CN103331172A - Preparation method for non-Pt non-H anode catalyst of proton exchange membrane fuel cell (PEMFC) - Google Patents
Preparation method for non-Pt non-H anode catalyst of proton exchange membrane fuel cell (PEMFC) Download PDFInfo
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Abstract
The invention aims to provide a preparation method for a non-Pt non-H anode catalyst of a proton exchange membrane fuel cell (PEMFC) to solve the problems of the conventional Ir-based catalyst preparation method. The method comprises the following steps: Ni ammonia complex cations are formed by taking strong ammonia solution as a complexant; Ni-Ir precursor is uniformly deposited on the surface of conductive carbon carrier due to the static attraction function between the Ni ammine complex cations and Ir complex anions under a water bath drying evaporation condition; finally, Ir and Ni are slowly released, reduced and alloyed from the complex compounds through hydrogen atmosphere heat treatment so as to form carbon carried Ir-Ni alloy catalyst of which the ingredients are uniform and the nano particles are distributed uniformly. According to the invention, the conventional Ir-based catalyst preparation method is greatly simplified; the surface of prepared catalyst is clean; the particle size of the catalyst is small; the catalyst is high in dispersion; the metal utilization ratio as well as the hadrogen and oxidization activity is effectively improved.
Description
Technical field
The invention belongs to the fuel cell technology field, particularly the preparation method of the non-platinum hydrogen of proton exchanging film fuel battery anode catalyst.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of device that chemical energy is converted to electric energy, it has outstanding features such as the startup fast of energy conversion efficiency height, environmental friendliness, room temperature, specific power and specific energy height, is acknowledged as one of electric supply installation of following main flow.Yet high cost is its real one of business-like key problem that realizes of puzzlement always, and its expensive main cause comes from a large amount of uses of noble metal catalyst platinum.React with respect to cathodic oxygen reduction, PEMFC anode hydrogen oxidation reaction has overpotential and approaches zero, the fast characteristics of kinetic reaction speed, be expected to be issued to application request in the situation of using non-platinum catalyst, therefore, the non-platinum anode catalyst of development high efficiency, low cost is significant.
In various non-platinum anode catalyst, iridium is catalyst based owing to have that catalysis hydroxide reaction overpotential approaches zero, reaction rate is higher, is considered to most possibly replace the anode catalyst of platinum.At present, the synthetic main synthetic method that annealing combines with reducing gases of hydro-thermal that adopts that iridium is catalyst based: document [Int. J. Hydrogen. Energy, 2010,35:5528 – 5538] reported a kind of method with the synthetic IrV/C catalyst of hydrothermal reduction method, this method at first with ethylene glycol be reducing agent and solvent at 120 ℃ of hydrothermal reduction catalyst precursors, under 200 ℃ of reducing atmospheres, catalyst is carried out annealing in process then.Document [J. Phys. Chem. C, 2011,115:9894 – 9902] has been reported a kind of synthetic method of IrNi/C catalyst with core-casing structure, and this method is at first with NaBH
4For reducing agent reduces to metal precursor, after catalyst cleaned, again under reducing atmosphere to 600 ℃ of high-temperature process of catalyst.It is catalyst based that above method has all been prepared the iridium with certain hydroxide activity, yet, the method for preparing process is loaded down with trivial details, influence factor is many, and the elevated temperature heat reduction causes the catalyst granules particle diameter to increase, and catalyst activity can't satisfy the fuel cell application request.Chinese invention patent CN101411012A discloses a kind of " manufacture method of catalyst for fuel cell ", this invention is regulated by the pH value, make each slaine form hydroxide loading on conductive carrier, by two step heat treatable alloyizations, prepare the ternary alloy three-partalloy catalyst of platiniferous, base metal and iridium again.But this method exists, and power consumption is big, front and back purifying process complexity, catalyst particle size is big and the not high problem of catalytic activity, is difficult to satisfy the commercialization requirement.
