CN113363506A - Direct methanol fuel cell electrode and preparation method thereof - Google Patents
Direct methanol fuel cell electrode and preparation method thereof Download PDFInfo
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- CN113363506A CN113363506A CN202110783868.3A CN202110783868A CN113363506A CN 113363506 A CN113363506 A CN 113363506A CN 202110783868 A CN202110783868 A CN 202110783868A CN 113363506 A CN113363506 A CN 113363506A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000000446 fuel Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002071 nanotube Substances 0.000 claims abstract description 102
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 37
- 238000009713 electroplating Methods 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 7
- 229960001413 acetanilide Drugs 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910002849 PtRu Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 229910002669 PdNi Inorganic materials 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000012467 final product Substances 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- H01M4/8605—Porous electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- 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]
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Abstract
The invention belongs to the technical field of battery electrodes, and relates to a direct methanol fuel battery electrode and a preparation method thereof. The preparation method provided by the invention comprises the following steps: forming TiO2 nanotubes on the inner and outer surfaces of the pores of the porous titanium foil to obtain a TiO2 nanotube/porous titanium foil; in TiO2The surface of the nano tube/porous titanium foil is electroplated and deposited with a nano CoAg alloy to obtain CoAg-TiO2Nanotube/porous titanium foil; in the presence of CoAg-TiO2The surface of the nano tube/porous titanium foil is coated with polyaniline-poly (2-Acrylamide-2 methylpropanesulfonic acid) to obtain the direct methanol fuel cell electrode. The direct methanol fuel cell electrode has higher catalytic activity to methanol, strong anti-poisoning capability, low cost and long service life.
Description
Technical Field
The invention belongs to the technical field of battery electrodes, relates to a direct methanol fuel battery electrode and a preparation method thereof, and particularly relates to polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO2The nanotube/porous titanium foil direct methanol fuel cell electrode.
Background
The Direct Methanol Fuel Cell (DMFC) has the advantages of low energy consumption, high energy density, abundant methanol sources, low price, simple system, convenient operation, low noise and the like, is considered to be the most promising chemical power source for automobile power and other vehicles in the future, and attracts 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.
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. PtRuTiOXC 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 TiO22Is a semiconductorThe conductivity is not ideal, and the catalyst needs to be doped with C when in use, so that the performance and the application of the catalyst are influenced.
Disclosure of Invention
In view of the above, the present invention is directed to a direct methanol fuel cell electrode and a method for manufacturing the same, wherein the direct methanol fuel cell electrode has high catalytic activity to methanol, strong anti-poisoning ability, low cost, and long service life.
In order to achieve the above object, the present invention provides a direct methanol fuel cell electrode, which is made of polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO2Nanotube/porous titanium foil, the CoAg-TiO2The inner and outer surfaces of the pore of the nanotube/porous titanium foil are provided with CoAg-TiO2Porous titanium foil of nanotubes.
Further, the CoAg-TiO2The sum of the contents of the CoAg alloys in the nanotubes is CoAg-TiO21-3 wt% of the nanotube.
The invention also provides a preparation method of the direct methanol fuel cell electrode, which comprises the following steps:
(1) forming TiO on the inner and outer surfaces of the porous titanium foil pore2Nanotube to obtain TiO2Nanotube/porous titanium foil;
(2) TiO obtained in step (1)2The surface of the nano tube/porous titanium foil is electroplated and deposited with a nano CoAg alloy to obtain CoAg-TiO2Nanotube/porous titanium foil;
(3) CoAg-TiO obtained in step (2)2And coating polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) on the surface of the nanotube/porous titanium foil to obtain the direct methanol fuel cell electrode.
Further, in the above preparation method, the preparation method of the porous titanium foil comprises: cleaning titanium foil, and soaking in H2O2And (3) heating the titanium foil until the color of the titanium foil is dark blue, taking out the titanium foil, cleaning, drying, calcining in a muffle furnace at 300 ℃ for 30min, and taking out to obtain the porous titanium foil, wherein the porous titanium foil has a three-dimensional porous structure.
