CN100461511C - Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method - Google Patents
Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method Download PDFInfo
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- CN100461511C CN100461511C CNB2006101136926A CN200610113692A CN100461511C CN 100461511 C CN100461511 C CN 100461511C CN B2006101136926 A CNB2006101136926 A CN B2006101136926A CN 200610113692 A CN200610113692 A CN 200610113692A CN 100461511 C CN100461511 C CN 100461511C
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- porphyrin
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Existing catalysts are noble metals generally, which are costly and easy poisoning. Active component of the disclosed catalyst is transition metal nitride. Carrier is activated carbon powder Vulcan XC-72. Percentage content of mass of transition metal nitride in active component is 1-6%. The preparation method includes steps: dissolving macrocyclic compound of transition metal, Vulcan XC-72 into organic solvent, and carrying out ultrasonic action for 30-60 minutes; stirring up and drying out the said solution under normal temperature, and obtaining powder after drying; loading the powder to closed container and letting ammonia into the container; controlling temperature of heat treatment at 600-1000 deg.C, and time as 0.5-10h so as to obtain the catalyst after natural cooling. Area ratio activity of carbon carried platinum catalyst is 1.5mA/cm2, and the disclosed carbon carried nitride catalyst reaches to 3.1 mA/cm2. Features are: simple flow and easy controlled procedure.
Description
Technical field
The invention belongs to the fuel-cell catalyst field.
Background technology
Direct methanol fuel cell is a kind of of Proton Exchange Membrane Fuel Cells, is electrolyte with the solid polymer membrane, uses liquid or gas methyl alcohol to act as a fuel.It is a kind of of fuel cell, has the plurality of advantages of fuel cell: do not pollute, quiet efficient, help environmental protection.Also having does not in addition need middle the reformation or reforming unit, and volume in light weight is little, battery design and simple to operateization.Owing to above-mentioned plurality of advantages, be particularly suitable for the removable power supply of various uses, as mobile phone, notebook computer and electric vehicle power sources etc.
In direct methanol fuel cell, the Pt/C catalyst is often used as the cathodic oxygen reduction eelctro-catalyst, is that people study maximum a kind of fuel-cell catalysts.Because precious metals pt is less relatively, price comparison is expensive, has limited its practical application and commercialization fully, must develop a kind of oxygen reduction electro-catalyst that on a small quantity or does not contain noble metal that contains.Wherein the heat treatment of carbon-supported metal porphyrin compound in this respect application obtain bigger progress, have good catalytic activity and stability, and the methanol tolerance performance arranged, promise to be the catalyst that replaces noble metal.Performance and commercialization in direct methanol fuel cell at present requires to have the problem of big gap to also have one to be exactly the methyl alcohol penetrate proton exchange membrane arrival negative electrode of anode, and can carry at carbon commonly used oxidation takes place on the platinum cathode, make catalyst poisoning, this not only makes methyl alcohol can not get sufficient application, and has a strong impact on the performance of battery.
Just have been found that transition metal macrocyclic compound can be used for the catalyst of hydrogen reduction the sixties in 20th century, but these transition metal huge legendary turtle compounds are unsettled eelctro-catalysts when directly using.At this phenomenon, [Faubert G, Lalande G, Cote R, etal.Electrochimica Acta[J], 1996,41 (10): 1689-1701.] etc. the people is adsorbed on iron, cobalt tetraphenylporphyrin on the carbon black respectively, heat-treats under argon gas is saturated, and heat treated temperature is at 100-1000 ℃. can improve activity of such catalysts and stability by heat treatment, up to now, people's research mostly is under inert atmosphere fuel-cell catalyst to be heat-treated.Existing catalyst is generally noble metal, the expensive and easy poisoning of price comparison.
Summary of the invention
The invention provides a kind of cathode in direct methanol fuel cells non-precious metal catalyst, it is characterized in that, active component is a transition metal nitride, and carrier is a Vulcan XC-72 activated carbon powder, and wherein the quality percentage composition of transition metal nitride is 1-6% in the active component.
Have extremely similar character because nickel, iron, manganese all belong to transition metal, its porphyrin also has similar character, so also have similar hydrogen reduction character after the heat treatment in ammonia.
The present invention also provides a kind of preparation method of cathode in direct methanol fuel cells non-precious metal catalyst, it is characterized in that, may further comprise the steps:
1) transition metal macrocyclic compound, Vulcan XC-72 activated carbon powder are dissolved in the organic solvent ultrasonic 30-60 minute; Wherein transition metal macrocyclic compound is for being one of the monokaryon porphyrin of central metal ion and derivative thereof with molybdenum, cobalt, nickel, iron, manganese; Organic solvent is one of oxolane, ethanol, acetone, isopropyl alcohol, N-N dimethyl formamide, N-N dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, pyridine or ether; The mass ratio of transition metal macrocyclic compound and Vulcan XC-72 activated carbon powder is 1:9-1:1 in solvent;
2) above-mentioned solution is stirred evaporate to dryness at normal temperatures, 60-80 ℃ of drying obtains powder;
3) with above-mentioned steps 2) powder that the obtains closed container of packing into, feed ammonia, the flow of ammonia is 0.5-31/min, and controlling heat treated temperature is 600-1000 ℃, and heat treatment time is 0.5-10h, and lowering the temperature naturally obtains catalyst.
