CN111029594A - Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell - Google Patents
Black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cell Download PDFInfo
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- CN111029594A CN111029594A CN201911410422.5A CN201911410422A CN111029594A CN 111029594 A CN111029594 A CN 111029594A CN 201911410422 A CN201911410422 A CN 201911410422A CN 111029594 A CN111029594 A CN 111029594A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000002071 nanotube Substances 0.000 claims abstract description 94
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009792 diffusion process Methods 0.000 claims abstract description 16
- 229920000557 Nafion® Polymers 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003466 welding Methods 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims description 111
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 41
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000007731 hot pressing Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002052 molecular layer Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 231100000572 poisoning Toxicity 0.000 abstract description 8
- 230000000607 poisoning effect Effects 0.000 abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910002849 PtRu Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 229910002669 PdNi Inorganic materials 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
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- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a black phosphorus-TiO 2 nanotube/Ti anode direct methanol fuel cell, which comprises a cell shell and a membrane electrode arranged in the cell shell, wherein an air chamber is arranged between the cell shell and the membrane electrode, and a methanol gas reaction chamber is arranged in the membrane electrode; the membrane electrode comprises a cathode diffusion layer, a cathode catalyst layer, a Nafion membrane and TiO with a nano black phosphorus layer deposited on the surface from outside to inside2nanotube/Ti; the cathode diffusion layer is connected with the battery shell through a welding point to form a cathode output end, and black phosphorus-TiO2The nanotube/Ti anode is connected with the battery shell through a welding point to form an anode output end, the top end of the methanol gas reaction chamber is provided with a feed hole and a feed seal for sealing the feed holeA cover with a feed hole for introducing gaseous methanol, an air flow hole communicated with the air chamber on the battery case, a water discharge hole at the bottom of the air chamber, and black phosphorus-TiO2The bottom of the nanotube/Ti anode is provided with CO2A discharge orifice. The battery of the invention has the advantages of low cost, high catalytic activity and strong CO poisoning resistance.
Description
Technical Field
The invention relates to the technical field of direct methanol fuel cells, in particular to black phosphorus-TiO2nanotube/Ti anode direct methanol fuel cells.
Background
Direct Methanol Fuel Cells (DMFC) have the advantages of low energy consumption, high energy density, abundant Methanol sources, low price, simple system, convenient operation, low noise and the like, are considered to be the most promising chemical power sources for automobile power and other vehicles in the future, and attract people's attention. One of the most critical materials of DMFCs is the electrode catalyst, which directly affects the performance, stability, service life, and manufacturing cost of the cell. Noble metal Pt has excellent catalytic performance under low temperature (less than 80 ℃), the electrode catalyst of the DMFC at present takes Pt as a main component, wherein the PtRu catalyst has stronger CO poisoning resistance and higher catalytic activity than pure Pt and is considered as the best catalyst of the DMFC at present, but the utilization rate in the DMFC cannot meet the requirement of commercialization due to the defects of high price, easy dissolution of Ru and the like. A great deal of research is carried out to prepare the multi-element composite catalyst so as to improve the catalytic activity and the CO poisoning resistance. Nano TiO22Is a semiconductor material which is researched and applied more in recent years, and people research and prepare a multi-element composite catalyst by taking the semiconductor material as a carrier or doping the semiconductor material to improve the catalytic activity and the CO poisoning resistance, such as TiO2Doping e.g. PtRuTiOX/C and Au/TiO2PtRu catalysts or as supports for preparing, e.g. PtNi/TiO2、PdAg/TiO2、PdNi/TiO2Or non-metal doping, etc., can reduce the consumption of noble metal Pt in the catalyst or prepare non-platinum catalyst, reduce the manufacturing cost of the catalyst, improve the catalytic performance and CO poisoning resistance, and has application prospect. But TiO22The conductivity is not ideal for semiconductors, and the catalyst needs to be doped with C when in use, so that the property is influencedCan be applied.
Black phosphorus is a two-dimensional material which has been studied more recently and has a higher conductivity, a lower band gap energy, a higher specific surface area, such as with TiO2The composite catalyst is used as a methanol catalyst, can improve the catalytic performance and the CO poisoning resistance of methanol, and is not reported when being used for a direct methanol fuel cell electrode.