Further, in the preparation method, the thickness of the titanium foil is 0.1-0.2 mm.
Further, in the above preparation method, the cleaning treatment is: and (3) ultrasonic degreasing of the titanium foil in acetone for 15 minutes, cleaning with methanol or ethanol, treating in 1mol/L HF for 10 minutes, taking out, ultrasonic cleaning with secondary distilled water for 3 times, and drying to obtain the cleaned titanium foil.
Further, in the above preparation method, the heating is: heating for 40-60 min at 90 ℃.
Further, in the above preparation method, the step (1) is specifically: carrying out electrolytic reaction on the porous titanium foil in electrolyte, taking out, washing, drying, roasting at 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2Nanotube/porous titanium foil; the electrolyte is 0.5 to 1 percent of HF and 1mol/L of H2SO4The mixed solution of (1); the electrolytic potential of the electrolytic reaction is 20V, and the time of the electrolytic reaction is 30-120 minutes.
Further, in the above preparation method, the step (2) is specifically: adding TiO into the mixture2The nanotube/porous titanium foil is used as a cathode and is placed in electroplating solution for electroplating at room temperature to obtain CoAg-TiO2Nanotube/porous titanium foil; the components of the electroplating solution are as follows: 0.01mol/L AgNO30.01mol/L of CoSO4And 20g/L of H3BO3(ii) a The PH of the electroplating solution is 4.4; the current density of the electroplating is 5mA/cm2The time is 30-90 min.
Further, in the above preparation method, the step (3) is specifically: subjecting the CoAg-TiO to2Putting the nanotube/porous titanium foil into HCl solution, performing ultrasonic dispersion for 30min, adding aniline, o-phenylenediamine, 2-acrylamide-2-methylpropanesulfonic acid and p-acetanilide at 5 ℃, after vigorously stirring for 30min, dropping ammonium persulfate solution under stirring, reacting for 6h, repeatedly washing the product with 0.1mol/L HCl solution until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 8h to obtain polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO2The nanotube/porous titanium foil is used for direct methanol fuel cell electrodes; wherein aniline and 2-propyleneThe molar ratio of the amide-2-methylpropanesulfonic acid is 2:1, and the aniline and the TiO are2The molar ratio of the nanotubes is 3-1: 1.
Compared with the prior art, in the direct methanol fuel cell electrode provided by the invention, TiO is added2The specific surface area of the nano tube/porous titanium foil is high, and the CoAg alloy deposited on the surface of the nano tube/porous titanium foil can regulate and control and greatly reduce TiO2While being able to extract TiO2The conductivity of the nanotube is improved, the catalytic performance of the nanotube is improved, meanwhile, the surface of the nanotube is coated with the porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) with high conductivity, which is beneficial to the adsorption of methanol, the electronic conductivity and the catalytic activity of the catalyst can be further improved, and the synergistic effect of the polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) and the poly (2-acrylamide-2-methylpropanesulfonic acid) improves the TiO2Catalytic oxidation performance to methanol. Meanwhile, CO and other intermediate products generated by methanol oxidation are easy to adsorb and transfer to CoAg-TiO2The nanotube surface is deeply oxidized into CO as a final product2Can improve the nano TiO2The composite catalyst has CO poisoning resisting capacity, and the cost of CoAg and polymer is far lower than that of Pt, Ru and other noble metals, and the CoAg-TiO coated with polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid)2The amount of the nano tube/porous titanium foil is small, so that the cost of the catalyst can be greatly reduced, and the catalyst is CoAg-TiO2The nano tube/porous titanium foil coated polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) battery electrode is used as a direct methanol fuel battery anode, and the battery performance can be improved.