Described monokaryon derivatives of porphyrin is the tetramethoxy porphyrin, tetrasulfonic acid base porphyrin, tetraphenylporphyrin, one of octaethylporphyrin.
In the step 1) in organic solvent the content of activated carbon be 0.02-9g/L, the content of transition metal macrocyclic compound is 0.02-1g/L.
This method technological process is simple, and process is easy to control.By the direct methanol fuel cell catalyst of this method preparation, X-ray diffraction analysis is the result show, resulting activity of such catalysts component is a nitride.The model of transmission electron microscope is JEM-2010F, and the lens analysis result shows that resultant catalyst granules particle diameter is little, is 4-6nm substantially, is uniformly dispersed.All raw materials that the present invention uses are not noble metals, thereby have realized the base metalization of catalyst.The carbon of preparation is carried nitride catalyst and normally used carbon supported platinum catalyst, be prepared into electrode, adopt the monocell three-electrode system to carry out electro-chemical test, the cathodic polarization curve test result shows, under identical test condition, the area specific activity of carbon supported platinum catalyst is 1.5mA/cm
2Carbon of the present invention carries nitride catalyst, has then reached 3.1mA/cm
2Quite and the former 2 times.In the direct methanol fuel cell noble metal catalyst, cathod catalyst is poisoned and has been had a strong impact on the performance of battery, cathodic polarization curve test shows as a result has or not the curve of methyl alcohol front and back not have substantially to change, illustrate that this catalyst has anti methanol toxication ability preferably. under the monocell three-electrode system, carry out electro-chemical test equally, the timing current curve shows that this catalyst oxidation current attenuation ratio in acid solution is slower, has stability preferably.
Prepared catalyst adopts the monocell three-electrode system to carry out electro-chemical test.To electrode is smooth platinized platinum electrode, and reference electrode is the mereurous sulfate electrode, and all for this electrode, electrolyte is 0.5mol/l H to current potential as described below
2SO
4Solution and 0.5mol/l H
2SO
4+ 0.5mol/lCH
3OH, logical 30 minutes N before the experiment
2Or O
2Gas, sweep speed are 10mV/s.The electro-chemical test instrument is U.S. EG﹠amp; The Model 273A type constant potential/electric current instrument of G company.
Description of drawings:
Accompanying drawing 1 is the X ray diffracting spectrum of the catalyst that provided of the embodiment of the invention 4.
Accompanying drawing 2 is that the catalyst that provided of the embodiment of the invention 1 is at 0.5MH
2Cathodic polarization curve in the SO4 solution.
Accompanying drawing 3 is lens photos of the catalyst that provided of the embodiment of the invention 2.
Accompanying drawing 4 is stability curves of the catalyst that provided in the embodiment of the invention 1.
Accompanying drawing 5 is that the catalyst that provided in the embodiment of the invention 4 is at 0.5MH
2SO
4And 0.5MH
2SO
4+ 0.5CH
3Linear scan curve among the OH.
Embodiment:
Also in conjunction with the accompanying drawings the present invention is explained in detail below by embodiment.
Embodiment 1
Is that 1:9 is dissolved in the oxolane with molybdenum tetraphenylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio, ultrasonic 60 minutes; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 1l/min, and controlling heat treated temperature is 700 ℃, reacts 3h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN/C catalyst.The lens photo shows that the particle diameter of MoN is that 5-6nm. is obtained by cathodic polarization curve accompanying drawing 2, and the reduction take-off potential of oxygen on catalyst is-0.1V that the area specific activity is 3.1mA/cm
2, and carbon supported platinum catalyst area specific activity is 1.5mA/cm under the relative rotation speed situation consistent with sweep speed
2, having increased by 1 times, catalytic activity is better than carbon supported platinum catalyst.When having methyl alcohol to exist, the polarization curve of catalyst does not have significant change, and methanol tolerance character has been described.Accompanying drawing 4 is the timing current curve of catalyst, and this curve shows that oxidation current is undamped substantially, catalyst stable relatively good.
Embodiment 2.
