CN1577927A - Low-temperature fuel cell platinum-tin base anode catalyst - Google Patents
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Abstract
The present invention relates to fuel cell technology, and is especially one kind anode catalyst for proton exchange film type fuel cell to convert chemical energy into electric energy. When the catalyst is used in low temperature direct alcohol proton exchange film fuel cell, the low temperature fuel cell oxidizes alcohol directly into CO2 while releasing electrons to realize the high efficiency conversion from chemical energy to electric energy. The present invention adopts cheap tin for modulating noble metal catalyst platinum, and the direct alcohol fuel cell has obviously improved performance even if in case of reduced platinum anode carrying amount.
Description
Technical Field
The invention relates to a fuel cell technology, in particular to a proton exchange membrane type fuel cell anode catalyst for converting chemical energy into electric energy.
Background
The fuel cell has the advantages of high energy conversion efficiency, no pollution, no noise and the like, is attracted by attention in recent years, particularly the Proton Exchange Membrane Fuel Cells (PEMFCs) have higher power density than other types of fuel cells, and have the greatest advantages of low working temperature, quick start, wide working area and sensitive response, and are suitable for places with frequent start. It can be used for building dispersed power station, also can be used as movable power source, and is applicable to civil and military use. The fuel cell can be used as a fuel by using hydrogen, can also directly adopt a fuel liquid, particularly a liquid fuel, does not need an intermediate conversion device, has the advantages of simple system structure, high volume energy density, convenient fuel supplement and the like, is particularly suitable for being used as a small-sized movable power supply, such as a mobile phone, a notebook computer, an electric vehicle power supply and the like, has potential application prospects in the fields of transportation, medical treatment, communication, military and the like, and is more and more favored by international researchers and enterprises at home and abroad. Methanol has simple structure and higher reaction activity, is the first choice fuel of low-temperature direct liquid fuel cells, and recently has more reports on detailed preparation and assembly technology and performance data of direct methanol fuel cells, wherein Germany has successfully assembled a battery pack which is 4.2L in volume and consists of 71 single cells, and the power of the battery pack reaches 500W. However, methanol has low boiling point, is volatile and has high toxicity, so that the methanol can stimulate optic nerves of people and cause blindness when being used excessively. In addition, the perfluor sulfonic acid membrane is widely used as a solid electrolyte in the proton exchange membrane fuel cell at present, and the permeability of methanol in the electrolyte is high, so that a large amount of methanol permeates from an anode to a cathode, the performance of the direct methanol fuel cell is deteriorated, most obviously, the open-circuit voltage of the cell is far lower than the theoretical electromotive force, and the open-circuit voltage is also a great obstacle for preventing the commercialization of the direct methanol fuel cell. Therefore, it is necessary to search for other liquid fuels to replace toxic methanol, and at the same time, it is helpful to expand the development of low temperature direct liquid fuel cells, enhance their competitiveness, and promote their commercialization process. Ethanol is the simplest chain alcohol, can be produced in large quantities by fermentation of sugar-containing organic matter, can also be produced from biomass, is widely available, is a renewable energy source, and is far less toxic than methanol. In view of the potential application prospects of ethanol in fuel cells, its electrocatalytic oxidation has been widely studied.
When ethanol is directly used as fuel, the chemical reaction of the electrodes in the cell is as follows:
electrochemical oxidation reaction of ethanol as anode:
electrochemical reduction reaction of cathode with oxygen:
the overall cell reaction is:
the cell standard electrochemical potential was 1.145V (vs NHE) with ethanol as fuel. Compared with a direct methanol fuel cell, the direct ethanol fuel cell has higher specific energy density (8.00kWh/kg ethanol vs. 6.09kWh/kg methanol) and higher energy conversion efficiency (96.9% ethanol and 96.7% methanol). In conclusion, the direct use of ethanol as a fuel has a greater attraction for low temperature fuel cells.
Current research on ethanol in fuel cell related specialties has focused primarily on the reformation of ethanol to produce hydrogen for fueling hydrogen/oxygen proton exchange membrane fuel cells. This requires a complete set of ethanol reforming and gas purification equipment, and the system is complex, reducing the efficiency of the fuel cell system. For example, as described in literature [ Ioannides, t.neurophylides, s., j.power SourCes ], under ideal reforming conditions, the system efficiency is 60% at low load and 30-35% at maximum power density. Few direct ethanol fuels are reported in the literature at present.