Drawings
FIG. 1 shows RuNi/TiO obtained in comparative example 12The nanotube electrode and the direct methanol fuel cell electrode provided by the embodiment 2 of the invention have H of 1mol/L2SO4And a cyclic voltammogram at 100mV/s in 1mol/L methanol solution;
FIG. 2 shows the concentration of H in 1mol/L in a commercial PtRu/C catalyst2SO4And a cyclic voltammogram at 100mV/s in 1mol/L methanol solution.
Detailed Description
The present invention will be further illustrated by the following specific examples, which are carried out on the premise of the technical scheme of the present invention, and it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1: preparation of porous titanium foil
(1) Pretreatment of the titanium foil: ultrasonically removing oil in acetone for 15 minutes, cleaning with methanol or ethanol, treating with 1mol/L HF for 10 minutes, ultrasonically cleaning with secondary distilled water for 3 times, and drying;
(2) forming a porous titanium foil: soaking the cleaned titanium foil in H2O2Heating to 90 ℃ in the medium, continuing heating for 40-60 min until H2O2And (3) taking out the titanium foil after the titanium foil is slightly dark blue, washing the titanium foil for a plurality of times by using distilled water and absolute ethyl alcohol, drying the titanium foil, calcining the titanium foil in a muffle furnace at 300 ℃ for 30min, and taking out the titanium foil to obtain the porous titanium foil with the three-dimensional porous structure.
Example 2
(1) 0.6g of the porous titanium foil prepared in the example 1 is put in an electrolyte for electrolytic reaction; composition of the electrolyte: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 30 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2Nanotube/porous titanium foil, weight 649.26 mg;
(2) TiO obtained in the step (1)2The nanotube/porous titanium foil is used as a cathode for electroplating, and the composition and the process conditions of the electroplating solution are as follows:
after the electroplating is finished, washing with deionized water and drying to obtain the CoAg-TiO2Nanotube/porous titanium foil, weight 650mg, CoAg alloy content and CoAg-TiO content21.48% of the nanotubes.
(3) Leading the CoAg-TiO obtained in the step (2) to be2Nanotube/porous titanium foil (among others)CoAg-TiO250mg of nano tube) is put into 150mL of 2mol/L HCl solution, ultrasonic dispersion is carried out for 30min, 116mg of aniline, 67.5mg of o-phenylenediamine, 518mg of 2-acrylamide-2-methylpropanesulfonic acid and 42mg of p-acetanilide are added at the temperature of 5 ℃, after vigorous stirring is carried out for 30min, 50mL of 285mg ammonium persulfate solution dissolved by 2mol/L HCl is dripped under stirring to initiate polymerization reaction for 6h, the product is repeatedly washed by 0.1mol/L HCl solution until the filtrate is colorless, vacuum drying is carried out for 8h at the temperature of 60 ℃, and the high-conductivity porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO is prepared2The nanotube/porous titanium foil direct methanol fuel cell electrode.
Example 3
(1) 0.6g of the porous titanium foil prepared in the example 1 is put in an electrolyte for electrolytic reaction; composition of the electrolyte: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 30 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2Nanotube/porous titanium foil, weight 649.26 mg;
(2) TiO obtained in the step (1)2The nanotube/porous titanium foil is used as a cathode for electroplating, and the composition and the process conditions of the electroplating solution are as follows:
after the electroplating is finished, washing with deionized water and drying to obtain the CoAg-TiO2Nanotube/porous titanium foil with a weight of 650.74mg, the sum of the contents of the CoAg alloys being CoAg-TiO22.91% of the nanotubes.
(3) Leading the CoAg-TiO obtained in the step (2) to be2Nanotube/porous titanium foil (of which CoAg-TiO)250.74mg of nanotube) was put into 150mL of a 2mol/L HCl solution, ultrasonically dispersed for 30min, 118mg of aniline, 68.5mg of o-phenylenediamine, 525.6mg of 2-acrylamido-2-methylpropanesulfonic acid, and 42.6mg of p-acetanilide were added at 5 ℃, vigorously stirred for 30min, and 50mL of a solution of 2mol/L HCl was added dropwise with stirring285mg ammonium persulfate solution to initiate polymerization reaction for 6h, repeatedly washing the product with 0.1mol/L HCl solution until the filtrate is colorless, and drying the product in vacuum at 60 ℃ for 8h to prepare the high-conductivity porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO2The nanotube/porous titanium foil direct methanol fuel cell electrode.
