CN105107541A - Preparing method for high-activity and high-stability composite catalyst for fuel cells - Google Patents
Preparing method for high-activity and high-stability composite catalyst for fuel cells Download PDFInfo
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Abstract
The invention provides a preparing method for a high-activity and high-stability composite catalyst for fuel cells and belongs to the technical field of fuel cells. The preparing method includes the steps that firstly, the surface of a Pt/C catalyst is wrapped by a layer of dopamine, and the dopamine is used for adsorbing a metal precursor through the good adsorbing performance on metal cations; secondly, silicon dioxide is used for packaging a polymer, the pyrolysis losses and heat treatment morphology conversion of a polymer precursor are controlled through morphology fixing and range limiting functions of the silicon dioxide, alloy nano particles and an N-doped carbon modified layer are further synthesized through high-temperature pyrolysis under the surface segregation effect of platinum and transition metal, and the low-platinum-nonmetal composite structure catalyst with the hollow alloy nano particles wrapped by N-doped carbon is constructed. According to the preparing method for the high-activity and high-stability composite catalyst for the fuel cells, migration agglomerating and growing in the sintering process of the catalyst are overcome, the size of the particles is effectively controlled, the catalyst has high high-activity surface area, operation is simple, industrial production is easy, and the catalyst can be widely applied to the fuel cells with proton exchange membranes serving as electrolytes.
Description
Technical field:
The invention belongs to fuel cell field, particularly a kind of preparation method of high activity and high stability fuel cell composite catalyst.
Background technology:
Fuel cell is a kind of is directly the device of electric energy by chemical energy, have that energy conversion efficiency is high, environmental friendliness, room temperature start fast, specific power and the outstanding feature such as specific energy is high, be considered to following electric automobile and the most promising electrochmical power source of other civilian occasion.In the process of fuel cell industrialization, its Cost Problems and life problems are the key problems of its development of puzzlement always.Current, the main cause that fuel cell cost remains high is a large amount of uses of precious metals pt, expensive due to Pt, scarcity of resources, when the non-precious metal catalyst not finding catalytic performance and Pt to compare favourably, the consumption of reduction Pt, the utilization rate of raising Pt have become more urgent.In order to reduce costs, Pt with the form high dispersive of nano-scale particle on the carbon carrier, because the electronic structure otherness between Pt and carbon carrier is larger, weak interaction is only relied on to be attached on together, Pt nano particle is easy in carrier surface migration, reunites and grow up, catalyst surface area is caused to reduce, active reduction.In addition, the carbon of high-ratio surface is under fuel cell operating conditions, and especially air cathode, easily corrodes, and then causes the loss of catalyst.Therefore, develop a kind of high activity, high stability fuel-cell catalyst significant.
Recent domestic has done large quantifier elimination for the activity of fuel-cell catalyst and stability.Chinese patent 200910054736.6 discloses " a kind of low platinum carbon-supported nano Pd-Pt alloy catalyst preparation method and application thereof ", first by Na
2pdCl
4with K
2ptCl
4mixing adds dispersant and complexing agent, add carbon carrier excusing from death vibration to starch with raw materials carbon, again reducing agent is joined with reducing metal ion Pd and Pt in the material carbon slurry prepared, namely obtain carbon carrier nanometer Pd-Pt alloy catalyst by being separated, washing, dry.As compared to traditional Pt/C with Pd/C catalyst, catalyst prepared by the method has higher activity and stability in Oxidation of Formic Acid process, but this complicated process of preparation, required time is long and efficiency is low, be unfavorable for the suitability for industrialized production of catalyst, and in the process of raw materials carbon slurry, the speed of metal ion codeposition is inconsistent, causes the size of the nano particle finally obtained to can not get good control.Chinese invention patent 2013154105370 discloses " a kind of fuel-cell catalyst preparation method of efficient stable ", the method first will have graphite-like structure by the method for in situ chemical oxidative polymerization, be easy to graphited polyaniline-coated at Pt/C catalyst surface, then under transition metal salt catalysis, high temperature pyrolysis forms N doping carbon-coating, N doping carbon-coating not only can as the second activated centre, catalytic activity is strengthened with Pt is collaborative, improve catalytic activity, and the N doping carbon-coating being coated on carbon surface can stop Pt nano particle in the migration of carbon support to a certain extent, reunion is grown up, improve the activity of catalyst to a certain extent.But this kind of method does not carry out confinement process to catalyst, the migration of nano particle in the loss of nitrogen and heat treatment process can not be stoped completely to reunite and grow up, and catalyst activity is still not high.
Summary of the invention:
The object of the invention is, for the weak point of existing conventional P t based alloy catalyst synthetic method, to provide a kind of preparation method of high activity and high stability fuel cell composite catalyst.The present invention is first at the coated one deck dopamine of Pt/C catalyst surface, the absorption property utilizing dopamine good to transition-metal cation carrys out adsorbing metal presoma, then with silica, polymer is encapsulated, utilize solid and the confinement effect of silica, control pyrolysis loss and the conversion of heat treatment pattern of polymer precursor, high temperature pyrolysis, by the surface segregation effect one-step synthesis alloy nano particle of platinum and transition metal and nitrogen-doped carbon decorative layer, constructs the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated hollow alloy nano particle.Like this, not only overcome the migration of catalyst in sintering process and reunite and grow up, reach the effect effectively controlling particle size, and finally also assures that the high activity specific area of catalyst.
