CN103331172B - 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 field of fuel cell technology, particularly the preparation method of a proton exchanging film fuel battery non-platinum hydrogen anode catalyst.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of device chemical energy being converted to electric energy, it has that energy conversion efficiency is high, environmental friendliness, room temperature start fast, specific power and the outstanding feature such as specific energy is high, is acknowledged as one of electric supply installation of following main flow.But high cost is perplex it really to realize one of business-like key problem always, the main cause of its high cost comes from a large amount of uses of noble metal catalyst platinum.Relative to Cathodic oxygen reduction, PEMFC anode hydrogen oxidation reaction have overpotential close to zero, the fast feature of kinetic reaction speed, be expected to using the situation of non-platinum catalyst to be issued to application request, therefore, the non-platinum anode catalysts of development high efficiency, low cost is significant.
In various non-platinum anode catalysts, iridium based catalyst due to have catalysis hydroxide reaction overpotential close to zero, reaction rate is higher, is considered to the anode catalyst most possibly replacing platinum.At present, the synthesis of iridium based catalyst mainly adopts Hydrothermal Synthesis and reducing gases to anneal the method combined: document [Int.J.Hydrogen.Energy, 2010,35:5528 – 5538] report a kind of method of synthesizing IrV/C catalyst with hydrothermal reduction method, the method first with ethylene glycol be reducing agent and solvent at 120 DEG C of hydrothermal reduction catalyst precursors, then under 200 DEG C of reducing atmospheres, annealing in process is carried out to catalyst.Document [J.Phys.Chem.C, 2011,115:9894 – 9902] reports a kind of synthetic method of IrNi/C catalyst with core-casing structure, and the method is first with NaBH
4for reducing agent reduces to metal precursor, after catalyst is cleaned, more under reducing atmosphere to catalyst 600 DEG C of high-temperature process.Above method has all prepared the iridium based catalyst with certain hydroxide activity, but, said method preparation process is loaded down with trivial details, influence factor is many, and high-temperature hot reduction causes catalyst granules particle diameter to increase, and catalyst activity cannot meet fuel cell application request.Chinese invention patent CN101411012A discloses one " manufacture method of catalyst for fuel cell ", this invention is regulated by pH value, each slaine is made to form hydroxide loading on conductive carrier, again by two-step thermal processing alloying, prepare the ternary alloy catalyst of platiniferous, base metal and iridium.But the problem that the method exists, and power consumption is large, front and back purifying process is complicated, catalyst particle size is comparatively large and catalytic activity is not high, is difficult to meet commercialization requirement.
Summary of the invention
The object of the invention is, for existing iridium based catalyst preparation method Problems existing, to provide the preparation method of a proton exchanging film fuel battery non-platinum hydrogen anode catalyst.The present invention is that first complexing agent forms nickel ammonia complexing cation with concentrated ammonia liquor; Then, under water bath method condition, utilize the electrostatic attraction effect between nickel ammonia complexing cation and iridium complex anion that nickel iridium presoma is deposited in conducting carbon support surface equably; Finally by hydrogen atmosphere heat treatment, the carbon that Ir, Ni synchronous slow, reduction, alloying forming component from complex compound are homogeneous, nano particle is evenly distributed is made to carry iridium nickel alloy catalyst.The present invention enormously simplify traditional iridium based catalyst preparation method, and prepared catalyst surface is clean, particle diameter is little, high dispersive, and using rate of metal and hydroxide activity effectively improve.
The object of the present invention is achieved like this: the preparation method of a proton exchanging film fuel battery non-platinum hydrogen anode catalyst, its concrete grammar step comprises
(1) functionalization of carbon carrier
Take 1 gram of commercially available Vulcan XC-72 carbon dust, add the mixed solution 150 milliliters that 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio is 1 ︰ 4, ultrasonic and after stirring 3 hours, dilute with ultra-pure water, leave standstill and leach supernatant liquor after 24 hours, through repeatedly centrifuge washing, dry, after grinding, obtain functionalization Vulcan XC-72 carbon dust.