Disclosure of Invention
In view of the above, the present invention is to provide a black phosphorus-TiO2The direct methanol fuel cell with the nanotube/Ti anode has the advantages of low catalyst cost, high catalytic activity and CO poisoning resistance.
In order to solve the technical problem, the invention provides black phosphorus-TiO2The nanotube/Ti anode direct methanol fuel cell comprises a cell shell and a membrane electrode arranged in the cell shell, wherein an air chamber is arranged between the cell shell and the membrane electrode, and a methanol gas reaction chamber is arranged in the membrane electrode; the membrane electrode comprises a cathode diffusion layer, a cathode catalyst layer, a Nafion membrane and black phosphorus-TiO from outside to inside2nanotube/Ti anode, said black phosphorus-TiO2The nanotube/Ti anode is TiO with a nano black phosphorus layer deposited on the surface2nanotube/Ti;
the cathode diffusion layer and the battery shell are connected through a welding point to form a cathode output end, and the black phosphorus-TiO2The nano tube/Ti anode is connected with the battery shell through a welding point to form an anode output end, the top end of the methanol gas reaction chamber is provided with a feed hole and a feed sealing cover for sealing the feed hole, the feed hole is used for leading gaseous methanol in, the battery shell is provided with an air flow through hole communicated with the air chamber, the bottom of the air chamber is provided with a water discharge hole, and the black phosphorus-TiO is2The bottom of the nanotube/Ti anode is provided with CO2A discharge orifice.
Preferably, the cathode output end and the anode output end are made of stainless steel, copper or titanium materials.
Preferably, the charging sealing cover is made of polytetrafluoroethylene materials.
Preferably, the preparation method of the membrane electrode comprises the following steps:
1) placing the porous titanium tube in acetone for ultrasonic degreasing for 15min, and then cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying;
2) carrying out anodic oxidation on the porous titanium tube obtained by pretreatment in the step 1) in electrolyte, wherein the electrolyte comprises the following components: 0.5 to 1% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 30-120 min; after the electrolysis is finished, washing the porous titanium tube with deionized water, drying the porous titanium tube, and roasting the porous titanium tube for 3 hours in a muffle furnace at the temperature of 500 ℃ to generate TiO on the inner and outer surfaces of the porous titanium tube2Nanotube to obtain TiO2nanotube/Ti;
3) heat-treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min;
4) adding TiO into the mixture2Placing the nanotube/Ti in a tube furnace, and placing the red phosphorus obtained by the step 3) on the inner and outer surfaces of the tube furnace at a rate of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 600-1000 ℃, preserving heat for 4-5 h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, cooling to form a black phosphorus nano-layer deposited on the TiO2Preparing black phosphorus-TiO on the inner and outer surfaces of the nano tube/Ti2nanotube/Ti anode;
5) spraying cathode catalyst slurry on the surface of the PTFE membrane to obtain a cathode catalyst layer;
6) subjecting the black phosphorus-TiO to2And respectively placing the nanotube/Ti anode and the cathode catalyst layer on two sides of a Nafion membrane, hot-pressing, removing the PTFE membrane, and then adding a cathode diffusion layer on one side of the cathode catalyst layer for hot-pressing to obtain the membrane electrode.
Compared with the prior art, the invention forms TiO on the inner and outer surfaces of the porous titanium tube after the porous titanium tube is subjected to anodic oxidation and roasting2Nanotubes, then on TiO2The nano-tube surface is compounded with nano black phosphorus to form black phosphorus-TiO2Nanotube anodesCatalytic layer of black phosphorus-TiO2nanotube/Ti anode. TiO22The nano-tube composite black phosphorus nano-layer can improve TiO2The conductivity of the nanotube is only 0.3-2 eV because of the band gap energy of the black phosphorus, and the TiO2The band gap energy of the nanotube is 3.2eV, the black phosphorus nanolayer and the TiO2The compounding of the nano tube can regulate and control and greatly reduce TiO2The band gap of the nanotubes. TiO22The synergistic effect of the nanotube and the black phosphorus improves the black phosphorus-TiO2The catalytic oxidation performance of the nanotube anode catalyst layer on methanol; meanwhile, when the direct methanol fuel cell is used, CO and other intermediate products generated by methanol oxidation are absorbed and transferred to black phosphorus/TiO2The nanotube anode catalyst is on the surface and is deeply oxidized into final product CO2Thus, the CO poisoning resistance of the battery of the present invention is improved. The price of P is far lower than that of noble metals such as Pt, Ru and the like, and the P is in black phosphorus-TiO2The amount of nanotubes is small, so that the cost of the catalyst can be greatly reduced.