Summary of the invention
The objective of the invention is the problem at the catalyst based preparation method's existence of existing iridium, the preparation method of the non-platinum hydrogen of proton exchanging film fuel battery anode catalyst is provided.The present invention is that complexing agent at first forms nickel ammino Heyang ion with the concentrated ammonia liquor; Under the water bath method condition, utilize the electrostatic attraction effect between nickel ammino Heyang ion and iridium complex anion that nickel iridium presoma is deposited in the conductive carbon carrier surface equably then; By hydrogen atmosphere heat treatment, make Ir, the Ni carbon that synchronous slow, reduction, alloying formation uniform component, nano particle are evenly distributed from complex compound carry the iridium nickel alloy catalyst at last.The present invention has simplified the catalyst based preparation method of traditional iridium greatly, prepared catalyst surface cleaning, little, the high dispersive of particle diameter, and using rate of metal and hydroxide activity effectively improve.
The object of the present invention is achieved like this: the preparation method of the non-platinum hydrogen of proton exchanging film fuel battery anode catalyst, its concrete grammar step comprises
(1) functionalization of carbon carrier
Get the 500ml round-bottomed flask, take by weighing the commercially available Vulcan XC-72 carbon dust of 1 gram, add 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio and be 150 milliliters of the mixed solutions of 1 ︰ 4, ultrasonic and stir 3 hours after, with ultra-pure water dilution, leave standstill after 24 hours and leach supernatant liquor, through centrifuge washing repeatedly, oven dry obtains functionalization Vulcan XC-72 carbon dust after the grinding.
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.1～2 ︰ 0.05～1 ︰ 0.2～2 by functionalization Vulcan XC-72 Tan Fen ︰ iridium Qian Qu Ti ︰ nickel Qian Qu Ti ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, iridium presoma, nickel presoma and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 10～60 minutes forms homodisperse functionalization Vulcan XC-72 carbon dust suspension, and wherein the mass concentration of functionalization Vulcan XC-72 carbon dust is 3～25 mg/ml; Add iridium presoma, nickel presoma and natrium citricum then successively, ultrasonic dispersion earlier 10～60 minutes, continue to stir 6～24 hours, be that 28% ammoniacal liquor is regulated pH value to 11～13 with mass concentration again, sealing was stirred 6～24 hours, dry, pulverize 50～80 ℃ of water-baths then, obtain carbon and carry the iridium nickel complex.
Wherein said iridium presoma is one of them of the inferior iridium acid of chloro-iridic acid, iridium sodium chloride, chlorine sodium; The nickel presoma is one of them of nickel chloride, nickelous sulfate, nickel nitrate.
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 1～8 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is 300～700 ℃ of heat treatment 1～3 hour under the mixed atmosphere of 100～800 ml/min, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
After the present invention adopts technique scheme, mainly contain following advantage:
(1) the present invention utilizes the electrostatic attraction effect between nickel ammino Heyang ion and iridium complex anion that nickel iridium presoma is deposited in the conductive carbon carrier surface equably; By hydrogen atmosphere heat treatment, make the growth course of crystal and Ir, Ni synchronous from the reduction slowly-releasing of complex compound at last, thus the superfine nano particle that obtains the chemical composition homogeneous and be evenly distributed, and using rate of metal and catalyst activity improve greatly.
(2) need not the hydrothermal reduction step, directly with reducing gases annealing in process synthetic catalyst, last simple cleaning can obtain cleaning surfaces, high dispersive, highly active catalyst, and operation is simple, and environmental protection and economy is applicable to large-scale commercial applications production.
(3) than existing commercialization platinum based catalyst, the carbon of this method preparation carries the iridium nickel alloy catalyst and has tangible cost advantage, can effectively reduce the fuel cell cost.
The inventive method is simple, handling safety, low production cost.Adopt the carbon of the present invention's preparation to carry the iridium nickel alloy catalyst and have catalysis hydroxide performance efficiently, alternative platinum based catalyst is applied to fuel cell field, Proton Exchange Membrane Fuel Cells hydrogen anode particularly, and can realize the large-scale commercial applications production of catalyst.
Description of drawings
The carbon that Fig. 1 makes for embodiment 1 carries high resolution transmission electron microscopy (TEM) figure of iridium nickel alloy catalyst when multiplication factor is 100000 times.