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, iridium presoma, nickel presoma and natrium citricum is taken respectively by mass ratio 1 ︰ 0.1 ~ 2 ︰ 0.05 ~ 1 ︰ 0.2 ~ 2 of functionalization Vulcan XC-72 Tan Fen ︰ iridium Qian Qu Ti ︰ nickel Qian Qu Ti ︰ natrium citricum; First add in deionized water by functionalization Vulcan XC-72 carbon dust, ultrasonic disperse 10 ~ 60 minutes, form homodisperse functionalization Vulcan XC-72 carbon dust suspension, wherein the mass concentration of functionalization Vulcan XC-72 carbon dust is 3 ~ 25 mg/ml; Then iridium presoma, nickel presoma and natrium citricum is added successively, first ultrasonic disperse 10 ~ 60 minutes, continue stirring 6 ~ 24 hours, be ammoniacal liquor adjust ph to 11 ~ 13 of 28% again by mass concentration, sealing stirring 6 ~ 24 hours, then dry 50 ~ 80 DEG C of water-baths, pulverize, obtain carbon and carry iridium nickel complex.
Wherein said iridium presoma be chloro-iridic acid, iridium sodium chloride, chlorine sub-iridium acid sodium one of them; Nickel presoma be nickel chloride, nickelous sulfate, nickel nitrate one of them.
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 1 ~ 8, total gas flow rate is 300 ~ 700 DEG C of heat treatment 1 ~ 3 hour under the mixed atmosphere of 100 ~ 800 ml/min, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries 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 ammonia complexing cation and iridium complex anion that nickel iridium presoma is deposited in conducting carbon support surface equably; Finally by hydrogen atmosphere heat treatment, make the growth course of crystal synchronous from the reduction slowly-releasing of complex compound with Ir, Ni, thus obtain the homogeneous and superfine nano particle be evenly distributed of chemical composition, using rate of metal and catalyst activity improve greatly.
(2) without the need to hydrothermal reduction step, directly with reducing gases annealing in process synthetic catalyst, last simple cleaning can obtain surface cleaning, high dispersive, highly active catalyst, and operation is simple, environmental protection and economy, is applicable to large-scale commercial and produces.
(3) compared to existing commercialization platinum based catalyst, carbon prepared by the method carries iridium nickel alloy catalyst and has obvious cost advantage, can effectively reduce fuel cell cost.
The inventive method is simple, handling safety, low production cost.The carbon adopting the present invention to prepare carries iridium nickel alloy catalyst and has efficient catalysis hydroxide performance, and alternative platinum based catalyst is applied to fuel cell field, particularly Proton Exchange Membrane Fuel Cells hydrogen anode, and the large-scale commercial that can realize catalyst is produced.
Accompanying drawing explanation
Fig. 1 is that the carbon that embodiment 1 obtains carries the high resolution transmission electron microscopy of iridium nickel alloy catalyst when multiplication factor is 100000 times (HRTEM) figure.
Fig. 2 is that the obtained carbon of embodiment 1 carries iridium nickel alloy catalyst and with the cyclic voltammetry curve figure of Britain Jonhson-Matthey company trade Pt/C (the platinum mass percent 40%) catalyst of contrast experiment 1.Curve A is that the carbon prepared with embodiment 1 carries iridium nickel alloy catalyst for working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the saturated 0.1 mol/L high chloro acid solution of nitrogen is electrolyte, and sweep speed is the cyclic voltammetry curve figure under 50 millivolts of/second conditions.Curve B is for working electrode with Britain Jonhson-Matthey company trade Pt/C catalyst, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the saturated 0.1 mol/L high chloro acid solution of nitrogen is electrolyte, and sweep speed is the cyclic voltammetry curve figure under 50 millivolts of/second conditions.Wherein on working electrode, iridium nickel dead weight capacity and platinum carrying capacity are 1.25 micrograms, curve A, and the scanning number of turns of B is the 50th circle.
Fig. 3 is that the obtained carbon of embodiment 1 carries iridium nickel alloy catalyst and with the hydroxide linear scan curve map of Britain Jonhson-Matthey company trade Pt/C (the platinum mass percent 40%) catalyst of contrast experiment 1.Curve A is that the carbon prepared with embodiment 1 carries iridium nickel alloy catalyst for working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol/L 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 for working electrode with Britain Jonhson-Matthey company trade Pt/C catalyst, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the saturated 0.1 mol/L high chloro acid solution of hydrogen is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.Wherein on working electrode, iridium nickel dead weight capacity and platinum carrying capacity are 1.25 micrograms, and electrode rotary speed is 1600 revs/min.