The direct methanol fuel cell provided by the invention can convert black phosphorus-TiO into black phosphorus2The nanotube/Ti is used as an anode, so that the comprehensive performance is improved, and the nanotube/Ti can be used as a power battery of portable devices such as mobile phones, notebook computers and mobile phones and power batteries of motorcycles, automobiles and the like, and can realize industrial application; the fuel cell can be made into a micro fuel cell, a battery pack or a large electric fuel cell according to the actual use requirement, and can be made into various shapes according to the actual application requirement.
Drawings
FIG. 1 is a cross-sectional view of a direct methanol fuel cell provided by the present invention;
FIG. 2 is a top view of a direct methanol fuel cell provided by the present invention;
FIG. 3 is a cross-sectional view of the direct methanol fuel cell of FIG. 2, taken in rotation at A-A;
FIG. 4 is a cross-sectional view of a membrane electrode in a DMFC according to the present invention;
wherein, 1-sensor shell, 2-air chamber, 3-cathode output end, 4-membrane electrode, 5-anode output end, 6-porous titanium tube, 7-methanol gas reaction chamber, 8-cathode diffusion layer, 9-cathode catalyst layer, 10-Nafion film, 11-TiO2Nanotube, 12-nano black phosphorus layer, 13-air flow hole, 14-SO2Discharge hole, 15-water discharge hole, 16-gas filtering cap, 17-sealing cover for charging.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
As shown in figure 1, the invention provides black phosphorus-TiO2The nanotube/Ti anode direct methanol fuel cell comprises a cell shell 1 and a membrane electrode 4 arranged in the cell shell 1, wherein an air chamber 2 is arranged between the cell shell 1 and the membrane electrode 4, and a methanol gas reaction chamber 7 is arranged in the membrane electrode 4.
As shown in FIG. 4, the membrane electrode 4 comprises a cathode diffusion layer 8, a cathode catalyst layer 9, a Nafion membrane 10 and black phosphorus-TiO from outside to inside2nanotube/Ti anode of, among others, black phosphorus-TiO2The nanotube/Ti anode is TiO with a nano black phosphorus layer 12 deposited on the surface2nanotube/Ti, TiO2The nano tube/Ti is the compound TiO on the inner and outer surfaces of the porous titanium tube 62The nanotubes 11.
As shown in FIGS. 2 and 3, the cathode diffusion layer 8 and the battery case 1 are connected by a welding point to form a cathode output terminal 3, black phosphorus-TiO2The nanotube/Ti anode is connected with the battery shell 1 through a welding point to form an anode output end 5, the top end of the methanol gas reaction chamber 7 is provided with a feed hole 16 and a feed sealing cover 17 for sealing the feed hole 16, wherein the feed hole 16 is used for leading in gaseous methanol, the battery shell 1 is also provided with an air flow through hole 13 communicated with the air chamber 2, the bottom of the air chamber 2 is provided with a water discharge hole 15, and the black phosphorus-TiO is black phosphorus2CO is arranged at the bottom of the nanotube/Ti anode2A discharge orifice 14.
In the invention, the cathode output end 3 and the anode output end 5 are preferably made of stainless steel, copper or titanium materials; the feed sealing cap 17 is preferably made of polytetrafluoroethylene.
