CN112830467A - Method for preparing MOF carbon material with porous structure and catalyst slurry of proton exchange membrane fuel cell comprising carbon material - Google Patents
Method for preparing MOF carbon material with porous structure and catalyst slurry of proton exchange membrane fuel cell comprising carbon material Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 239000000446 fuel Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002002 slurry Substances 0.000 title claims abstract description 37
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000012922 MOF pore Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- -1 transition metal salt Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
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- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical class FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011165 process development Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
Abstract
The invention discloses a method for preparing a porous MOF carbon material, which comprises the following steps: s1: respectively dissolving an organic ligand and a transition metal salt in a certain amount of solvent to prepare a solution with a certain concentration, then measuring a certain volume of transition metal salt solution, dropwise adding the transition metal salt solution into the organic ligand solution, and magnetically stirring at room temperature; s2: obtaining white precipitate, centrifugally washing, drying, and carbonizing at high temperature to obtain the MOF porous carbon material. By adding the catalyst slurry into the proton exchange membrane fuel cell, the conductivity of the slurry is optimized, the mass transfer efficiency in the membrane electrode is improved, the electrochemical active area and the mass specific activity are improved, and the method has certain significance for the subsequent slurry process development.
Description
Technical Field
The invention belongs to the field of proton exchange membrane fuel cell catalysts, and particularly relates to a method for preparing a porous MOF carbon material and a proton exchange membrane fuel cell catalyst slurry containing the carbon material.
Background
With the progress of society, environmental and energy problems are becoming more and more prominent, and countries in the world are searching and developing new clean energy to reduce the dependence on fossil fuel and protect the environment. Fuel cells, one of the most potential electrochemical devices, can deliver chemical energy from a fuel (e.g., hydrogen, methanol, etc.) and an oxidant (e.g., air) continuously to a consumer with virtually zero contamination of the product. The fuel cell may be classified into an alkaline fuel cell, a phosphoric acid fuel cell, a molten carbonate fuel cell, a proton exchange membrane fuel cell, a solid oxide fuel cell, and the like according to the difference of electrolytes in the fuel cell, wherein the Proton Exchange Membrane Fuel Cell (PEMFC) is most expected to be a power source of an electric vehicle due to its advantages of high power density, high energy conversion efficiency, low temperature start, environmental friendliness, and the like. The proton exchange membrane fuel cell consists of a Membrane Electrode (MEA) and a bipolar plate (with gas flow channels). The membrane electrode is a most core component of the proton exchange membrane fuel cell and structurally comprises a gas diffusion layer, a catalyst layer and a proton exchange membrane, and then the membrane electrode is formed by hot pressing. The membrane electrode is a multi-phase substance transmission and electrochemical reaction site for energy conversion in the proton exchange membrane fuel cell, relates to three-phase interface reaction and a complex mass and heat transfer process, and directly determines the performance, the service life and the cost of the proton exchange membrane fuel cell.
When the proton exchange membrane fuel cell outputs electric energy outwards, the electrode potential deviates from the equilibrium potential due to the influence of factors such as dynamics, and the like, namely polarization occurs. In general, common polarization arises from: (1) the mass transfer of the reaction gas on the reaction interface is not enough to provide electrode reaction to cause concentration difference; (2) ohmic resistance is generated when electrons and protons are transmitted in the battery electrode, the membrane and the current collector; (3) slower electrochemical reduction kinetics of the reactants and lower activation resistance due to catalytic activity; (4) hydrogen gas leakage (hydrogen gas permeating the membrane to the cathode), etc. At present, in order to overcome the polarization-causing situation and improve the efficiency and the service life of the membrane electrode, researchers can optimize the membrane electrode by changing two aspects of the process for preparing the membrane electrode and the components of slurry.
With the progress of society, environmental and energy problems are becoming more and more prominent, and countries in the world are searching and developing new clean energy to reduce the dependence on fossil fuel and protect the environment. Fuel cells, one of the most potential electrochemical devices, can deliver chemical energy from a fuel (e.g., hydrogen, methanol, etc.) and an oxidant (e.g., air) continuously to a consumer with virtually zero contamination of the product. The fuel cell may be classified into an alkaline fuel cell, a phosphoric acid fuel cell, a molten carbonate fuel cell, a proton exchange membrane fuel cell, a solid oxide fuel cell, and the like according to the difference of electrolytes in the fuel cell, wherein the Proton Exchange Membrane Fuel Cell (PEMFC) is most expected to be a power source of an electric vehicle due to its advantages of high power density, high energy conversion efficiency, low temperature start, environmental friendliness, and the like. The proton exchange membrane fuel cell consists of a Membrane Electrode (MEA) and a bipolar plate (with gas flow channels). The membrane electrode is a most core component of the proton exchange membrane fuel cell and structurally comprises a gas diffusion layer, a catalyst layer and a proton exchange membrane, and then the membrane electrode is formed by hot pressing. The membrane electrode is a multi-phase substance transmission and electrochemical reaction site for energy conversion in the proton exchange membrane fuel cell, relates to three-phase interface reaction and a complex mass and heat transfer process, and directly determines the performance, the service life and the cost of the proton exchange membrane fuel cell.