Fig. 4 is the monocell polarization curve of embodiment 1 and contrast test 2.
In figure: curve a carries electrode prepared by iridium nickel alloy catalyst for anode with the carbon that embodiment 1 is obtained, iridium nickel carrying capacity is 0.2 milli gram/cm, the electrode obtained with the commercialization Pt/C catalyst (platinum mass percent 40%) of Jonhson-Matthey company of Britain is for negative electrode, platinum carrying capacity is 0.3 milli gram/cm, voltage-current density (V-j) curve of the monocell be assembled into, operating condition: battery temperature 80 DEG C, with pure hydrogen for fuel, pure oxygen is oxidant, anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, negative electrode O
2flow velocity 300 ml/min.
Curve A carries electrode prepared by iridium nickel alloy catalyst for anode with the carbon that embodiment 1 is obtained, iridium nickel carrying capacity is 0.2 milli gram/cm, the electrode obtained with the commercialization Pt/C catalyst (platinum mass percent 40%) of Jonhson-Matthey company of Britain is for negative electrode, platinum carrying capacity is 0.3 milli gram/cm, power density-current density (P-j) curve of the monocell be assembled into, operating condition: battery temperature 80 DEG C, with pure hydrogen for fuel, pure oxygen is oxidant, anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, negative electrode O
2flow velocity 300 ml/min.
Curve b is contrast test 2 is voltage-current density (V-j) curve of the monocell that anode and cathode is assembled into the electrode that the commercialization Pt/C of Jonhson-Matthey company of Britain (platinum mass percent 40%) catalyst obtains, anode platinum carrying capacity is 0.2 milli gram/cm, negative electrode platinum carrying capacity is 0.3 milli gram/cm, operating condition: battery temperature 80 DEG C, with pure hydrogen for fuel, pure oxygen is oxidant, anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, negative electrode O
2flow velocity 300 ml/min.
Curve B is contrast test 2 is power density-current density (P-j) curve of the monocell that anode and cathode is assembled into the electrode that the commercialization Pt/C catalyst (platinum mass percent 40%) of Jonhson-Matthey company of Britain is obtained, anode platinum carrying capacity is 0.2 milli gram/cm, negative electrode platinum carrying capacity is 0.3 milli gram/cm, operating condition: battery temperature 80 DEG C, with pure hydrogen for fuel, pure oxygen is oxidant, anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, negative electrode O
2flow velocity 300 ml/min.
Fig. 5 is that carbon prepared by embodiment 2 ~ 4 carries the hydroxide linear scan curve map of iridium nickel alloy catalyst.
In figure: curve A is that the carbon prepared with embodiment 2 carries iridium nickel alloy catalyst for working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the 0.1 mol/L 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 the carbon prepared with embodiment 3 carries iridium nickel alloy catalyst for working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol/L 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 the carbon prepared with embodiment 4 carries iridium nickel alloy catalyst for working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, and the 0.1 mol/L high chloro acid solution that hydrogen is saturated is electrolyte, sweep speed be under 10 millivolts of/second conditions hydroxide linear scan curve.
In Fig. 5, on each hydrogen oxidation anode test job electrode, iridium nickel carrying capacity is 1.25 micrograms, and electrode rotary speed is 1600 revs/min.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment 1
(1) functionalization of carbon carrier
Take 1 gram of commercially available Vulcan XC-72 carbon dust, add the mixed solution 150 milliliters that 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio is 1 ︰ 4, ultrasonic and after stirring 3 hours, dilute with ultra-pure water, leave standstill and leach supernatant liquor after 24 hours, through repeatedly centrifuge washing, dry, after grinding, obtain functionalization Vulcan XC-72 carbon dust.
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum is taken respectively by mass ratio 1 ︰ 0.45 ︰ 0.13 ︰ 1.17 of functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 30 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 8 mg/ml; Then add chloro-iridic acid, nickel chloride and natrium citricum successively, first ultrasonic disperse 20 minutes, continue stirring 12 hours, be the ammoniacal liquor adjust ph to 12 of 28% again by mass concentration, sealing stirring 18 hours, then dries 60 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 6, total gas flow rate is the lower 500 DEG C of heat treatments of the mixed atmosphere of 350 ml/min 2 hours, then naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
(4) carbon carries the transmission electron microscope test of iridium nickel alloy catalyst
The carbon prepared carries high-resolution-ration transmission electric-lens (HRTEM) photo that iridium nickel alloy catalyst transmissioning electric mirror test obtains in Fig. 1.