Literature [ f.haga, t.nakajima, h.miya and s.mishima, cat.lett., ] hydrogen production by partial oxidative reforming of ethanol, using Ni and Co as catalysts, respectively. Although the process adopts cheap metal as a catalyst, C-C bonds in ethanol molecules are required to be broken in the reforming reaction, and ethylene is easily formed on the surface of the Ni catalyst by ethanol to form carbon deposit, so that the catalyst is inactivated. Document [ s.cavallaro and s.freni, int.j.hydrogen Energy, ] reforming ethanol to produce hydrogen at around 300 ℃ using Cu/Zn/Al as catalyst. The catalyst has stable performance and does not generate by-products such as methane, ethylene and the like. However, the reforming process is endothermic and requires external energy, and in actual operation, the external energy is somewhat completed by the discharge of the fuel cell, which inevitably reduces the energy output of the fuel cell.
One of the main problems of the low-temperature direct ethanol fuel cell with the proton exchange membrane as the electrolyte is how to improve the electrocatalytic oxidation activity of ethanol at the anode at low temperature. The ethanol molecule contains a C-C single bond, and in the electrochemical oxidation process of the ethanol, the breakage of the C-C single bond is related to whether electrons can be completely released and the effective utilization rate of the fuel. The novel high-efficiency anode catalyst is beneficial to ensuring the breakage of C-C bonds in ethanol molecules. Meanwhile, more carbon-containing intermediates are generated in the electrochemical oxidation process of the ethanol, and the intermediates are firmly adsorbed on the surface of noble metal such as platinum (Pt) and the like, so that the intermediates are not easy to eliminate, and the smooth proceeding of the reaction is hindered. Therefore, there is a need to develop a platinum (Pt) -based multi-component catalyst. The noble metals and the cheap metals form a bi-component or multi-component catalyst, so that the catalytic activity and the stability of the noble metals can be effectively improved, and the addition of other metals is also beneficial to improving the utilization rate of the noble metals. Unlike the research situation of direct methanol fuel cells, a platinum ruthenium (PtRu) catalyst is a methanol anode catalyst which is relatively accepted at present, and no catalyst has relatively ideal catalytic activity for the electrochemical oxidation of ethanol at present. In view of the similarity of the molecular structures of ethanol and methanol, some researchers directly transplanted a methanol anode catalyst into ethanol electrocatalytic oxidation reaction, for example, documents [3] and [4] conducted catalyst mechanism and single cell studies by directly using platinum ruthenium (PtRu) or the like as an ethanol electrocatalyst, but even at operating temperatures as high as 145 ℃ or even higher, the electrochemical oxidation reaction activity of ethanol on the platinum ruthenium (PtRu) catalyst was inferior to that of methanol, and the maximum power density of the cell using platinum ruthenium (PtRu) as an anode catalyst was only one third of that of a direct methanol fuel cell. Therefore, the research and development of the anode catalyst with high catalytic activity and low price are the key points of the research and development of the direct ethanol fuel cell.
Disclosure of Invention
The invention provides a platinum-tin (Pt/Sn) based anode catalyst for direct electrocatalytic oxidation of ethanol, and a direct ethanol fuel cell shows better performance when the catalyst is used as an anode.
The invention provides a method for converting chemical energy into electric energy by directly carrying out electrocatalytic oxidation on ethanol at a low temperature, and provides an anode catalyst with low price and excellent performance for the electrocatalytic reaction. The invention includes the preparation of platinum (Pt) based ethanol anode catalysts by a variety of methods, including simultaneous and step-wise loading of platinum (Pt) and other metals. Comparing the activity of the catalyst through the performance of the ethanol electrocatalytic oxidation reaction at low temperature, and screening the anode catalyst suitable for the ethanol low-temperature direct electrocatalytic oxidation reaction.
The invention specifically comprises the following contents:
1. the catalyst of the invention is based on platinum tin. Contains one or more of other transition metals or does not contain other elements.
2. The atomic ratio of the platinum and tin elements in the catalyst is 0.01-99.
3. The catalyst may be a supported catalyst.
4. When preparing the supported platinum-tin-based catalyst, platinum and tin can be simultaneously supported or can be supported step by step.