When the proton exchange membrane fuel cell outputs electric energy outwards, the electrode potential deviates from the equilibrium potential due to the influence of factors such as dynamics, and the like, namely polarization occurs. In general, common polarization arises from: (1) the mass transfer of the reaction gas on the reaction interface is not enough to provide electrode reaction to cause concentration difference; (2) ohmic resistance is generated when electrons and protons are transmitted in the battery electrode, the membrane and the current collector; (3) slower electrochemical reduction kinetics of the reactants and lower activation resistance due to catalytic activity; (4) hydrogen gas leakage (hydrogen gas permeating the membrane to the cathode), etc. At present, in order to overcome the polarization-causing situation and improve the efficiency and the service life of the membrane electrode, researchers can optimize the membrane electrode by changing two aspects of the process for preparing the membrane electrode and the components of slurry.
The related patents are as follows:
CN102255085
the catalyst slurry for preparing the catalytic membrane electrode of the proton exchange membrane fuel cell controls the catalyst slurry to be in a colloidal state by changing the composition and the adding sequence of the organic solvent in the slurry, thereby improving the pore structure of the catalytic layer of the prepared catalytic membrane electrode and improving the performance of the cell.
CN109713331
The catalyst slurry is colloid prepared from Pt-C catalyst, perfluorinated sulfonic resin, alcohol solvent and multi-walled carbon nano tubes, and the catalyst slurry is optimized by systematically changing the mass of the multi-walled carbon nano tubes added and the proportion of different resins and carbon, so that the conductivity of the slurry is optimized, the conductivity of a catalyst layer is improved, and the specific activity of the electrochemical activity area and the mass of the membrane electrode are greatly improved. The invention has great significance for the subsequent slurry process development and the reduction of platinum load, namely the reduction of the membrane electrode cost.
However, when the membrane electrode is prepared by using the components and processes of some existing catalyst slurries, the catalyst utilization rate is not high, the porosity of the catalyst layer is very low, the gas diffusion process is not facilitated, and when a single cell test is performed, obvious polarization exists and the performance is poor. New catalyst slurry optimization methods are awaited for further study.
Metal-organic framework Materials (MOFs) have unique crystalline state porosity, flexible tailorable characteristics, and excellent characteristics of ultra-high specific surface area active sites, adjustable pore structures, large surface areas, and the like, and have been widely used in the fields of biomedicine, gas adsorption, sensors, catalysis, supercapacitors, lithium ion batteries, and the like. Through a high-temperature carbonization process, the functionalized porous carbon material with the MOF structure can be obtained, the porous carbon material not only has excellent conductive rows, but also can provide a good gas transmission channel due to the pore channel structure which is regularly and uniformly distributed, the mass transfer efficiency can be well improved under the synergistic effect of the porous carbon material and catalyst particles, and the performance of a membrane electrode is improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and provides a method for preparing a porous MOF carbon material and a proton exchange membrane fuel cell catalyst slurry containing the same, aiming at optimizing the preparation process of the catalyst slurry and improving the performance of a membrane electrode.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method of making a porous MOF carbon material comprising the steps of:
s1: respectively dissolving an organic ligand and a transition metal salt in a certain amount of solvent to prepare a solution with a certain concentration, then measuring a certain volume of transition metal salt solution, dropwise adding the transition metal salt solution into the organic ligand solution, and magnetically stirring at room temperature;
s2: obtaining white precipitate, centrifugally washing, drying, and carbonizing at high temperature to obtain the MOF porous carbon material.
The organic ligand can be any one of hexamethylenetetramine, terephthalic acid, trimesic acid, 2-hydroxy terephthalic acid, maleic anhydride, terephthalic acid, 2-amino terephthalic acid, 2-methylimidazole and 1, 4-naphthalene dicarboxylic acid, the solvent for dissolving the organic ligand and the transition metal salt can be any one of deionized water, methanol, absolute ethyl alcohol, N-dimethylformamide and ionic liquid, the high-temperature carbonization temperature is 500-800 ℃, and the high-temperature carbonization time is 2-8 hours.