(5) catalyst is at the electrochemical property test of three-electrode system
The carbon taken obtained by 1 milligram of (3) step carries iridium nickel alloy catalyst and joins in 800 microliter anhydrous ethanol, after sonic oscillation is uniformly dispersed for 10 minutes, microsyringe is drawn 5 microlitres and is evenly coated in vitreous carbon rotating disk electrode (r.d.e), keeps 2 hours at 60 DEG C.As working electrode, using platinum loop electrode and silver/silver chlorate (Ag/AgCl) electrode as auxiliary electrode and reference electrode, in the perchloric acid solution of saturated 0.1 mol/L of nitrogen, cyclic voltammetry scan 50 encloses with activating catalyst and evaluates the electrochemical active surface of catalyst.Sweep speed is 50 millivolts/second, and sweep limits is-0.282 ~ 0.828 volt (relative to silver/silver chloride electrode), curve A in the 50th circle cyclic voltammetry curve corresponding diagram 2.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of the saturated 0.1mol/L of hydrogen, the rotating speed of rotation electrode is 1600 revs/min, sweep speed 10 millivolts/second, sweep limits-0.315 ~ 0.1 volt (relative to silver/silver chloride electrode), as shown in Fig. 3 curve A.
(6) pretreatment of carbon paper
Carbon paper is cut to the small rectangle sheet of long 3.1 centimetres, wide 2.4 centimetres, and carbon paper is immersed in ethanol water, vibrate 30 minutes under Ultrasonic Conditions.
(7) preparation of anode of proton exchange membrane fuel cell
The mass ratio carrying iridium nickel alloy Cuiization Ji ︰ perfluorinated sulfonic resin by the carbon that embodiment 1 is obtained is that 3 ︰ 1 take carbon and carry iridium nickel alloy catalyst and perfluorinated sulfonic resin (mass concentration is 5%), controlling iridium nickel content is 0.2 milli gram/cm, then be solvent shaken well under Ultrasonic Conditions with ethanol, be uniformly coated on several times on carbon paper that step (6) processes and obtain anode of proton exchange membrane fuel cell 60 DEG C of oven dry.
(8) preparation of fuel battery cathode with proton exchange film
The ratio being 3 ︰ 1 in the mass ratio of the commercialization Pt/C Cuiization Ji ︰ perfluorinated sulfonic resin of Jonhson-Matthey company of Britain takes Pt/C catalyst and perfluorinated sulfonic resin (mass concentration is 5%), controlling platinum content is 0.3 milli gram/cm, then be solvent shaken well under Ultrasonic Conditions with ethanol, be uniformly coated on several times on carbon paper that step (6) processes and obtain fuel battery cathode with proton exchange film 60 DEG C of oven dry.
(9) preparation of " membrane electrode " assembly and monocell performance evaluation
Be placed between anode of proton exchange membrane fuel cell and negative electrode by Nafion112 film, under 135 DEG C and 5 MPa, hot pressing is after 120 seconds, takes out and is cooled to room temperature, " membrane electrode " assembly of obtained fuel cell.Then " membrane electrode " assembly is loaded fuel cell fixture to evaluate.With pure hydrogen for fuel, pure oxygen is oxidant, battery testing temperature 80 DEG C, and anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, negative electrode O
2flow velocity 300 ml/min.Monocell polarization curve is tested under constant potential condition, record current potential with the situation of change of current density, curve a in corresponding diagram 4, recording power density with the situation of change of current density, curve A in corresponding diagram 4.
Embodiment 2
Step (1) is with step (1) in embodiment 1.
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, iridium sodium chloride, nickel nitrate and natrium citricum is taken respectively by mass ratio 1 ︰ 0.51 ︰ 0.11 ︰ 1 of functionalization Vulcan XC-72 Tan Fen ︰ chlorine iridium Suan Na ︰ Xiao Suan Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 30 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 15 mg/ml; Then add iridium sodium chloride, nickel nitrate and natrium citricum successively, first ultrasonic disperse 20 minutes, continue stirring 15 hours, be the ammoniacal liquor adjust ph to 11.5 of 28% again by mass concentration, sealing stirring 15 hours, then dries 60 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 4, total gas flow rate is the lower 500 DEG C of heat treatments of the mixed atmosphere of 500 ml/min 2 hours, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method with step (5) in embodiment 1, curve A in hydroxide linear scan result corresponding diagram 5.