5. The preparation method of the catalyst which is preferably adopted by the invention and the steps thereof are as follows:
(1) respectively preparing a platinum compound, a tin compound and other transition metal compounds into solutions, or preparing the platinum compound, the tin compound and one or more other transition metal compounds into a solution containing platinum and one or more other transition metal elements according to a certain atomic ratio. Other transition metals include elements from groups VIB and VIIIB of the periodic table, especially ruthenium, tungsten, palladium, and the like; the solvent used comprises water, or a mixed solvent formed by mixing a plurality of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion, or a mixed solvent formed by mixing one of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol with water, or a mixed solvent formed by mixing a plurality of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion and water.
(2) And dispersing the carrier with a solvent to prepare carrier slurry. The carrier comprises various materials which are stable under acidic and/or alkaline conditions, and the preferred carrier comprises various carbon materials such as activated carbon, carbon black and carbon nano tubes, or various carbon materials loaded with metal, such as carbon-loaded platinum, carbon-loaded nickel and the like. The solvents used include: water, or one of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol, or a mixed solvent formed by mixing several of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion, or a solvent formed by mixing one of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol with water, or a mixed solvent formed by mixing several of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion and water.
(3) Preparing various alkali solutions. These alkaline materials include various kinds of hydroxide compounds, alkali metal carbonates, etc., and the most preferable alkaline materials include hydroxides and carbonates of sodium and potassium. The solvents used include: water, or one of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol, or a mixed solvent formed by mixing several of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion, or a solvent formed by mixing one of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol with water, or a mixed solvent formed by mixing several of C2-C8 monohydric alcohol, dihydric alcohol and trihydric alcohol in any proportion and water.
(4) And (3) mixing the mixtures prepared in the steps (1), (2) and (3) according to a certain proportion to make the pH of the formed mixture alkaline.
(5) And (4) heating the mixed solution in the step (4), keeping the temperature at 60-250 ℃ and keeping the time for 15-600 minutes.
(6) Adding a settling promoter, and adjusting the pH to be acidic. The settling promoting agent comprises various acid gases and various acid aqueous solutions.
(7) And (3) filtering and washing the mixture prepared in the step (6), and drying in vacuum at 40-200 ℃ to obtain the highly dispersed nano-scale platinum-tin-based catalyst. The catalyst can be directly used or treated under the condition of treating for 0.1-72 hours at 40-1000 ℃ in various atmospheres.
(8) And preparing the prepared catalyst into an electrode.
(9) And (3) adopting a proton exchange membrane as an electrolyte, taking the electrode prepared in the step (8) as an ethanol electrocatalytic oxidation anode, and assembling an oxygen electrocatalytic reduction cathode into a membrane electrode assembly by adopting a platinum-carbon (Pt/C) catalyst. The anode side is filled with ethanol water solution, and the cathode side is filled with oxygen or air.
Comparison of the present invention with the related art:
literature [ j.t.wang, s.wasmus, r.f.savinerl, j.electrochem.soc.]And document [ a.s.aric oa, p.creti, p.l.antonuci, v.antonuci, electrochem.solid State Lett.]Platinum ruthenium (PtRu) is adopted to catalyze the electrochemical oxidation reaction of ethanol. Platinum ruthenium (PtRu) catalysts have proven to be suitable methanol electrochemical oxidation catalysts, showing better methanol electrocatalytic activity and CO poisoning resistance in direct methanol fuel cells and hydrogen-oxygen proton exchange membrane fuel cells, and in view of this, it is understood that platinum ruthenium (PtRu) is used as the anode of direct ethanol fuel cells. The modified proton exchange membrane is adopted to increase the operating temperature of the fuel cell, and can improve the electro-oxidation activity of ethanol on platinum ruthenium (PtRu), thereby improving the performance of the direct ethanol fuel cell. However, despite increasing the operating temperature to 145 ℃, the performance of direct ethanol fuel cells is still less than that of direct methanol fuel cells using the same anode catalystCan be used. The invention adopts platinum-tin catalyst and conventional Nafion®The proton exchange membrane does not need to modify the electrolyte, and the performance of the direct ethanol fuel cell is equivalent to that of a direct methanol fuel cell adopting the same anode catalyst even at 90 ℃.
The invention is characterized in that:
1. the performance of the direct ethanol fuel cell is obviously improved even under the condition of reducing the loading capacity of a platinum anode by adopting the tin modulated noble metal catalyst platinum with low price and rich reserves. FIG. 1 shows the performance comparison results of the direct ethanol fuel cell using platinum carbon (Pt/C) and platinum tin carbon (PtSn/C) as anode catalysts.