The carbon that Fig. 2 makes for embodiment 1 carry the iridium nickel alloy catalyst and with contrast experiment 1 the commercialization Pt/C(of Britain Jonhson-Matthey company platinum mass percent 40%) the cyclic voltammetry curve figure of catalyst.Curve A is that to carry the iridium nickel alloy catalyst be working electrode to the carbon with embodiment 1 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the saturated 0.1 mol high chloro acid solution of nitrogen is electrolyte, and sweep speed is 50 millivolts of/second cyclic voltammetry curve figure under the condition.Curve B is to be working electrode with the commercialization Pt/C of Britain Jonhson-Matthey company catalyst, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the saturated 0.1 mol high chloro acid solution of nitrogen is electrolyte, and sweep speed is 50 millivolts of/second cyclic voltammetry curve figure under the condition.Wherein iridium nickel dead weight capacity and platinum carrying capacity are 1.25 micrograms on the working electrode, and curve A, the scanning number of turns of B are the 50th circle.
The carbon that Fig. 3 makes for embodiment 1 carry the iridium nickel alloy catalyst and with contrast experiment 1 the commercialization Pt/C(of Britain Jonhson-Matthey company platinum mass percent 40%) the hydroxide linear scan curve map of catalyst.Curve A is that to carry the iridium nickel alloy catalyst be working electrode to the carbon with embodiment 1 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol high chloro acid solution that hydrogen is saturated is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.Curve B is to be working electrode with the commercialization Pt/C of Britain Jonhson-Matthey company catalyst, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the saturated 0.1 mol high chloro acid solution of hydrogen is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.Wherein iridium nickel dead weight capacity and platinum carrying capacity are 1.25 micrograms on the working electrode, and the electrode rotary speed is 1600 rev/mins.
Fig. 4 is the monocell polarization curve of embodiment 1 and contrast test 2.
Among the figure: curve a is that the electrode that carries iridium nickel alloy catalyst preparation with the carbon that embodiment 1 makes is anode, iridium nickel carrying capacity is 0.2 milligram/square centimeter, the electrode that makes with the commercialization Pt/C catalyst (platinum mass percent 40%) of Britain Jonhson-Matthey company is negative electrode, the platinum carrying capacity is 0.3 milligram/square centimeter, voltage-to-current density (V-j) curve of the monocell that is assembled into, operating condition: 80 ℃ of battery temperatures, be fuel with pure hydrogen, pure oxygen is oxidant, the anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode O
2Flow velocity 300 ml/min.
Curve A is that the electrode that carries iridium nickel alloy catalyst preparation with the carbon that embodiment 1 makes is anode, iridium nickel carrying capacity is 0.2 milligram/square centimeter, the electrode that makes with the commercialization Pt/C catalyst (platinum mass percent 40%) of Britain Jonhson-Matthey company is negative electrode, the platinum carrying capacity is 0.3 milligram/square centimeter, power density-the current density of the monocell that is assembled into (P-j) curve, operating condition: 80 ℃ of battery temperatures, be fuel with pure hydrogen, pure oxygen is oxidant, the anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode O
2Flow velocity 300 ml/min.
Curve b is that contrast test 2 is with the commercialization Pt/C(platinum mass percent 40% of Britain Jonhson-Matthey company) electrode that makes of catalyst is voltage-to-current density (V-j) curve of the monocell that is assembled into of anode and cathode, anode platinum carrying capacity is 0.2 milligram/square centimeter, negative electrode platinum carrying capacity is 0.3 milligram/square centimeter, operating condition: 80 ℃ of battery temperatures, be fuel with pure hydrogen, pure oxygen is oxidant, the anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode O
2Flow velocity 300 ml/min.
The curve B electrode that to be contrast test 2 make with the commercialization Pt/C catalyst (platinum mass percent 40%) of Britain Jonhson-Matthey company is power density-current density (P-j) curve of the monocell that is assembled into of anode and cathode, anode platinum carrying capacity is 0.2 milligram/square centimeter, negative electrode platinum carrying capacity is 0.3 milligram/square centimeter, operating condition: 80 ℃ of battery temperatures, be fuel with pure hydrogen, pure oxygen is oxidant, the anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode O
2Flow velocity 300 ml/min.