Embodiment 3
Step (1) is with step (1) in embodiment 1
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chlorine sub-iridium acid sodium, nickelous sulfate and natrium citricum is taken respectively by mass ratio 1 ︰ 0.1 ︰ 0.05 ︰ 0.2 of functionalization Vulcan XC-72 Tan Fen ︰ chlorine sub-iridium Suan Na ︰ Liu Suan Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 60 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 25 mg/ml; Then add chlorine sub-iridium acid sodium, nickelous sulfate and natrium citricum successively, first ultrasonic disperse 10 minutes, continues stirring 6 hours, be the ammoniacal liquor adjust ph to 11 of 28% again by mass concentration, sealing stirring 6 hours, then dries 50 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex is being 1 ︰ 1 in hydrogen gas ︰ argon gas volume ratio, total gas flow rate is the lower 700 DEG C of heat treatments of the mixed atmosphere of 100 ml/min 1 hour, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method with step (5) in embodiment 1, curve B in hydroxide linear scan result corresponding diagram 5.
Embodiment 4
Step (1) is with step (1) in embodiment 1.
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum is taken respectively by mass ratio 1 ︰ 2 ︰ 1 ︰ 2 of functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 10 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 3 mg/ml; Then add chloro-iridic acid, nickel chloride and natrium citricum successively, first ultrasonic disperse 60 minutes, continue stirring 24 hours, be the ammoniacal liquor adjust ph to 13 of 28% again by mass concentration, sealing stirring 24 hours, then dries 80 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex.
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 8, total gas flow rate is the lower 300 DEG C of heat treatments of the mixed atmosphere of 800 ml/min 3 hours, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
(4) catalyst is at the electrochemical property test of three-electrode system
Electrochemical test method with step (5) in embodiment 1, curve C in hydroxide linear scan result corresponding diagram 5.
Contrast experiment 1
Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst is step (5) in the electrochemical property test of three-electrode system is with embodiment 1, curve B in the volt-ampere curve figure corresponding diagram 2 of wherein cyclic voltammetry scanning the 50th circle; Curve B in hydroxide linear scan curve corresponding diagram 3.
Contrast experiment 2
(1) preparation of Proton Exchange Membrane Fuel Cells catalysis electrode
The ratio being 3 ︰ 1 in the mass ratio of the commercialization Pt/C Cuiization Ji ︰ perfluorinated sulfonic resin of Jonhson-Matthey company of Britain takes Pt/C catalyst and perfluorinated sulfonic resin (mass concentration is 5%), then be solvent shaken well under Ultrasonic Conditions with ethanol, be uniformly coated on the carbon paper of process in embodiment 1 step (4) several times, controlling anode platinum content is 0.3 milli gram/cm, negative electrode platinum content is 0.3 milli gram/cm, and it is cloudy to obtain Proton Exchange Membrane Fuel Cells catalysis electrode respectively 60 DEG C of oven dry, anode.
(2) the monocell performance evaluation of Proton Exchange Membrane Fuel Cells catalysis electrode
The Proton Exchange Membrane Fuel Cells catalysis electrode prepared using (1) step is as anode and cathode.Be placed between negative electrode and anode by Nafion112 film, under 135 DEG C and 5 MPa, hot pressing is after 120 seconds, takes out and is cooled to room temperature, " membrane electrode " assembly of obtained fuel cell.Then " membrane electrode " assembly is loaded fuel cell fixture to evaluate.With pure hydrogen for fuel, pure oxygen is oxidant, battery testing temperature 80 DEG C, and anode and cathode back pressure is 200 kPas (absolute pressures), anode hydrogen flow rate 200 ml/min, cathode oxygen flow velocity 300 ml/min.
Monocell polarization curve is tested under constant potential condition, record current potential with the situation of change of current density, curve b in corresponding diagram 4, recording power density with the situation of change of current density, curve B in corresponding diagram 4.