2. When cheap platinum-tin-carbon is used as anode catalyst to replace expensive platinum-ruthenium-carbon, the performance of the direct ethanol fuel cell is obviously improved under the condition of keeping the platinum anode loading fixed, and the maximum output power density is increased by about one time. FIG. 2 shows the performance comparison results of the direct ethanol fuel cell using Pt-Ru-C (PtRu/C) and Pt-Sn-C (PtSn/C) as anode catalysts.
3. Platinum tin carbon (PtSn/C) is used as an anode catalyst of the proton exchange membrane fuel cell, methanol (direct methanol fuel cell at the moment) and ethanol (direct ethanol fuel cell at the moment) are respectively used as fuels, the performance of the direct ethanol fuel cell is superior to that of the direct methanol fuel cell in a larger current density range, and the maximum output power density of the two cells is similar. Figure 3 is a comparison of the performance of two fuel cells using the same anode catalyst.
4. The expensive ruthenium metal (PtSn-Ru carbon PtSnRu/C) is continuously added into the cheap Pt-Sn-C (PtSn/C). The two catalysts are used as anodes to prepare direct ethanol fuel cells. When platinum tin ruthenium carbon is used as an anode catalyst, although the amount of noble metal (platinum ruthenium) used in the anode is increased and the price of the catalyst is also increased, the performance of the direct ethanol fuel cell is reduced.
5. The atomic ratio of platinum to tin (Pt/Sn) in the platinum to tin carbon (PtSn/C) anode catalyst affects the electrocatalytic activity of ethanol.
6. The method of changing the solvent composition is adopted to ensure that the metal particles in the prepared catalyst are uniformly distributed, and the particle diameter is in a nanometer range.
Drawings
FIG. 1 shows the respective use of platinum-carbon (Pt/C) and platinum-tin-carbon(PtSn/C) as anode catalyst, and comparing the performance of the direct ethanol fuel cell;Pt/C，2.0mgPt/cm2；Pt1Sn1/C，1.3mgPt/cm2(ii) a The electrolyte is Nafion®-115 a membrane; the fuel is 1.0mol/L ethanol water solution; the cathode catalyst is Pt/C, and the metal dosage is 1.0mgPt/cm2(ii) a The cell operating temperature was 90 ℃.
FIG. 2 is a graph showing the performance comparison of a direct ethanol fuel cell using platinum ruthenium carbon (PtRu/C) and platinum tin carbon (PtSn/C) as anode catalysts, respectively;
Pt1Ru1/C，1.3mgPt/cm2；
Pt1Sn1/C，1.3mgPt/cm2(ii) a The electrolyte is Nafion®-115 a membrane; the fuel is 1.0mol/L ethanol water solution; the cathode catalyst is Pt/C, and the metal dosage is 1.0mgPt/cm2(ii) a The cell operating temperature was 90 ℃.
FIG. 3 is a comparison of performance of two fuel cells using the same anode catalyst; the dosage of the anode noble metal is 1.3mgPt/cm2(ii) a The electrolyte is Nafion®-115 a membrane; the cathode catalyst is Pt/C, and the metal dosage is 1.0mgPt/cm2(ii) a The battery operating temperature is 90 ℃;
a direct methanol fuel cell;◆ -direct ethanol fuel cell.
FIG. 4 is the result of electron microscopy (TEM) analysis of a Pt-Sn-C PtSn/C catalyst and its particle size distribution; a. electron microscope results of PtSn/C catalyst. And B, counting the metal particles in the electron microscope photo of the PtSn/C catalyst.
Detailed Description
The invention is described in detail below by way of examples:
catalyst preparation example 1: preparation of platinum-tin-carbon (PtSn/C) (32 PtSn%, Pt/Sn ═ 1) catalyst
And weighing active carbon XC-72R 2 g, and ultrasonically oscillating and dispersing the active carbon for 30 minutes by using 150 ml of ethylene glycol to prepare carbon slurry. Measuring 20 ml of chloroplatinic acid/ethylene glycol solution (29.5 mg of platinum/ml), measuring 10 ml of stannic chloride ethanol solution (35 mg of tin/ml), mixing, dropwise adding the mixture into carbon slurry after ultrasonic oscillation for 20 minutes, dropwise adding 1.5 mol/L sodium hydroxide/ethylene glycol solution 15 ml after stirring for 4 hours by introducing argon to remove oxygen, continuously stirring for 4 hours, heating to 130 ℃ for 4 hours, then cooling to 25 ℃, adjusting the pH value to 2.5 by using 1.5 mol/L dilute hydrochloric acid solution, stirring for 6 hours, filtering and washing, and vacuum drying at 70 ℃ overnight. A catalyst of 20 wt.% platinum (Pt) -12 wt.% tin (Sn) was obtained. The yield is 97%, and the transmission electron microscope and X-ray diffraction experiment result shows that the size of the bi-component noble metal particles is below 3.0 nanometers, refer to FIG. 4.