The invention provides a preparation method of a membrane electrode 4, which comprises the following steps:
1) placing the porous titanium tube in acetone for ultrasonic degreasing for 15min, and then cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying;
2) carrying out anodic oxidation on the porous titanium tube obtained by pretreatment in the step 1) in electrolyte, wherein the electrolyte comprises the following components: 0.5 to 1% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 30-120 min; after the electrolysis, washing the porous titanium tube with deionized water, drying the porous titanium tube, and roasting the porous titanium tube in a muffle furnace at 500 ℃ for 3 hours to generate TiO on the inner and outer surfaces of the porous titanium tube2Nanotube to obtain TiO2nanotube/Ti;
3) heat-treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min;
4) adding TiO into the mixture2Placing the nanotube/Ti in a tube furnace, and placing the red phosphorus obtained by the step 3) on the inner and outer surfaces of the tube furnace at a rate of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 600-1000 ℃, preserving heat for 4-5 h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, cooling to form a black phosphorus nano-layer, and depositing the black phosphorus nano-layer on TiO2Preparing black phosphorus-TiO on the inner and outer surfaces of the nano tube/Ti2nanotube/Ti anode;
5) spraying cathode catalyst slurry on the surface of the PTFE membrane to obtain a cathode catalyst layer;
6) mixing black phosphorus-TiO2The nanotube/Ti anode and cathode catalyst layers are respectively arranged on two sides of a Nafion membrane, hot pressing is carried out, the PTFE membrane is removed, and a cathode diffusion layer is added on one side of the cathode catalyst layer for hot pressing to obtain the membrane electrode.
Specifically, in order to prepare the membrane electrode 4, the porous titanium tube is firstly placed in acetone for ultrasonic degreasing for 15min, then is cleaned by methanol or ethanol, and then is cleaned by 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying.
After the porous titanium tube is treated, placing the porous titanium tube in electrolyte for anodic oxidation, wherein the adopted electrolyte preferably contains 0.5-1% of HF and 1mol/L of H2SO4More preferably, it contains 0.8% of HF and 1mol/L of H2SO4(ii) a The electrolysis potential is preferably 20V, and the electrolysis time is preferably 30-120 min, and more preferably 80 min; after the electrolysis is finished, washing the product with deionized water, drying the product, and roasting the product for 3 hours in a muffle furnace at the temperature of 500 ℃ to obtain the product with TiO on the inner and outer surfaces2Porous titanium tubes of nanotubes, i.e. TiO2nanotube/Ti.
In order to remove oxides and impurities on the surface of red phosphorus, the red phosphorus is preferably subjected to a heat treatment at a temperature of 200 ℃ for 2 hours. Then cooling the red phosphorus to normal temperature, and grinding the red phosphorus for 15min to obtain the red phosphorus with fine and uniform particles.
For preparing black phosphorus-TiO2nanotube/Ti anode, preferably TiO to be obtained2Placing the nanotube/Ti in a tube furnace, and placing the red phosphorus obtained by treatment on the inner and outer surfaces of the tube furnace at a rate of 5cm per minute3Introducing argon into the tubular furnace at the rate, heating to 600-1000 ℃, preferably to 650-1000 ℃, keeping the temperature for 4-5 hours, cooling to 350 ℃ at the rate of 5 ℃ per minute, keeping the temperature for 2 hours, cooling to form a black phosphorus nano-layer, and depositing the black phosphorus nano-layer on TiO2Preparing black phosphorus-TiO on the inner and outer surfaces of the nano tube/Ti2nanotube/Ti anode.
Spraying cathode catalyst slurry on the surface of a PTFE membrane to obtain a cathode catalyst layer, and then spraying the cathode catalyst layer and the black phosphorus-TiO2The nanotube/Ti anode is respectively arranged on two sides of a Nafion membrane, hot pressing is carried out, a PTFE membrane is removed, and a cathode diffusion layer is added on one side of a cathode catalyst layer for hot pressing to obtain the membrane electrode.
In order to further illustrate the present invention, the following detailed description is given with reference to examples.
Example 1
(1) Pretreatment of the porous titanium tube: placing a porous titanium tube in a tube CUltrasonic degreasing in ketone for 15min, and cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying.
(2)TiO2Preparation of nanotubes/Ti: carrying out anodic oxidation on the porous titanium tube obtained after the pretreatment in electrolyte, wherein the electrolyte comprises the following components: 0.8% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 80 min; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to obtain TiO formed on the inner and outer surfaces2Porous titanium tubes of nanotubes, i.e. TiO2nanotube/Ti.
