
Example 3
In step (1), terephthalic acid was replaced with p-terphenyl-4, 4' dicarboxylic acid, and the remaining steps and parameters were the same as in example 1. The prepared MOF-based laminated composite proton exchange membrane is marked as MN-C @ Nafion.
Comparative example 1
A commercial Nafion117 membrane was selected as comparative example 1, noted Nafion 117.
Comparative example 2
80mL of 0.25 wt% Nafion solution was directly mixed with 40mg of MN-C (prepared by step (1) of example 3), and after the solvent was evaporated to dryness, the dried mixture powder was compressed at 20MPa to give a tablet, which was designated as comparative example 2 as MN-C + Nafion.
The membranes of examples 1-3 and comparative examples 1-2 were subjected to proton conductivity tests:
proton conductivity (. sigma., S.cm) of the membrane was measured using a ParStat MC 1000 electrochemical workstation manufactured by Princeton-1) The oscillating voltage is 10mV, and the scanning frequency range is 1M-10 Hz. The test temperature and humidity were controlled by a MTS-740 type membrane test unit manufactured by Scribner Associates inc. The stabilization time at each test temperature and humidity was 1 h.
Proton conductivity was calculated from the following formula:
wherein R is a film resistance (Ω), L is a film thickness (cm), and A is a contact area (cm) of the film with the electrode2)。
Proton conductivity results for MN-A @ Nafion at 20% relative humidity: at 30 ℃, the membrane impedance was measured to be 1.73. omega. and the proton conductivity was calculated to be 3.58 mS. cm-1(ii) a The membrane impedance was measured to be 0.91. omega. at 50 ℃ and the proton conductivity was calculated to be 6.86 mS. cm-1(ii) a At 80 ℃, the membrane impedance is measured to be 0.37 omega, and the proton conductivity is calculated to be 16.56mS cm-1。
Proton conductivity results for MN-B @ Nafion at 20% relative humidity: at 30 ℃, the membrane impedance was measured to be 0.97. omega. and the proton conductivity was calculated to be 7.18 mS. cm-1(ii) a The membrane impedance was measured to be 0.52. omega. at 50 ℃ and the proton conductivity was calculated to be 13.44 mS. cm-1(ii) a The membrane impedance was measured to be 0.25. omega. at 80 ℃ and the proton conductivity was calculated to be 27.97 mS. cm-1。
Proton conductivity results for MN-C @ Nafion at 20% relative humidity: at 30 ℃, the membrane impedance was measured to be 0.69. omega. and the proton conductivity was calculated to be 10.72 mS. cm-1(ii) a The membrane impedance was measured to be 0.42. omega. at 50 ℃ and the proton conductivity was calculated to be 17.64 mS. cm-1(ii) a At 80 ℃, the membrane impedance is measured to be 0.20 omega, and the proton conductivity is calculated to be 36.12mS cm-1。
Proton conductivity results of Nafion117 at 20% relative humidity: at 30 ℃, the membrane impedance was measured to be 15.19. omega. and the proton conductivity was calculated to be 2.41 mS. cm-1(ii) a The membrane impedance was measured at 50 ℃ to be 8.32. omega. and the proton conductivity was calculated to be 4.4 mS. cm-1(ii) a At 80 ℃, the membrane impedance is measured to be 3.53 omega, and the proton conductivity is calculated to be 10.36mS cm-1。
The temperature-proton conductivity of the membranes of each example and comparative example 1 were compared under the same humidity conditions, as shown in fig. 1.
Proton conductivity results of MN-C @ Nafion at 80 ℃ and different humidity: the membrane impedance was measured to be 0.17. omega. under the condition of 30% RH, and the proton conductivity was calculated to be 40.76 mS. cm-1(ii) a The membrane impedance was measured to be 0.14. omega. under the condition of 50% RH, and the proton conductivity was calculated to be 50.87 mS. cm-1(ii) a The membrane impedance was measured to be 0.08. omega. under the condition of 80% RH, and the proton conductivity was calculated to be 92.58 mS. cm-1。
The proton conductivity results of the Nafion117 membrane under the conditions of temperature of 80 ℃ and different humidity: the membrane impedance was measured to be 3.18. omega. under the condition of 30% RH, and the proton conductivity was calculated to be 11.50 mS. cm-1(ii) a The membrane impedance was measured to be 1.38. omega. under the condition of 50% RH, and the proton conductivity was calculated to be 26.54 mS. cm-1(ii) a The membrane impedance was measured to be 0.45. omega. under the condition of 80% RH, and the proton conductivity was calculated to be 82.16 mS. cm-1。
The proton conductivity results of the MN-C + Nafion membrane under different humidity and at the temperature of 80 ℃ are as follows: the membrane impedance was measured to be 9.24. omega. under the condition of 30% RH, and the proton conductivity was calculated to be 6.06 mS. cm-1(ii) a The membrane impedance was measured to be 4.32. omega. under the condition of 50% RH, and the proton conductivity was calculated to be 12.95 mS. cm-1(ii) a The membrane impedance was measured to be 1.79. omega. under the condition of 80% RH, and the proton conductivity was calculated to be 31.23 mS. cm-1。
The humidity-proton conductivity of the membranes of example 3, comparative example 1 and comparative example 2 were compared under the same temperature conditions, as shown in fig. 2.