Result of the test of the present invention:
As can be seen from Figure 1, it is little that the carbon prepared by the present invention carries iridium nickel alloy catalyst particle, high dispersive, and domain size distribution is 1.1 ~ 3.5nm, and average grain diameter is 2.1nm.
As can be seen from Figure 2, cyclic voltammetry is carried out when theoretical metal ladings is identical, carbon prepared by the present invention carries iridium nickel alloy catalyst compared with Britain Jonhson-Matthey company trade Pt/C catalyst, and the electrochemical surface area obtained by cyclic voltammetry curve is larger.
As can be seen from Figure 3, in the hydroxide linear scan test carried out when theoretical metal ladings is identical, carbon prepared by the present invention carries iridium nickel alloy catalyst compared with Britain Jonhson-Matthey company trade Pt/C catalyst, carrying current increases to some extent than Jonhson-Matthey company trade Pt/C, shows that the catalytic activity that carbon prepared by the present invention carries the hydroxide of iridium nickel alloy catalyst is better than Jonhson-Matthey company trade Pt/C catalyst.
Fig. 4 is the Jonhson-Matthey company trade Pt/C electrode of employing identical platinum carrying capacity is under the condition of negative electrode, and the carbon adopting the present invention to prepare respectively carries iridium nickel alloy catalyst and Jonhson-Matthey company trade Pt/C is the monocell curve map that anode unit dresses up fuel cell.As can be seen from Figure 4, when anode metal carrying capacity is identical, carbon prepared by the present invention carries the operating voltage of iridium nickel alloy catalyst and electrode power is enough to the commercialization Pt/C electrode that matches in excellence or beauty.
As can be seen from Figure 5, all kinds of carbon prepared by the present invention carry iridium nickel alloy catalyst in hydroxide linear scan test, all show good hydroxide catalytic activity.
Claims (6)
1. the preparation method of a proton exchanging film fuel battery non-platinum hydrogen anode catalyst, its concrete grammar step comprises
(1) functionalization of carbon carrier
Take 1 gram of commercially available Vulcan XC-72 carbon dust, add the mixed solution 150 milliliters that 30% Guo Yangization Qing ︰ concentrated sulfuric acid volume ratio is 1 ︰ 4, ultrasonic and after stirring 3 hours, dilute with ultra-pure water, leave standstill and leach supernatant liquor after 24 hours, through repeatedly centrifuge washing, dry, after grinding, obtain functionalization Vulcan XC-72 carbon dust;
It is characterized in that:
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, iridium presoma, nickel presoma and natrium citricum is taken respectively by mass ratio 1 ︰ 0.1 ~ 2 ︰ 0.05 ~ 1 ︰ 0.2 ~ 2 of functionalization Vulcan XC-72 Tan Fen ︰ iridium Qian Qu Ti ︰ nickel Qian Qu Ti ︰ natrium citricum; First add in deionized water by functionalization Vulcan XC-72 carbon dust, ultrasonic disperse 10 ~ 60 minutes, form homodisperse functionalization Vulcan XC-72 carbon dust suspension, wherein the mass concentration of functionalization Vulcan XC-72 carbon dust is 3 ~ 25 mg/ml; Then iridium presoma, nickel presoma and natrium citricum is added successively, first ultrasonic disperse 10 ~ 60 minutes, continue stirring 6 ~ 24 hours, be ammoniacal liquor adjust ph to 11 ~ 13 of 28% again by mass concentration, sealing stirring 6 ~ 24 hours, then dry 50 ~ 80 DEG C of water-baths, pulverize, obtain carbon and carry iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 1 ~ 8, total gas flow rate is 300 ~ 700 DEG C of heat treatment 1 ~ 3 hour under the mixed atmosphere of 100 ~ 800 ml/min, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
2. according to the preparation method of a proton exchanging film fuel battery according to claim 1 non-platinum hydrogen anode catalyst, it is characterized in that described iridium presoma be chloro-iridic acid, iridium sodium chloride, chlorine sub-iridium acid sodium one of them; Nickel presoma be nickel chloride, nickelous sulfate, nickel nitrate one of them.