Catalyst preparation example 2: preparation of platinum tin ruthenium carbon (PtSnRu/C) (42 PtRu%, Pt/Sn/Ru ═ 1) catalyst
The active carbon XC-72R is treated by 5mol/L nitric acid solution in advance, and 5.8 g of active carbon is weighed and dispersed by 400 ml of ethylene glycol for 30 minutes by ultrasonic oscillation after being dried for 4 hours at 200 ℃ to prepare carbon slurry. 5.4 g of chloroplatinic acid (containing 2.0 g of platinum) was dissolved in 50 ml of ethylene glycol, and 2.7 g of ruthenium trichloride (containing 1.0 g of ruthenium) was dissolved in 50 ml of a dilute hydrochloric acid solution of tin chloride (containing 1.2 g of tin) to prepare a mixed solution of tin and ruthenium. Dropping the mixed solution of tin and ruthenium into the solution of platinum, ultrasonically oscillating for 20 minutes, transferring into carbon slurry, introducing argon to remove oxygen, stirring for 5 hours, adjusting the pH value to 13 by using 1 mol/L sodium hydroxide/ethylene glycol solution, continuously stirring for 4 hours, heating to 135 ℃, keeping for 4 hours, then cooling to room temperature of 25 ℃, adjusting the pH value to 2.5, stirring for 3 hours, and filtering. The filter cake was dried under vacuum at 85 ℃ for 8 hours to give a catalyst of 20 wt.% platinum (Pt) -12 wt.% tin (Sn) -10 wt.% ruthenium (Ru). The transmission electron microscope and X-ray diffraction experiment result show that the size of the bi-component noble metal particles is below 2.5 nanometers, and refer to FIG. 4.
Catalyst preparation example 3: preparation of platinum-tin-carbon (PtSn/C) (26 PtSn%, Pt/Sn ═ 2) catalyst
21 wt.% platinum carbon (Pt/C) catalyst was used as a carrier, and tin was supported. 2 g of 21 wt.% platinum carbon (Pt/C) was weighed out and dispersed with 100 ml of ethylene glycol for 30 minutes with shaking to obtain a slurry mixture. Adding 10 ml of tin tetrachloride ethanol solution (12.7 mg of tin/ml) into the slurry mixture, deoxidizing with argon, stirring for 2 hours, adjusting the pH value to 13.5 with 1.0mol/L of sodium hydroxide ethanol solution, heating to 120 ℃, keeping for 1 hour, then cooling to room temperature, adding 150 ml of deionized water, adjusting the pH value to 3 with dilute hydrochloric acid solution, stirring for 1 hour, filtering, washing, and vacuum-drying at 80 ℃ overnight. A catalyst of 20 wt.% platinum (Pt) -6 wt.% tin (Sn) was obtained. The transmission electron microscope and the X-ray diffraction experiment result show that the size of the bi-component noble metal particles is below 3.0 nanometers, and refer to FIG. 4.
Catalyst preparation example 4: preparation of platinum tin ruthenium carbon (PtSnRu/C) (37 PtRu%, Pt/Sn/Ru 2/2/1) catalyst
A catalyst of 21 wt.% platinum (Pt) -12.6 wt.% tin-carbon (Sn/C) was used as a support, and ruthenium was supported. 9.5 g of platinum tin on carbon was weighed out and dispersed for 45 minutes with 200 ml of ethylene glycol with shaking to obtain a slurry mixture. 40 ml of aqueous ruthenium trichloride solution (12.5 mg of ruthenium/ml) is added into the slurry mixture, argon is used for removing oxygen and stirring for 1.5 hours, 1.0mol/L of sodium hydroxide ethanol solution is used for adjusting the pH value to 13.5, the temperature is raised to 130 ℃ and kept for 1 hour, then the temperature is reduced to room temperature, 150 ml of deionized water is added, the pH value is adjusted to 2 by dilute hydrochloric acid solution, the mixture is filtered and washed after being stirred for 1 hour, and the mixture is dried in vacuum at 80 ℃ overnight. A catalyst of 20 wt.% platinum (Pt) -12 wt.% tin (Sn) -5 wt.% ruthenium (Ru) was obtained. The transmission electron microscope and the X-ray diffraction experiment result show that the size of the bi-component noble metal particles is below 3.0 nanometers, and refer to FIG. 4.