Fig. 5 carries the hydroxide linear scan curve map of iridium nickel alloy catalyst for the carbon of embodiment 2～4 preparations.
Among the figure: curve A is that to carry the iridium nickel alloy catalyst be working electrode to the carbon with embodiment 2 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the 0.1 mol high chloro acid solution that hydrogen is saturated is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.
Curve B is that to carry the iridium nickel alloy catalyst be working electrode to the carbon with embodiment 3 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol high chloro acid solution that hydrogen is saturated is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.
Curve C is that to carry the iridium nickel alloy catalyst be working electrode to the carbon with embodiment 4 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol high chloro acid solution that hydrogen is saturated is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.
Among Fig. 5 on each hydroxide anode test job electrode iridium nickel carrying capacity be 1.25 micrograms, the electrode rotary speed is 1600 rev/mins.
The specific embodiment
Below in conjunction with the specific embodiment, further specify the present invention.
Embodiment 1
(1) functionalization of carbon carrier
Get the 500ml round-bottomed flask, take by weighing the commercially available Vulcan XC-72 carbon dust of 1 gram, add 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio and be 150 milliliters of the mixed solutions of 1 ︰ 4, ultrasonic and stir 3 hours after, with ultra-pure water dilution, leave standstill after 24 hours and leach supernatant liquor, through centrifuge washing repeatedly, oven dry obtains functionalization Vulcan XC-72 carbon dust after the grinding.
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.45 ︰ 0.13 ︰ 1.17 by functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 30 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 8 mg/ml; Add chloro-iridic acid, nickel chloride and natrium citricum then successively, ultrasonic dispersion earlier 20 minutes continues to stir 12 hours, be that 28% ammoniacal liquor is regulated pH value to 12 with mass concentration again, sealing was stirred 18 hours, dried, pulverized 60 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 6 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 500 ℃ of heat treatments of the mixed atmosphere of 350 ml/min 2 hours, cooling naturally under mixed atmosphere then, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
(4) carbon carries the transmission electron microscope test of iridium nickel alloy catalyst
The carbon for preparing carries the iridium nickel alloy catalyst and obtains high-resolution-ration transmission electric-lens (TEM) photo among Fig. 1 with transmissioning electric mirror test.
(5) catalyst is at the electrochemical property test of three-electrode system
Taking by weighing 1 milligram of (3) prepared carbon of step carries the iridium nickel alloy catalyst and joins in the 800 microlitre absolute ethyl alcohols, after sonic oscillation was uniformly dispersed in 10 minutes, microsyringe is drawn 5 microlitres and evenly is coated on the vitreous carbon rotating disk electrode (r.d.e), and 60 ℃ kept 2 hours down.As working electrode, respectively as auxiliary electrode and reference electrode, cyclic voltammetry scan 50 circles are estimated with activating catalyst and to the electro-chemical activity surface area of catalyst in the perchloric acid solution of 0.1 saturated mol of nitrogen with platinum loop electrode and silver/silver chlorate (Ag/AgCl) electrode.Sweep speed is 50 millivolts/second, and sweep limits is-0.282～0.828 volt (with respect to silver/silver chloride electrode), curve A in the 50th circle cyclic voltammetry curve corresponding diagram 2.After catalyst carried out surface active, test linear scan volt-ampere curve in the perchloric acid solution of the saturated 0.1mol/L of hydrogen, the rotating speed of rotation electrode is 1600 rev/mins, 10 millivolts/second of sweep speeds, sweep limits-0.315～0.1 volt (with respect to silver/silver chloride electrode) is shown in Fig. 3 curve A.
(6) preliminary treatment of carbon paper
Carbon paper is cut to long 3.1 centimetres, wide 2.4 centimetres small rectangle sheet, and carbon paper is immersed in the ethanol water, vibration is 30 minutes under the ultrasonic wave condition.