The organic ligand is hexamethylenetetramine with the concentration of 0.01-1.5M, and the transition metal salt is nitrate of Ni2+ with the concentration of 0.05-0.5M.
The temperature of the high-temperature carbonization is 650-750 ℃.
5. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon material comprising the steps of:
s1: mixing 5-20 wt% of high molecular polymer proton conductor, 0.1-20 wt% of water and 10-80 wt% of non-alcohol organic solvent together, and oscillating for 0.5-3 h by using ultrasonic waves or a stirrer to uniformly disperse the mixture to obtain dispersion liquid with a nearly colloid form.
S2: and (3) mixing 2-20 wt% of Pt/C catalyst particles, 1-50 wt% of alcohol and the dispersion liquid obtained in the step S1 together, and oscillating for 0.5-3 h by using ultrasonic waves or a stirrer to uniformly mix the mixture to prepare the required catalyst slurry.
The Pt/C catalyst is a 40% Pt/C catalyst.
The high molecular polymer proton conductor is selected from any one of perfluorinated sulfonic acid resin, sulfonated trifluorostyrene resin and polymethylphenylsulfonic acid siloxane resin, and the organic solvent is any one of butyl formate, ethyl acetate, butyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether and N, N-dimethylformamide.
The high molecular polymer proton conductor is perfluorosulfonic acid resin, and the organic solvent is butyl acetate.
The alcohol is one or more of absolute ethyl alcohol, isopropanol, ethylene glycol, glycerol, propanol and glycerol.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a porous carbon material with an MOF structure, which is added into catalyst slurry of a proton exchange membrane fuel cell, so that the conductivity of the slurry is optimized, the mass transfer efficiency in a membrane electrode is improved, and the electrochemical active area and the mass specific activity are improved. The invention has certain significance for the subsequent slurry process development.
Drawings
FIG. 1 is a flow diagram of the overall process of the present invention;
FIG. 2 is a transmission electron micrograph of a MOF structure porous carbon material synthesized and prepared according to the present invention;
FIG. 3 is a graph comparing I-V curves of single cells prepared in comparative example and example 1.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided to facilitate better understanding of the technical solutions by the related art through the description of the embodiments with reference to the accompanying drawings
The preparation method of the MOF structure porous carbon material used in the invention comprises the following steps: 4.0g of nickel nitrate hexahydrate (Ni (NO3) 2.6H 2O) is weighed into 60mL of absolute ethyl alcohol and dissolved for 20min by ultrasonic waves. 2.0g of hexamethyleneimine is weighed and added into 100mL of absolute ethyl alcohol, and dissolved for 20min by ultrasonic. Then, an ethanol solution of nickel nitrate was added dropwise to an anhydrous ethanol solution of hexamethyleneimine at room temperature to obtain a white precipitate. After centrifugation, the mixture is baked for 2 hours at 80 ℃ and carbonized for 2 hours at high temperature of 750 ℃ in H2/Ar mixed gas to obtain the porous carbon material. The transmission electron micrograph is shown in FIG. 2.
Comparative example preparation of Pt/C catalyst slurry
15.0g of butyl acetate were weighed into a beaker, 6.2g of a Nafion (5%) solution from DuPont was added and mixed by sonication. Then 11.0g of isopropanol was added, and ultrasonic oscillation was carried out for 30min to obtain a colloidal dispersion. 0.37g of JM Pt/C catalyst with the weight percentage of Pt being 40 percent is weighed and added into the dispersion liquid, ultrasonic dispersion is carried out for 60min, and stirring is carried out continuously, thus obtaining uniform catalyst slurry.
Example 1 preparation of Pt/C catalyst slurry with addition of MOF-structured porous carbon Material
The difference from the comparative example is that 0.022g of MOF structure porous carbon material is finally weighed and added into the dispersion liquid, and the mixture is ultrasonically dispersed for 60min and continuously stirred to obtain uniform catalyst slurry.
Preparation and testing of Membrane electrodes
The slurry prepared by the method is used for preparing the membrane electrode: uniformly dispersing the catalyst slurry on a transfer film (F46 film) by an ultrasonic spraying machine, and drying under vacuum at 120 ℃ for 8h to remove the solvent. Then, the catalyst layer on the transfer film was transferred onto an NRE-212 membrane of DuPont on a hot press, and the upper and lower heating plates of the hot press were continuously pressed at 140 ℃ under a pressure of 50kg/cm2 for 3 min. Carbon paper of TGP-H-060 type of Toray company was placed on both sides of the membrane electrode, and the membrane electrode was pressed and tested.