Example 5: direct ethanol fuel cell preparation
The platinum (Pt) based catalyst anode catalyst prepared in the embodiment 2-4 adopts Nafion®-115 perfluorosulfonic acid membrane (a perfluorosulfonic acid membrane number manufactured by Du Pont Co., Ltd.) as an electrolyte to prepare a single cell. 67.0mg of platinum tin carbon (PtSn/C) (20 wt.% Pt, 12 wt.% Sn) was weighed and mixed with an appropriate amount of H2O and C2H5Mixing with mixed solvent of OH, adding 5% Nafion®150.0mg, ultrasonically oscillating uniformly, and brushing to 10Cm2On the diffusion layer of (a), an anode was prepared, wherein the platinum loading was 1.3mg/Cm2. 50.0mg of 20 wt.% platinum-carbon (Pt/C) catalyst (commercially available from Johnson Matthey corporation) was weighed out with an appropriate amount of H2O and C2H5Adding 20% polytetrafluoroethylene aqueous solution 62.5mg into mixed solvent composed of OH, uniformly shaking with ultrasonic vibration, and coating to 10Cm2Diffusion layer ofThus, a cathode was prepared. Spraying 5% Nafion on the surface of the cathode and anode catalyst layer®Solution at a loading of 1.0mg/Cm2. Then with Nafion®And (3) hot-pressing the (-115) perfluorosulfonic acid membrane at 130 ℃ for 2 minutes to obtain a membrane electrode assembly, and placing one or more stainless steel nets on two sides of the membrane electrode assembly respectively to assemble single cells. The polar plate is a stainless steel plate, and the effective area of the battery is 9Cm2. 1.0mol/L ethanol water solution is introduced into the anode side, and the flow rate is 1.0 ml/min. Oxygen is introduced into the cathode side, and the pressure is 0.2 MPa. Heating to 90 deg.C, activating, and discharging. And after the discharge performance of the battery is stable, measuring the polarization curve of the battery, wherein the performance curve is shown in attached figures 1, 2 and 3. In addition, a commercial catalyst platinum ruthenium carbon (PtRu/C) (20 wt.% Pt, 10 wt.% Ru), a self-made platinum ruthenium carbon (PtRu/C) (20 wt.% Pt, 10 wt.% Ru), and a self-made platinum tin carbon (PtSn/C) (20 wt.% Pt-6 wt.% Sn) of Johnson Matthey were used as anode electrocatalysts, respectively, and anodes were prepared according to the above steps to assemble single cells.
Claims (12)
1. A low-temperature fuel cell platinum-tin-based anode catalyst is characterized in that after the catalyst is used in a low-temperature direct ethanol proton exchange membrane fuel cell, the low-temperature fuel cell directly oxidizes ethanol into carbon dioxide at the anode, and simultaneously releases electrons, so that the high-efficiency conversion of chemical energy and electric energy is realized.
2. The platinum-tin-based anode catalyst according to claim 1, wherein a proton exchange membrane is used as an electrolyte and a platinum-tin-based catalyst is used as an anodic ethanol electrooxidation catalyst.
3. The platinum-tin-based anode catalyst according to claim 2, wherein the platinum-tin-based catalyst has an atomic ratio of platinum to tin of 0.01 to 99.
4. The platinum-tin-based anode catalyst according to claim 3, wherein the platinum-tin-based catalyst may be supported on a carrier having good electrical conductivity.
5. The platinum-tin-based anode catalyst according to claim 4, wherein the platinum-tin-based catalyst can be prepared by a variety of methods, and further transition metal promoters can be added on the basis of platinum tin.