Example 4
(1) 0.6g of the porous titanium foil prepared in the example 1 is put in an electrolyte for electrolytic reaction; composition of the electrolyte: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 60 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2The weight of the nanotube/porous titanium foil is 690 mg;
(2) TiO obtained in the step (1)2The nanotube/porous titanium foil is used as a cathode for electroplating, and the composition and the process conditions of the electroplating solution are as follows:
after the electroplating is finished, washing with deionized water and drying to obtain the CoAg-TiO2Nanotube/porous titanium foil with a weight of 691.48mg, the sum of the contents of the CoAg alloys being CoAg-TiO21.62% of the nanotubes.
(3) Leading the CoAg-TiO obtained in the step (2) to be2Nanotube/porous titanium foil (of which CoAg-TiO)291.48mg of nanotube) is put into 150mL of 2mol/L HCl solution, ultrasonic dispersion is carried out for 30min, 212.7mg of aniline, 123.5mg of o-phenylenediamine, 946.8mg of 2-acrylamide-2-methylpropanesulfonic acid and 76.8mg of p-acetanilide are added at the temperature of 5 ℃, after vigorous stirring for 30min, 50mL of 285mg ammonium persulfate solution dissolved by 2mol/L HCl is dripped under stirring to initiate polymerization reaction for 6h, the product is repeatedly washed by 0.1mol/L of HCl solution until the filtrate is colorless, vacuum drying is carried out for 8h at the temperature of 60 ℃, and the high-conductivity porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO is prepared2Nanotube and method of manufacturing the samePorous titanium foil direct methanol fuel cell electrodes.
Example 5
(1) 0.6g of the porous titanium foil prepared in the example 1 is put in an electrolyte for electrolytic reaction; composition of the electrolyte: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 90 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2The weight of the nano tube/porous titanium foil is 740 mg;
(2) TiO obtained in the step (1)2The nanotube/porous titanium foil is used as a cathode for electroplating, and the composition and the process conditions of the electroplating solution are as follows:
after the electroplating is finished, washing with deionized water and drying to obtain the CoAg-TiO2Nanotube/porous titanium foil with a weight of 742.22mg, the sum of the contents of the CoAg alloys being CoAg-TiO21.56% of the nanotubes.
(4) Leading the CoAg-TiO obtained in the step (2) to be2Nanotube/porous titanium foil (of which CoAg-TiO)291.48mg of nanotube) is put into 150mL of 2mol/L HCl solution, ultrasonic dispersion is carried out for 30min, 330.6mg of aniline, 192mg of o-phenylenediamine, 1472mg of 2-acrylamide-2-methylpropanesulfonic acid and 119.5mg of p-acetanilide are added at the temperature of 5 ℃, after vigorous stirring is carried out for 30min, 50mL of 285mg of ammonium persulfate solution dissolved by 2mol/L of HCl is dripped under stirring to initiate polymerization reaction for 6h, the product is repeatedly washed by 0.1mol/L of HCl solution until the filtrate is colorless, vacuum drying is carried out for 8h at the temperature of 60 ℃, and the high-conductivity porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO is prepared2The nanotube/porous titanium foil direct methanol fuel cell electrode.
Example 6
(1) 0.6g of the porous titanium foil prepared in the example 1 is put in an electrolyte for electrolytic reaction; composition of the electrolyte: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 60 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2The weight of the nanotube/porous titanium foil is 690 mg;
(2) TiO obtained in the step (1)2The nanotube/porous titanium foil is used as a cathode for electroplating, and the composition and the process conditions of the electroplating solution are as follows:
after the electroplating is finished, washing with deionized water and drying to obtain the CoAg-TiO2Nanotube/porous titanium foil with a weight of 692.22mg, the sum of the contents of the CoAg alloys being CoAg-TiO22.41% of the nanotubes.