(7) preparation of Proton Exchange Membrane Fuel Cells anode
The mass ratio that the carbon that makes by embodiment 1 carries iridium nickel alloy Cuiization Ji ︰ perfluorinated sulfonic resin is that 3 ︰ 1 take by weighing carbon and carry iridium nickel alloy catalyst and perfluorinated sulfonic resin (mass concentration is 5%), control iridium nickel content is 0.2 milligram/square centimeter, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be uniformly coated on several times on the carbon paper that step (6) handles and 60 ℃ of oven dry and obtain the Proton Exchange Membrane Fuel Cells anode.
(8) preparation of fuel battery cathode with proton exchange film
Be that the ratio of 3 ︰ 1 takes by weighing Pt/C catalyst and perfluorinated sulfonic resin (mass concentration is 5%) in the mass ratio of the commercialization Pt/C Cuiization Ji ︰ perfluorinated sulfonic resin of Britain Jonhson-Matthey company, the control platinum content is 0.3 milligram/square centimeter, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be uniformly coated on several times on the carbon paper that step (6) handles and 60 ℃ of oven dry and obtain fuel battery cathode with proton exchange film.
(9) preparation of " membrane electrode " assembly and monocell performance evaluation
The Nafion112 film is placed between Proton Exchange Membrane Fuel Cells anode and the negative electrode, and hot pressing was taken out and is cooled to room temperature after 120 second under 135 ℃ and 5 MPa pressure, made " membrane electrode " assembly of fuel cell.The fuel cell anchor clamps of then " membrane electrode " assembly being packed into are estimated.Be fuel with pure hydrogen, pure oxygen is oxidant, and 80 ℃ of battery testing temperature, anode and cathode back pressure are 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode O
2Flow velocity 300 ml/min.The monocell polarization curve is tested under the constant potential condition, and the record current potential is with the situation of change of current density, curve a in the corresponding diagram 4, and recording power density is with the situation of change of current density, curve A in the corresponding diagram 4.
Embodiment 2
Step (1) is with step (1) among the embodiment 1.
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.51 ︰ 0.11 ︰ 1 by functionalization Vulcan XC-72 Tan Fen ︰ chlorine iridium Suan Na ︰ Xiao Suan Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, iridium sodium chloride, nickel nitrate and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 30 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 15 mg/ml; Add iridium sodium chloride, nickel nitrate and natrium citricum then successively, ultrasonic dispersion earlier 20 minutes continues to stir 15 hours, be that 28% ammoniacal liquor is regulated pH value to 11.5 with mass concentration again, sealing was stirred 15 hours, dried, pulverized 60 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 4 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 500 ℃ of heat treatments of the mixed atmosphere of 500 ml/min 2 hours, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method is with step (5) among the embodiment 1, and hydroxide linear scan is curve A in the corresponding diagram 5 as a result.
Embodiment 3
Step (1) is with step (1) among the embodiment 1
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.1 ︰ 0.05 ︰ 0.2 by the inferior iridium Suan of functionalization Vulcan XC-72 Tan Fen ︰ chlorine Na ︰ Liu Suan Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, the inferior iridium acid of chlorine sodium, nickelous sulfate and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 60 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 25 mg/ml; Add the inferior iridium acid of chlorine sodium, nickelous sulfate and natrium citricum then successively, ultrasonic dispersion earlier 10 minutes continues to stir 6 hours, be that 28% ammoniacal liquor is regulated pH value to 11 with mass concentration again, sealing was stirred 6 hours, dried, pulverized 50 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is being 1 ︰ 1 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 700 ℃ of heat treatments of the mixed atmosphere of 100 ml/min 1 hour, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method is with step (5) among the embodiment 1, and hydroxide linear scan is curve B in the corresponding diagram 5 as a result.
Embodiment 4
Step (1) is with step (1) among the embodiment 1.
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 2 ︰ 1 ︰ 2 by functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 10 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 3 mg/ml; Add chloro-iridic acid, nickel chloride and natrium citricum then successively, ultrasonic dispersion earlier 60 minutes continues to stir 24 hours, be that 28% ammoniacal liquor is regulated pH value to 13 with mass concentration again, sealing was stirred 24 hours, dried, pulverized 80 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 8 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 300 ℃ of heat treatments of the mixed atmosphere of 800 ml/min 3 hours, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method is with step (5) among the embodiment 1, and hydroxide linear scan is curve C in the corresponding diagram 5 as a result.