Is that 1:1 is dissolved in the acetone with molybdenum octaethylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio, ultrasonic 50 minutes; Above-mentioned solution stirring at normal temperature evaporate to dryness, 60 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 0.5l/min, and controlling heat treated temperature is 700 ℃, reacts 4h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.Accompanying drawing 2 lens photos show that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Embodiment 3
Is that 2:3 is dissolved in the N-N dimethylacetylamide with molybdenum tetramethoxy porphyrin and Vulcan XC-72 activated carbon powder by mass ratio, ultrasonic 50 minutes; Above-mentioned solution stirring at normal temperature evaporate to dryness, 70 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 2l/min, and controlling heat treated temperature is 600 ℃, reacts 5h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.The lens photo shows that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Embodiment 4
Is that 2:3 is dissolved in the ethanol with molybdenum tetrasulfonic acid base porphyrin and Vulcan XC-72 activated carbon powder by mass ratio, ultrasonic 40 minutes; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 3l/min, and controlling heat treated temperature is 1000 ℃, reacts 4h under this temperature, stops heating then, is chilled to room temperature, obtains the MoN catalyst.Accompanying drawing 1XRD collection of illustrative plates show the component of gained catalyst be MoN and standard diagram coincide relatively good. the lens photo shows that the particle diameter of catalyst is that 5-6nm. accompanying drawing 5 is this catalyst 0.5MH
2SO
4And 0.5MH
2SO
4+ 0.5CH
3The OH cathodic polarization curve shows, the peak of methanol oxidation does not appear in catalyst when methyl alcohol exists, and the take-off potential of oxygen reduction cathode electric current is approaching in two kinds of solution, the significantly not negative phenomenon of moving, reduction current just reduces a little when methyl alcohol exists, this catalyst that illustrates that we prepare has good anti methanol toxication performance. show that by electrochemistry cathodic polarization curve and timing current curve the catalytic performance of this catalyst has reached the catalytic performance of carbon platinum-carrying electrocatalyst.
Embodiment 5
Is that 1:9 is dissolved in the tetrachloromethane with cobalt tetraphenylporphyrin and Vulcan XC-72 activated carbon powder by mass ratio, ultrasonic 30 minutes; Above-mentioned solution stirring at normal temperature evaporate to dryness, 80 ℃ of dryings.The powder-tight that obtains feeds ammonia in quartz glass tube, flow is 1l/min, and controlling heat treated temperature is 900 ℃, reacts 3h under this temperature, stops heating then, is chilled to room temperature, obtains the CoN catalyst.The lens photo shows that the particle diameter of catalyst is that 5-6nm. shows that by electrochemistry cathodic polarization curve and timing current curve this catalyst performance is better than the carbon platinum-carrying electrocatalyst.
Claims (1)
1. the preparation method of a cathode in direct methanol fuel cells non-precious metal catalyst is characterized in that, may further comprise the steps:
1) transition metal macrocyclic compound, Vulcan XC-72 activated carbon powder are dissolved in the organic solvent ultrasonic 30-60 minute; Wherein transition metal macrocyclic compound is for being one of the monokaryon porphyrin of central metal ion and derivative thereof with molybdenum, cobalt, nickel, iron, manganese; Described monokaryon derivatives of porphyrin is the tetramethoxy porphyrin, tetrasulfonic acid base porphyrin, tetraphenylporphyrin, one of octaethylporphyrin; Organic solvent is one of oxolane, ethanol, acetone, isopropyl alcohol, N-N dimethyl formamide, N-N dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, pyridine or ether; The mass ratio of transition metal macrocyclic compound and Vulcan XC-72 activated carbon powder is 1:9-1:1 in solvent; The content of activated carbon is 0.02-9g/L in organic solvent, and the content of transition metal macrocyclic compound is 0.02-1g/L;
2) above-mentioned solution is stirred evaporate to dryness at normal temperatures, 60-80 ℃ of drying obtains powder;
3) with above-mentioned steps 2) powder that the obtains closed container of packing into, feed ammonia, the flow of ammonia is 0.5-3l/min, and controlling heat treated temperature is 600-1000 ℃, and heat treatment time is 0.5-10h, and lowering the temperature naturally obtains catalyst.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2441108B1 (en) * | 2009-06-10 | 2014-07-02 | Toyota Jidosha Kabushiki Kaisha | Method for producing electrode catalyst for fuel cell |
| US8709964B2 (en) * | 2010-09-14 | 2014-04-29 | Basf Se | Process for producing a carbon-comprising support |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN102626649A (en) * | 2012-03-21 | 2012-08-08 | 重庆大学 | Oxygen reduction non-noble metal catalyst and preparation method thereof |
| CN103170355B (en) * | 2012-11-01 | 2015-10-21 | 周德璧 | A kind of air electrode metal nitride catalyst preparation method being applied to air cell |
| US10646595B2 (en) * | 2013-02-12 | 2020-05-12 | The Governing Council Of The University Of Toronto | Porphyrin compounds and their use as MRI contrast agents |
| CN104143643B (en) * | 2013-05-09 | 2016-06-15 | 中国科学院大连化学物理研究所 | A kind of fuel cell supported catalyst and application thereof |
| CN103247805B (en) * | 2013-05-09 | 2016-04-27 | 北京大学 | A kind of Non-noble metal electrocatalyst for fuel cell and preparation method thereof |
| JP6672935B2 (en) * | 2015-03-30 | 2020-03-25 | 東洋インキＳｃホールディングス株式会社 | Carbon catalyst, method for producing the same, catalyst ink, and fuel cell |
| KR101894920B1 (en) * | 2016-12-21 | 2018-09-04 | 현대자동차주식회사 | Non-noble metal based catalyst and method of manufacturing the same |
| CN111224114A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation and application of carbon-supported bimetallic nitride electrocatalyst |
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| CN1642635A (en) * | 2002-02-14 | 2005-07-20 | 孟山都技术公司 | Oxidation catalyst and process for its preparation and process for oxidation using it |
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