(5) Leading the CoAg-TiO obtained in the step (2) to be2Nanotube/porous titanium foil (of which CoAg-TiO)292.22mg of nanotube) is put into 150mL of 2mol/L HCl solution, ultrasonic dispersion is carried out for 30min, 214.4mg of aniline, 124.5mg of o-phenylenediamine, 954.5mg of 2-acrylamide-2-methylpropanesulfonic acid and 77.5mg of p-acetanilide are added at the temperature of 5 ℃, after vigorous stirring for 30min, 50mL of 285mg ammonium persulfate solution dissolved by 2mol/L of HCl is dripped under stirring to initiate polymerization reaction for 6h, the product is repeatedly washed by 0.1mol/L of HCl solution until the filtrate is colorless, vacuum drying is carried out for 8h at the temperature of 60 ℃, and the high-conductivity porous spongy polymer polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO is prepared2The nanotube/porous titanium foil direct methanol fuel cell electrode.
Comparative example 1: RuNi/TiO for direct methanol fuel cell2Nanotube electrode
RuNi/TiO for direct methanol fuel cell2The preparation method of the nanotube electrode comprises the following steps:
(1) pretreatment of a titanium plate: polishing a titanium plate by using metallographic abrasive paper, ultrasonically removing oil in acetone for 15 minutes, cleaning by using methanol or ethanol, treating by using 1mol/L HF for 10 minutes, ultrasonically cleaning by using secondary distilled water for 3 times, and drying.
(2)TiO2Preparation of nanotubes/Ti: carrying out anodic oxidation on the treated titanium plate in electrolyte, wherein the electrolyte comprises the following components: 0.5% -1% of HF, 1mol/L of H2SO4The electrolytic potential is 20V, and the electrolytic time is 30 minutes; after the electrolysis, washing with deionized water, drying, and roasting in a muffle furnace at 500-600 ℃ for 3 hours to obtain TiO2nanotube/Ti;
(3)RuNi/TiO2preparing a nanotube electrode: the prepared TiO is mixed with2The nanotube/Ti is used as a cathode for electroplating, the volume of the electroplating solution is 50mL, and the electroplating solution comprises the following components:
after the electroplating is finished, washing with deionized water and drying to obtain RuNi/TiO2A nanotube electrode.
RuNi/TiO for direct methanol Fuel cell obtained in comparative example 12Cyclic voltammograms of the nanotube electrode, commercial PtRu/C catalyst and direct methanol fuel cell electrode obtained in example 2 of the invention are shown in FIGS. 1 and 2, and from the cyclic voltammograms, it can be seen that the comparative example RuNi/TiO is comparable to the commercial PtRu/C catalyst2Nanotube electrode and polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO provided in embodiment 2 of the invention2The direct methanol fuel cell electrode of the nanotube/porous titanium foil has low methanol oxidation initial potential and low oxidation peak potential, has only one large oxidation peak for methanol and no intermediate product such as CO oxidation peak, and shows the comparative example RuNi/TiO2Nanotube electrode and polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO provided in embodiment 2 of the invention2The direct methanol fuel cell electrode of the nanotube/porous titanium foil has higher catalytic activity and toxicity resistance than the commercial PtRu/C catalyst. And comparative example RuNi/TiO2Compared with the nanotube electrode, the polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) coated CoAg-TiO provided by the embodiment 2 of the invention2The electrode of the direct methanol fuel cell electrode of the nanotube/porous titanium foil is shifted to the left by the oxidation peak potential of methanol, and the peak current is larger, which indicates that the electrode is opposite to the oxidation peak potential of methanolMethanol has higher catalytic performance.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. The direct methanol fuel cell electrode is characterized in that the direct methanol fuel cell electrode is formed by coating polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) with CoAg-TiO2Nanotube/porous titanium foil, the CoAg-TiO2The inner and outer surfaces of the pore of the nanotube/porous titanium foil are provided with CoAg-TiO2Porous titanium foil of nanotubes.