(3) Heat treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min.
(4) Black phosphorus-TiO2Preparation of nanotube/Ti anode: adding TiO into the mixture2Placing the nano-tubes/Ti in a tube furnace, and placing the red phosphorus obtained by the treatment in the step (3) on the inner surface and the outer surface of the tube furnace at the speed of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 650 ℃, preserving heat for 5h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, forming a black phosphorus nano-layer after cooling, and depositing on TiO2Inner and outer surfaces of nanotube/Ti to prepare the black phosphorus-TiO of this example2nanotube/Ti anode.
(5) And spraying the cathode catalyst slurry on the surface of the PTFE membrane to prepare a cathode catalyst layer.
(6) A cathode catalyst layer and the black phosphorus-TiO of this example2The nanotube/Ti anode is respectively arranged on two sides of a Nafion membrane, hot pressing is carried out, a PTFE membrane is removed, and a cathode diffusion layer is added on one side of a cathode catalyst layer for hot pressing to obtain the membrane electrode.
Example 2
(1) Pretreatment of the porous titanium tube: placing the porous titanium tube in acetone for ultrasonic degreasing for 15min, and then cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning with secondary distilled water for 3 times, treating with 1mol/L HF for 10min, and ultrasonically cleaning with secondary distilled water for 3 timesAnd (6) drying.
(2)TiO2Preparation of nanotubes/Ti: carrying out anodic oxidation on the porous titanium tube obtained by pretreatment in electrolyte, wherein the electrolyte comprises the following components: 0.8% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 80 min; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to obtain TiO formed on the inner and outer surfaces2Porous titanium tubes of nanotubes, i.e. TiO2nanotube/Ti.
(3) Heat treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min.
(4) Black phosphorus-TiO2Preparation of nanotube/Ti anode: adding TiO into the mixture2Placing the nano-tubes/Ti in a tube furnace, and placing the red phosphorus obtained by the treatment in the step (3) on the inner surface and the outer surface of the tube furnace at the speed of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 800 ℃, preserving heat for 4h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, forming a black phosphorus nano-layer after cooling, and depositing on TiO2Inner and outer surfaces of nanotube/Ti to prepare the black phosphorus-TiO of this example2nanotube/Ti anode.
(5) And spraying the cathode catalyst slurry on the surface of the PTFE membrane to prepare a cathode catalyst layer.
(6) A cathode catalyst layer and the black phosphorus-TiO of this example2The nanotube/Ti anode is respectively arranged on two sides of a Nafion membrane, hot pressing is carried out, a PTFE membrane is removed, and a cathode diffusion layer is added on one side of a cathode catalyst layer for hot pressing to obtain the membrane electrode.
Example 3
(1) Pretreatment of the porous titanium tube: placing the porous titanium tube in acetone for ultrasonic degreasing for 15min, and then cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying.
(2)TiO2Preparation of nanotubes/Ti: carrying out anodic oxidation on the porous titanium tube obtained by pretreatment in electrolyte, wherein the electrolyte comprises the following components: 0.8% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 80 min; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to obtain TiO formed on the inner and outer surfaces2Porous titanium tubes of nanotubes, i.e. TiO2nanotube/Ti.
(3) Heat treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min.
(4) Black phosphorus-TiO2Preparation of nanotube/Ti anode: adding TiO into the mixture2Placing the nano-tubes/Ti in a tube furnace, and placing the red phosphorus obtained by the treatment in the step (3) on the inner surface and the outer surface of the tube furnace at the speed of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 1000 ℃, preserving heat for 4h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, forming a black phosphorus nano-layer after cooling, and depositing on TiO2Inner and outer surfaces of nanotube/Ti to prepare the black phosphorus-TiO of this example2nanotube/Ti anode.
(5) And spraying the cathode catalyst slurry on the surface of the PTFE membrane to prepare a cathode catalyst layer.