3., according to the preparation method of a proton exchanging film fuel battery according to claim 1 non-platinum hydrogen anode catalyst, it is characterized in that step (2) ~ (3) of preparation method are specially:
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum is taken respectively by mass ratio 1 ︰ 0.45 ︰ 0.13 ︰ 1.17 of functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 30 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 8 mg/ml; Then add chloro-iridic acid, nickel chloride and natrium citricum successively, first ultrasonic disperse 20 minutes, continue stirring 12 hours, be the ammoniacal liquor adjust ph to 12 of 28% again by mass concentration, sealing stirring 18 hours, then dries 60 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex is being 1 ︰ 6 in hydrogen gas ︰ argon gas volume ratio, total gas flow rate is the lower 500 DEG C of heat treatments of the mixed atmosphere of 350 ml/min 2 hours, then naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
4., according to the preparation method of a proton exchanging film fuel battery according to claim 1 non-platinum hydrogen anode catalyst, it is characterized in that step (2) ~ (3) of preparation method are specially:
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, iridium sodium chloride, nickel nitrate and natrium citricum is taken respectively by mass ratio 1 ︰ 0.51 ︰ 0.11 ︰ 1 of functionalization Vulcan XC-72 Tan Fen ︰ chlorine iridium Suan Na ︰ Xiao Suan Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 30 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 15 mg/ml; Then add iridium sodium chloride, nickel nitrate and natrium citricum successively, first ultrasonic disperse 20 minutes, continue stirring 15 hours, be the ammoniacal liquor adjust ph to 11.5 of 28% again by mass concentration, sealing stirring 15 hours, then dries 60 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 4, total gas flow rate is the lower 500 DEG C of heat treatments of the mixed atmosphere of 500 ml/min 2 hours, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
5., according to the preparation method of a proton exchanging film fuel battery according to claim 1 non-platinum hydrogen anode catalyst, it is characterized in that step (2) ~ (3) of preparation method are specially:
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chlorine sub-iridium acid sodium, nickelous sulfate and natrium citricum is taken respectively by mass ratio 1 ︰ 0.1 ︰ 0.05 ︰ 0.2 of functionalization Vulcan XC-72 Tan Fen ︰ chlorine sub-iridium Suan Na ︰ Liu Suan Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 60 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 25 mg/ml; Then add chlorine sub-iridium acid sodium, nickelous sulfate and natrium citricum successively, first ultrasonic disperse 10 minutes, continues stirring 6 hours, be the ammoniacal liquor adjust ph to 11 of 28% again by mass concentration, sealing stirring 6 hours, then dries 50 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex is being 1 ︰ 1 in hydrogen gas ︰ argon gas volume ratio, total gas flow rate is the lower 700 DEG C of heat treatments of the mixed atmosphere of 100 ml/min 1 hour, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
6., according to the preparation method of a proton exchanging film fuel battery according to claim 1 non-platinum hydrogen anode catalyst, it is characterized in that step (2) ~ (3) of preparation method are specially:
(2) carbon carries the preparation of iridium nickel complex
Step (1) gained functionalization Vulcan XC-72 carbon dust, chloro-iridic acid, nickel chloride and natrium citricum is taken respectively by mass ratio 1 ︰ 2 ︰ 1 ︰ 2 of functionalization Vulcan XC-72 Tan Fen ︰ Lv Yi Suan ︰ Lvization Nie ︰ natrium citricum; First functionalization Vulcan XC-72 carbon dust is added in deionized water, ultrasonic disperse 10 minutes, form the functionalization Vulcan XC-72 carbon dust suspension that homodisperse mass concentration is 3 mg/ml; Then add chloro-iridic acid, nickel chloride and natrium citricum successively, first ultrasonic disperse 60 minutes, continue stirring 24 hours, be the ammoniacal liquor adjust ph to 13 of 28% again by mass concentration, sealing stirring 24 hours, then dries 80 DEG C of water-baths, pulverizes, obtain carbon and carry iridium nickel complex;
(3) carbon carries the preparation of iridium nickel alloy catalyst
The carbon of step (2) gained being carried iridium nickel complex in hydrogen gas ︰ argon gas volume ratio is 1 ︰ 8, total gas flow rate is the lower 300 DEG C of heat treatments of the mixed atmosphere of 800 ml/min 3 hours, naturally cool under mixed atmosphere, finally washing, vacuum drying obtains carbon and carries iridium nickel alloy catalyst.
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| 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 |
| 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 |
| CN113594483B (en) * | 2021-07-28 | 2023-03-21 | 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 |
| 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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