The contrast experiment 1
The commercialization Pt/C(of Britain Jonhson-Matthey company platinum mass percent 40%) catalyst the electrochemical property test of three-electrode system with embodiment 1 in step (5), wherein curve B in the volt-ampere curve figure corresponding diagram 2 of cyclic voltammetric test scan the 50th circle; Curve B in the hydroxide linear scan curve corresponding diagram 3.
The contrast experiment 2
(1) preparation of Proton Exchange Membrane Fuel Cells catalysis electrode
Be that the ratio of 3 ︰ 1 takes by weighing Pt/C catalyst and perfluorinated sulfonic resin (mass concentration is 5%) in the mass ratio of the commercialization Pt/C Cuiization Ji ︰ perfluorinated sulfonic resin of Britain Jonhson-Matthey company, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be uniformly coated on several times on the carbon paper of handling in embodiment 1 step (4), control anode platinum content is 0.3 milligram/square centimeter, the negative electrode platinum content is 0.3 milligram/square centimeter, and obtain Proton Exchange Membrane Fuel Cells catalysis electrode the moon, anode respectively 60 ℃ of oven dry.
(2) the monocell performance evaluation of Proton Exchange Membrane Fuel Cells catalysis electrode
Go on foot the Proton Exchange Membrane Fuel Cells catalysis electrode of preparation as anode and cathode with (1).The Nafion112 film is placed between negative electrode and the anode, and hot pressing was taken out and is cooled to room temperature after 120 second under 135 ℃ and 5 MPa pressure, made " membrane electrode " assembly of fuel cell.The fuel cell anchor clamps of then " membrane electrode " assembly being packed into are estimated.Be fuel with pure hydrogen, pure oxygen is oxidant, and 80 ℃ of battery testing temperature, anode and cathode back pressure are 200 kPas (absolute pressures), anode hydrogen gas flow velocity 200 ml/min, negative electrode oxygen gas flow rate 300 ml/min.
The monocell polarization curve is tested under the constant potential condition, and the record current potential is with the situation of change of current density, curve b in the corresponding diagram 4, and recording power density is with the situation of change of current density, curve B in the corresponding diagram 4.
Result of the test of the present invention:
As can be seen from Figure 1, it is little that the prepared carbon of the present invention carries iridium nickel alloy catalyst particle, high dispersive, and particle diameter is distributed as 1.1～3.5nm, and average grain diameter is 2.1nm.
As can be seen from Figure 2, under the identical situation of theoretical metal carrying capacity, carry out the cyclic voltammetric test, the prepared carbon of the present invention carries the iridium nickel alloy catalyst to be compared with the commercialization Pt/C of Britain Jonhson-Matthey company catalyst, and the electrochemical surface that is obtained by cyclic voltammetry curve is long-pending bigger.
As can be seen from Figure 3, in the hydroxide linear scan test of under the identical situation of theoretical metal carrying capacity, carrying out, the prepared carbon of the present invention carries the iridium nickel alloy catalyst to be compared with the commercialization Pt/C of Britain Jonhson-Matthey company catalyst, carrying current increases to some extent than the commercialization Pt/C of Jonhson-Matthey company, shows that the catalytic activity that carbon that the present invention prepares carries the hydroxide of iridium nickel alloy catalyst is better than the commercialization Pt/C of Jonhson-Matthey company catalyst.
Fig. 4 is under the condition of negative electrode for the Jonhson-Matthey company commercialization Pt/C electrode that adopts the identical platinum carrying capacity, and the carbon that adopts the present invention to prepare respectively carries the iridium nickel alloy catalyst and the commercialization Pt/C of Jonhson-Matthey company is the monocell curve map that anode is assembled into fuel cell.As can be seen from Figure 4, when the anode metal carrying capacity was identical, the carbon of the present invention preparation carried the operating voltage of iridium nickel alloy catalyst and the electrode power commercialization Pt/C electrode that is enough to match in excellence or beauty.
As can be seen from Figure 5, the prepared all kinds of carbon of the present invention carry the iridium nickel alloy catalyst in hydroxide linear scan test, all show good hydroxide catalytic activity.