(6) A cathode catalyst layer and the black phosphorus-TiO of this example2The nanotube/Ti anode is respectively arranged on two sides of a Nafion membrane, hot pressing is carried out, a PTFE membrane is removed, and a cathode diffusion layer is added on one side of a cathode catalyst layer for hot pressing to obtain the membrane electrode.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. Black phosphorus-TiO2The nanotube/Ti anode direct methanol fuel cell is characterized by comprising a cell shell and a membrane electrode arranged in the cell shell, wherein an air chamber is arranged between the cell shell and the membrane electrode, a methanol gas reaction chamber is arranged in the membrane electrode, and the membrane electrode comprises a cathode diffusion layer, a cathode catalyst layer, a Nafion membrane and black phosphorus-TiO from outside to inside2nanotube/Ti anode, said black phosphorus-TiO2The nanotube/Ti anode is TiO with a nano black phosphorus layer deposited on the surface2nanotube/Ti;
the cathode diffusion layer and the battery shell are connected through a welding point to form a cathode output end, and the black phosphorus-TiO2The nano tube/Ti anode is connected with the battery shell through a welding point to form an anode output end, the top end of the methanol gas reaction chamber is provided with a feed hole and a feed sealing cover for sealing the feed hole, the feed hole is used for leading gaseous methanol in, the battery shell is provided with an air flow through hole communicated with the air chamber, the bottom of the air chamber is provided with a water discharge hole, and the black phosphorus-TiO is2The bottom of the nanotube/Ti anode is provided with CO2A discharge orifice.
2. The black phosphorus-TiO of claim 12The nanotube/Ti anode direct methanol fuel cell is characterized in that the cathode output end and the anode output end are made of stainless steel, copper or titanium materials.
3. The black phosphorus-TiO of claim 12The direct methanol fuel cell with the nanotube/Ti anode is characterized in that the charging sealing cover is made of polytetrafluoroethylene material.
4. The black phosphorus-TiO of claim 12The nanotube/Ti anode direct methanol fuel cell is characterized in that the preparation method of the membrane electrode comprises the following steps:
1) placing the porous titanium tube in acetone for ultrasonic degreasing for 15min, and then cleaning with methanol or ethanol; then using 400g/L CrO3And 350g/L of H2SO4Treating for 3min, ultrasonically cleaning for 3 times with secondary distilled water, treating for 10min with 1mol/L HF, ultrasonically cleaning for 3 times with secondary distilled water, and drying;
2) carrying out anodic oxidation on the porous titanium tube obtained by pretreatment in the step 1) in electrolyte, wherein the electrolyte comprises the following components: 0.5 to 1% of HF, 1mol/L of H2SO4(ii) a The electrolytic potential is 20V, and the electrolytic time is 30-120 min; after the electrolysis is finished, washing the porous titanium tube with deionized water, drying the porous titanium tube, and roasting the porous titanium tube for 3 hours in a muffle furnace at the temperature of 500 ℃ to generate TiO on the inner and outer surfaces of the porous titanium tube2Nanotube to obtain TiO2nanotube/Ti;
3) heat-treating red phosphorus at 200 deg.C for 2 hr to remove surface oxide and impurities, cooling, and grinding for 15 min;
4) adding TiO into the mixture2Placing the nanotube/Ti in a tube furnace, and placing the red phosphorus obtained by the step 3) on the inner and outer surfaces of the tube furnace at a rate of 5cm per minute3Introducing argon into the tubular furnace at the rate of (1), heating to 600-1000 ℃, preserving heat for 4-5 h, then cooling to 350 ℃ at the rate of 5 ℃ per minute, preserving heat for 2h, cooling to form a black phosphorus nano-layer deposited on the TiO2Preparing black phosphorus-TiO on the inner and outer surfaces of the nano tube/Ti2nanotube/Ti anode;
5) spraying cathode catalyst slurry on the surface of the PTFE membrane to obtain a cathode catalyst layer;
6) subjecting the black phosphorus-TiO to2And respectively placing the nanotube/Ti anode and the cathode catalyst layer on two sides of a Nafion membrane, hot-pressing, removing the PTFE membrane, and then adding a cathode diffusion layer on one side of the cathode catalyst layer for hot-pressing to obtain the membrane electrode.
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