6. The platinum-tin-based anode catalyst according to claim 5, wherein the platinum-tin-based catalyst is prepared by the following method:
(1) dispersing the carrier by using a solvent to prepare a carrier suspension;
(2) dissolving a metal compound by using the solvent in the step (1), and carrying out ultrasonic oscillation and mixing for 5-60 minutes to prepare a solution;
(3) mixing the solution prepared in the step (2) with the carrier suspension according to the requirement of the metal atomic ratio, ultrasonically oscillating for 5-150 minutes, and stirring for 0.5-24 hours;
(4) adjusting the pH value of the solution prepared in the step (3) to be alkaline, ultrasonically oscillating for 5-600 minutes, stirring for 0.5-24 hours, and keeping at 40-250 ℃ for 0.5-12 hours;
(5) and (3) cooling the solution prepared in the step (4) to 0-50 ℃, adjusting the pH value to be acidic, stirring or heating for a period of time to promote precipitation, filtering, washing with deionized water, and vacuum-drying at 40-200 ℃ to obtain the platinum-tin-based catalyst.
7. The preparation method of claim 6, wherein the solvent in step (1) comprises water, or one of monohydric alcohol, dihydric alcohol and trihydric alcohol C2-C8, or a mixed solvent of monohydric alcohol, dihydric alcohol and trihydric alcohol C2-C8 in any proportion, or a mixed solvent of monohydric alcohol, dihydric alcohol and trihydric alcohol C2-C8 and water, or a mixed solvent of monohydric alcohol, dihydric alcohol and trihydric alcohol C2-C8 in any proportion and water.
8. The method according to claim 6, wherein the metal compound in step (2) is one or more selected from platinum, tin and other transition metals.
9. The method according to claim 6, wherein the solution of step (2) is adjusted to a basic pH and then the operation is carried out according to step (3).
10. The platinum-tin-based anode catalyst according to claim 4, wherein the platinum tin and other metal promoters may be deposited simultaneously or may be supported in steps; before use, the catalyst can be treated in different atmospheres at different temperatures or can be directly used without treatment.
11. The platinum-tin-based anode catalyst according to claim 4, wherein the carrier comprises various types of materials stable under acidic and/or alkaline conditions, and the preferred carrier comprises various types of carbon materials such as activated carbon, carbon black, carbon nanotubes, or various types of carbon materials loaded with metals such as platinum on carbon and nickel on carbon.
12. The method of claim 6, wherein the metal precursor solution comprises one or more of a platinum tin compound and other transition metal compounds.
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Cited By (4)
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| CN100364156C (en) * | 2005-11-04 | 2008-01-23 | 北京工业大学 | Platinum and platina bimetallic catalyst using SnO2 as double connection layer and preparing method |
| CN106711467A (en) * | 2017-01-10 | 2017-05-24 | 大连理工大学 | Preparation method and application of platinum and core-shell structure carbon composite electrocatalyst |
| CN112751044A (en) * | 2020-06-05 | 2021-05-04 | 浙江浙能技术研究院有限公司 | Anode material of solid oxide fuel cell and preparation method thereof |
| CN113903933A (en) * | 2021-09-29 | 2022-01-07 | 清华大学深圳国际研究生院 | Carbon-supported platinum-tin nano catalyst for long-life proton exchange membrane fuel cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07246336A (en) * | 1994-01-24 | 1995-09-26 | Tanaka Kikinzoku Kogyo Kk | Anode electrode catalyst for fuel cell and production thereof |
| EP1164651A1 (en) * | 2000-06-12 | 2001-12-19 | Asahi Glass Co., Ltd. | Electrode catalyst for polymer electrolyte fuel cell and method for its production |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100364156C (en) * | 2005-11-04 | 2008-01-23 | 北京工业大学 | Platinum and platina bimetallic catalyst using SnO2 as double connection layer and preparing method |
| CN106711467A (en) * | 2017-01-10 | 2017-05-24 | 大连理工大学 | Preparation method and application of platinum and core-shell structure carbon composite electrocatalyst |
| CN112751044A (en) * | 2020-06-05 | 2021-05-04 | 浙江浙能技术研究院有限公司 | Anode material of solid oxide fuel cell and preparation method thereof |
| CN112751044B (en) * | 2020-06-05 | 2022-06-17 | 浙江浙能技术研究院有限公司 | Anode material of solid oxide fuel cell and preparation method thereof |
| CN113903933A (en) * | 2021-09-29 | 2022-01-07 | 清华大学深圳国际研究生院 | Carbon-supported platinum-tin nano catalyst for long-life proton exchange membrane fuel cell and preparation method thereof |
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