Claims (6)
1. the preparation method of the non-platinum hydrogen of proton exchanging film fuel battery anode catalyst, its concrete grammar step comprises
(1) functionalization of carbon carrier
Get the 500ml round-bottomed flask, take by weighing the commercially available Vulcan XC-72 carbon dust of 1 gram, add 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio and be 150 milliliters of the mixed solutions of 1 ︰ 4, ultrasonic and stir 3 hours after, with ultra-pure water dilution, leave standstill after 24 hours and leach supernatant liquor, through centrifuge washing repeatedly, oven dry obtains functionalization Vulcan XC-72 carbon dust after the grinding;
It is characterized in that:
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.1～2 ︰ 0.05～1 ︰ 0.2～2 by functionalization Vulcan XC-72 Tan Fen ︰ iridium Qian Qu Ti ︰ nickel Qian Qu Ti ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, iridium presoma, nickel presoma and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 10～60 minutes forms homodisperse functionalization Vulcan XC-72 carbon dust suspension, and wherein the mass concentration of functionalization Vulcan XC-72 carbon dust is 3～25 mg/ml; Add iridium presoma, nickel presoma and natrium citricum then successively, ultrasonic dispersion earlier 10～60 minutes, continue to stir 6～24 hours, be that 28% ammoniacal liquor is regulated pH value to 11～13 with mass concentration again, sealing was stirred 6～24 hours, dry, pulverize 50～80 ℃ of water-baths then, obtain carbon and carry the iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 1～8 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is 300～700 ℃ of heat treatment 1～3 hour under the mixed atmosphere of 100～800 ml/min, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
2. according to the preparation method of the non-platinum hydrogen of the described proton exchanging film fuel battery of claim 1 anode catalyst, it is characterized in that described iridium presoma is one of them of chloro-iridic acid, iridium sodium chloride, the inferior iridium acid of chlorine sodium; The nickel presoma is one of them of nickel chloride, nickelous sulfate, nickel nitrate.
3. according to the preparation method of the non-platinum hydrogen of the described proton exchanging film fuel battery of claim 1 anode catalyst, it is characterized in that concrete preparation method's step (2)～(3):
(2) complexing of metal precursor supports
Mass ratio 1 ︰ 0.45 ︰ 0.13 ︰ 1.17 by functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 30 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 8 mg/ml; Add chloro-iridic acid, nickel chloride and natrium citricum then successively, ultrasonic dispersion earlier 20 minutes continues to stir 12 hours, be that 28% ammoniacal liquor is regulated pH value to 12 with mass concentration again, sealing was stirred 18 hours, dried, pulverized 60 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is being 1 ︰ 6 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 500 ℃ of heat treatments of the mixed atmosphere of 350 ml/min 2 hours, cooling naturally under mixed atmosphere then, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
4. according to the preparation method of the non-platinum hydrogen of the described proton exchanging film fuel battery of claim 1 anode catalyst, it is characterized in that concrete preparation method's step (2)～(3):
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.51 ︰ 0.11 ︰ 1 by functionalization Vulcan XC-72 Tan Fen ︰ chlorine iridium Suan Na ︰ Xiao Suan Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, iridium sodium chloride, nickel nitrate and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 30 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 15 mg/ml; Add iridium sodium chloride, nickel nitrate and natrium citricum then successively, ultrasonic dispersion earlier 20 minutes continues to stir 15 hours, be that 28% ammoniacal liquor is regulated pH value to 11.5 with mass concentration again, sealing was stirred 15 hours, dried, pulverized 60 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 4 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 500 ℃ of heat treatments of the mixed atmosphere of 500 ml/min 2 hours, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
5. according to the preparation method of the non-platinum hydrogen of the described proton exchanging film fuel battery of claim 1 anode catalyst, it is characterized in that concrete preparation method's step (2)～(3):