As can be seen from fig. 1 and 2, the proton conductivity of the membrane prepared by the present invention is superior to that of the commercial Nafion117 membrane. Meanwhile, the comparison of the data of example 3 and comparative example 2 shows that in the membrane prepared by the invention, Nafion and MOF have synergistic effect, and the specific structure of the membrane brings unique proton conduction performance; the mere mixing does not result in an improvement in the conductivity, indicating the superiority of the film-forming method.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (10)
- A preparation method of an MOF base laminated composite proton exchange membrane is characterized by comprising the following steps:1) preparing MOF nanosheets;2) preparing a MOF nanosheet layered membrane from the MOF nanosheets prepared in the step 1);3) and introducing a polymer into the MOF nanosheet layered membrane to obtain the MOF-based layered composite proton exchange membrane.
- 2. The method of making a MOF-based layered composite proton exchange membrane according to claim 1, wherein step 1) comprises: dissolving a ligand and a metal salt in a reaction solvent, adding a catalyst, reacting to form a colloidal suspension, carrying out ultrasonic treatment on the colloidal suspension, separating, washing and drying to obtain the MOF nanosheet.
- 3. The method of making a MOF-based laminated composite proton exchange membrane according to claim 2, wherein the metal salt is selected from at least one of transition metal salt and lanthanide metal salt; the ligand is at least one of aromatic carboxylic acid and nitrogen-containing heterocyclic compound;the molar ratio of the metal salt to the ligand is 1: 9-9: 1.
- 4. The method of making a MOF-based layered composite proton exchange membrane according to claim 3, wherein the metal salt is a mixture of cobalt chloride hexahydrate and nickel chloride hexahydrate, the molar ratio of cobalt chloride hexahydrate and nickel chloride hexahydrate is 1: 2-2: 1;the ligand is terephthalic acid, 4 '-biphenyldicarboxylic acid or p-terphenyl-4, 4' dicarboxylic acid.
- 5. The method of making a MOF-based laminated composite proton exchange membrane according to claim 2, wherein the reaction solvent comprises a first solvent selected from at least one of N, N-dimethylformamide, N-diethylformamide, tetrahydrofuran, pyrrolidone, dimethylsulfoxide, water, and ethanol; the volume ratio of the first solvent, water and ethanol is 20-10: 1;the catalyst is triethylamine.
- 6. The method of making a MOF-based laminated composite proton exchange membrane according to claim 2, wherein step 2) comprises: preparing MOF nanosheets into MOF nanosheet dispersion liquid; forming a film by using the MOF nanosheet dispersion liquid through suction filtration, spin coating, deposition or electrostatic atomization to obtain an MOF nanosheet layered film;the concentration of the MOF nanosheet dispersion is 0.1-5 g/L; the pressure of the suction filtration is 5-10 MPa.
- 7. The method of making a MOF-based layered composite proton exchange membrane according to claim 1, wherein step 3) comprises: dissolving a polymer in a second solvent to prepare a polymer solution, introducing the polymer in the polymer solution into the MOF nanosheet layered membrane through a suction filtration method, and drying to obtain the MOF-based layered composite proton exchange membrane; the pressure of the suction filtration is 5-10 MPa.
- 8. The preparation method of the MOF-based laminated composite proton exchange membrane according to claim 1 or 7, wherein the polymer is at least one of perfluorinated sulfonic acid resin and derivatives thereof, sulfonated polyarylether and derivatives thereof, sulfonated polyaryletherketone and derivatives thereof, and sulfonated polyethersulfoneketone and derivatives thereof, and the concentration of the polymer solution is 0.1-20 wt%.
- 9. An MOF-based laminated composite proton exchange membrane prepared by the preparation method of any one of claims 1 to 8.
- 10. Use of the MOF-based layered composite proton exchange membrane of claim 9 in a fuel cell.
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