The prepared catalytic membrane electrode is assembled into a single cell, and then the polarization curve under the hydrogen-oxygen condition is evaluated. The test conditions were: sufficient H2/air was fed into the cell holder via the piping system, the humidified dew point temperature was set at 65 ℃, the cell cathodes and anodes were both heated to 65 ℃, and the test results are shown in fig. 3. As can be seen from FIG. 3, the cell voltage of the single cell corresponding to the Pt/C catalyst slurry was about 0.60V at a current density of 600mA/cm2, and the cell voltage could be maintained only to 0.50V as the current density increased to 1100mA/cm 2. And when the current density of a single cell prepared by adding the MOF structure porous carbon material is 600mA/cm2, the cell voltage is as high as 0.65V, and the cell voltage can be kept to 0.57V when the current density is increased to 1100mA/cm 2. The result shows that the addition of the porous carbon material with the MOF structure is beneficial to the electronic conduction and mass transmission in the battery, and the voltage of the battery can be kept in a higher range in a medium and high current density area.
The invention is described above with reference to the accompanying drawings, it is obvious that the specific implementation of the invention is not limited by the above-mentioned manner, and it is within the scope of the invention to adopt various insubstantial modifications of the inventive concept and solution, or to apply the inventive concept and solution directly to other applications without modification.
Claims (9)
1. A method for preparing a MOF carbon material having a porous structure, comprising the steps of:
s1: respectively dissolving an organic ligand and a transition metal salt in a certain amount of solvent to prepare a solution with a certain concentration, then measuring a certain volume of transition metal salt solution, dropwise adding the transition metal salt solution into the organic ligand solution, and magnetically stirring at room temperature;
s2: obtaining white precipitate, centrifugally washing, drying, and carbonizing at high temperature to obtain the MOF porous carbon material.
2. A method of making a porous MOF carbon material according to claim 1 wherein: the organic ligand can be any one of hexamethylenetetramine, terephthalic acid, trimesic acid, 2-hydroxy terephthalic acid, maleic anhydride, terephthalic acid, 2-amino terephthalic acid, 2-methylimidazole and 1, 4-naphthalene dicarboxylic acid, the solvent for dissolving the organic ligand and the transition metal salt can be any one of deionized water, methanol, absolute ethyl alcohol, N-dimethylformamide and ionic liquid, the high-temperature carbonization temperature is 500-800 ℃, and the high-temperature carbonization time is 2-8 hours.
3. A method of making a porous MOF carbon material according to claim 2 wherein: the organic ligand is hexamethylenetetramine with the concentration of 0.01-1.5M, and the transition metal salt is nitrate of Ni2+ with the concentration of 0.05-0.5M.
4. A method of making a porous MOF carbon material according to claim 2 wherein: the temperature of the high-temperature carbonization is 650-750 ℃.
5. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon materials prepared by the method of any one of claims 1 to 4, characterized by comprising the following preparation steps:
s1: mixing 5-20 wt% of high molecular polymer proton conductor, 0.1-20 wt% of water and 10-80 wt% of non-alcohol organic solvent together, and oscillating for 0.5-3 h by using ultrasonic waves or a stirrer to uniformly disperse the mixture to obtain dispersion liquid with a nearly colloid form.
S2: and (3) mixing 2-20 wt% of Pt/C catalyst particles, 1-50 wt% of alcohol and the dispersion liquid obtained in the step S1 together, and oscillating for 0.5-3 h by using ultrasonic waves or a stirrer to uniformly mix the mixture to prepare the required catalyst slurry.
6. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon material according to claim 5 wherein: the Pt/C catalyst is a 40% Pt/C catalyst.
7. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon material according to claim 5 wherein: the high molecular polymer proton conductor is selected from any one of perfluorinated sulfonic acid resin, sulfonated trifluorostyrene resin and polymethylphenylsulfonic acid siloxane resin, and the organic solvent is any one of butyl formate, ethyl acetate, butyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether and N, N-dimethylformamide.
8. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon material according to claim 7 wherein: the high molecular polymer proton conductor is perfluorosulfonic acid resin, and the organic solvent is butyl acetate.
9. A proton exchange membrane fuel cell catalyst slurry comprising MOF carbon material according to claim 5 wherein: the alcohol is one or more of absolute ethyl alcohol, isopropanol, ethylene glycol, glycerol, propanol and glycerol.
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