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 0.1 ︰ 0.05 ︰ 0.2 by the inferior iridium Suan of functionalization Vulcan XC-72 Tan Fen ︰ chlorine Na ︰ Liu Suan Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, the inferior iridium acid of chlorine sodium, nickelous sulfate and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 60 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 25 mg/ml; Add the inferior iridium acid of chlorine sodium, nickelous sulfate and natrium citricum then successively, ultrasonic dispersion earlier 10 minutes continues to stir 6 hours, be that 28% ammoniacal liquor is regulated pH value to 11 with mass concentration again, sealing was stirred 6 hours, dried, pulverized 50 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is being 1 ︰ 1 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 700 ℃ of heat treatments of the mixed atmosphere of 100 ml/min 1 hour, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
6. according to the preparation method of the non-platinum hydrogen of the described proton exchanging film fuel battery of claim 1 anode catalyst, it is characterized in that concrete preparation method's step (2)～(3):
(2) carbon carries the preparation of iridium nickel complex
Mass ratio 1 ︰ 2 ︰ 1 ︰ 2 by functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum takes by weighing step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum respectively; Earlier functionalization Vulcan XC-72 carbon dust is added in the deionized water, ultrasonic dispersion 10 minutes, forming homodisperse mass concentration is the functionalization Vulcan XC-72 carbon dust suspension of 3 mg/ml; Add chloro-iridic acid, nickel chloride and natrium citricum then successively, ultrasonic dispersion earlier 60 minutes continues to stir 24 hours, be that 28% ammoniacal liquor is regulated pH value to 13 with mass concentration again, sealing was stirred 24 hours, dried, pulverized 80 ℃ of water-baths then, obtained carbon and carried the iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
It is 1 ︰ 8 in Qing Qi ︰ argon gas volume ratio that the carbon of step (2) gained is carried the iridium nickel complex, total gas flow rate is the following 300 ℃ of heat treatments of the mixed atmosphere of 800 ml/min 3 hours, cooling naturally under mixed atmosphere, washing, vacuum drying at last obtains carbon and carries the iridium nickel alloy catalyst.
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| CN110635146A (en) * | 2019-08-23 | 2019-12-31 | 同济大学 | High-performance Pt-based tri-alloy catalyst and preparation method thereof |
| CN110828832A (en) * | 2018-08-07 | 2020-02-21 | 深圳渝鹏新能源汽车检测研究有限公司 | Preparation method of iridium-based catalyst for anode of hydrogen-oxygen fuel cell |
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| CN107275653A (en) * | 2017-08-03 | 2017-10-20 | 重庆大学 | A kind of preparation method of fuel cell hydroxide non-platinum catalyst |
| CN108470917A (en) * | 2018-04-19 | 2018-08-31 | 华南理工大学 | A kind of carbon carries difunctional electrocatalysis material of compound and preparation method thereof between iridium manganese Metal |
| CN108470917B (en) * | 2018-04-19 | 2020-06-19 | 华南理工大学 | Carbon-supported iridium-manganese intermetallic compound bifunctional electrocatalytic material and preparation method thereof |
| CN110828832A (en) * | 2018-08-07 | 2020-02-21 | 深圳渝鹏新能源汽车检测研究有限公司 | Preparation method of iridium-based catalyst for anode of hydrogen-oxygen fuel cell |
| CN111244486A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Preparation and application of graphite type carbon nitride and carbon composite carrier supported Ir catalyst |
| CN110635146A (en) * | 2019-08-23 | 2019-12-31 | 同济大学 | High-performance Pt-based tri-alloy catalyst and preparation method thereof |
| CN111085195A (en) * | 2019-12-30 | 2020-05-01 | 宁波中科科创新能源科技有限公司 | Metal alloy catalyst and preparation method thereof |
| CN111085195B (en) * | 2019-12-30 | 2022-12-27 | 宁波中科科创新能源科技有限公司 | Metal alloy catalyst and preparation method thereof |
| CN113594483A (en) * | 2021-07-28 | 2021-11-02 | 宁波中科科创新能源科技有限公司 | Preparation method of PtCo intermetallic compound catalyst and fuel cell |
| CN113871640A (en) * | 2021-09-24 | 2021-12-31 | 中汽创智科技有限公司 | Anti-reversal catalyst for fuel cell and preparation method and application thereof |
| CN113871640B (en) * | 2021-09-24 | 2024-01-16 | 中汽创智科技有限公司 | Fuel cell anti-reverse electrode catalyst and preparation method and application thereof |
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