2. The direct methanol fuel cell electrode of claim 1 wherein the CoAg-TiO2The sum of the contents of the CoAg alloys in the nanotubes is CoAg-TiO21-3 wt% of the nanotube.
3. A preparation method of a direct methanol fuel cell electrode is characterized by comprising the following steps:
(1) forming TiO on the inner and outer surfaces of the porous titanium foil pore2Nanotube to obtain TiO2Nanotube/porous titanium foil;
(2) TiO obtained in step (1)2The surface of the nano tube/porous titanium foil is electroplated and deposited with a nano CoAg alloy to obtain CoAg-TiO2Nanotube/porous titanium foil;
(3) CoAg-TiO obtained in step (2)2And coating polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) on the surface of the nanotube/porous titanium foil to obtain the direct methanol fuel cell electrode.
4. The method according to claim 3, wherein the porous titanium foil is prepared by: cleaning titanium foil, and soaking in H2O2And (3) heating the titanium foil until the color of the titanium foil is dark blue, taking out the titanium foil, cleaning, drying, calcining in a muffle furnace at 300 ℃ for 30min, and taking out to obtain the porous titanium foil, wherein the porous titanium foil has a three-dimensional porous structure.
5. The method according to claim 4, wherein the titanium foil has a thickness of 0.1 to 0.2 mm.
6. The production method according to claim 4, wherein the cleaning treatment is: and (3) ultrasonic degreasing of the titanium foil in acetone for 15 minutes, cleaning with methanol or ethanol, treating in 1mol/L HF for 10 minutes, taking out, ultrasonic cleaning with secondary distilled water for 3 times, and drying to obtain the cleaned titanium foil.
7. The method of claim 4, wherein the heating is: heating for 40-60 min at 90 ℃.
8. The preparation method according to claim 3, wherein the step (1) is specifically: carrying out electrolytic reaction on the porous titanium foil in electrolyte, taking out, washing, drying, roasting at 500-600 ℃ for 3 hours to form TiO on the inner and outer surfaces of the pores of the porous titanium foil2Nanotube to obtain TiO2Nanotube/porous titanium foil;
the electrolyte is 0.5 to 1 percent of HF and 1mol/L of H2SO4The mixed solution of (1);
the electrolytic potential of the electrolytic reaction is 20V, and the time of the electrolytic reaction is 30-120 minutes.
9. The preparation method according to claim 3, wherein the step (2) is specifically: adding TiO into the mixture2The nanotube/porous titanium foil is used as a cathode and is placed in electroplating solution for electroplating at room temperature to obtain CoAg-TiO2Nanotube/porous titanium foil;
the components of the electroplating solution are as follows: 0.01mol/L AgNO30.01mol/L of CoSO4And 20g/L of H3BO3；
The PH of the electroplating solution is 4.4;
the current density of the electroplating is 5mA/cm2The time is 30-90 min.
10. The preparation method according to claim 3, wherein the step (3) is specifically: subjecting the CoAg-TiO to2Putting the nanotube/porous titanium foil into HCl solution, performing ultrasonic dispersion for 30min, adding aniline, o-phenylenediamine, 2-acrylamide-2-methylpropanesulfonic acid and p-acetanilide at 5 ℃, after vigorously stirring for 30min, dropping ammonium persulfate solution under stirring, reacting for 6h, repeatedly washing the product with 0.1mol/L HCl solution until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 8h to obtain polyaniline-poly (2-acrylamide-2-methylpropanesulfonic acid) -coated CoAg-TiO2The nanotube/porous titanium foil is used for direct methanol fuel cell electrodes;
wherein the molar ratio of aniline to 2-acrylamide-2-methylpropanesulfonic acid is 2:1, and aniline and TiO2The molar ratio of the nanotubes is 3-1: 1.
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