The object of the present invention is achieved like this: a kind of preparation method of high activity and high stability fuel cell composite catalyst, and its concrete grammar step comprises:
(1) in-situ polymerization of dopamine and adsorb transition metal ions
First, the ratio being 1 ︰ 0.7 ~ 1:3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1 ~ 1:3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 ~ 2 mg/ml, by ultrasonic 10 ~ 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 ~ 1:3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 ~ 24 hours under 0 ~ 30 DEG C of condition, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 ~ 1:5 by Pt and transition metal mole ratio again and add transition metal precursor, stir and within 2 ~ 24 hours, make its abundant adsorbing metal cation.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate or silicic acid triethyl are that 1 ︰ 0.7 ~ 1:3 takes ethyl orthosilicate or silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 1 ~ 6, stirring was transferred in culture dish after 10 ~ 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace, under nitrogen or argon tube furnace is warming up to 600 ~ 1000 DEG C, the flow velocity controlling inert gas is 50 ~ 500 ml/min, and keep 0.5 ~ 3 hour at 600 ~ 1000 DEG C, after product cooling, last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 0.7 ~ 1:3, stir 8 ~ 24 hours, finally that product is centrifugal, washing, dry, low platinum-Nonmetallic Composite Structure the catalyst of the nitrogen-doped carbon coated PtM alloy nano particle of high activity and high stability is obtained after grinding.
Wherein said transition metal precursor be iron chloride, ferric nitrate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride one of them.
After the present invention adopts technique scheme, mainly contain following effect:
(1) " hollow " structure, prepared by the present invention can improve the utilization rate of Pt, reduces catalyst amount.
(2) the N/C clad of the catalyst, prepared by the present invention can suppress the migration of Pt base hollow nano particle reunion to be grown up, and improves catalyst stability.
(3) the N/C clad of the catalyst, prepared by the present invention as the second catalytic active center, can improve catalyst activity further.
(4), the inventive method simple economy, be affected by human factors little, production cost is low, easy to utilize.
Adopting the hollow structure nitrogen prepared of the present invention to mix carbon modification-low platinum composite catalyst, to can be applicable to PEM be electrolytical fuel cell, as the field such as hydrogen-oxygen proton exchange membrane fuel cell, DMFC.With the fuel-cell catalyst that the present invention manufactures, can electric automobile be widely used in, various spacecraft, portable electric appts, as video camera, notebook computer, electronic toy etc.
Accompanying drawing illustrates:
Fig. 1 is high power transmission electron microscope (TEM) photo that the nitrogen-doped carbon modification-low platinum composite catalyst of embodiment 1 gained is observed when multiplication factor is 73000 times.
Fig. 2 is nitrogen-doped carbon modification-low platinum composite catalyst and the hydrogen reduction linear scan curve of Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst in rotating disk electrode (r.d.e) of embodiment 1 ~ 4 gained.
In figure: curve 1 ~ 4 is for working electrode with the nitrogen-doped carbon modification-low platinum composite catalyst of embodiment 1 ~ 4 preparation, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the high chloro acid solution of saturated 0.1 mol/L of oxygen is electrolyte, and sweep speed is the hydrogen reduction linear scan curve under 10 millivolts of/second conditions.
Curve 5 is Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst is working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the high chloro acid solution of saturated 0.1 mol/L of oxygen is electrolyte, and sweep speed is the hydrogen reduction linear scan curve under 10 millivolts of/second conditions.
Fig. 3 is embodiment 1, embodiment 5 and embodiment 6 are modified with the nitrogen-doped carbon of contrast test 1 gained-low platinum composite catalyst and the hydrogen reduction linear scan curve of Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst in rotating disk electrode (r.d.e).
In figure: curve 1 ~ 3 is for working electrode with the nitrogen-doped carbon modification-low platinum composite catalyst prepared by embodiment 1,5,6, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, with the high chloro acid solution of saturated 0.1 mol/L of oxygen for electrolyte, sweep speed is the hydrogen reduction linear scan curve under the condition of 10 millivolts/second.
Curve 4 is Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst is working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the high chloro acid solution of saturated 0.1 mol/L of oxygen is electrolyte, and sweep speed is the hydrogen reduction linear scan curve under 10 millivolts of/second conditions.
Fig. 4 is the hydrogen reduction linear scan curve in the stability test of Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst in contrast test 2 in rotating disk electrode (r.d.e).
In figure: curve 1 ~ 3 is for working electrode with Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the high chloro acid solution of saturated 0.1 mol/L of oxygen is electrolyte, sweep speed be aging under the condition of 10 millivolts/second before, aging 2000 circle after and aging 4000 circle after hydrogen reduction linear scan curve.
Hydrogen reduction linear scan curve in the stability test of the nitrogen-doped carbon modification-low platinum composite catalyst that Fig. 5 is embodiment 1 in rotating disk electrode (r.d.e).
In figure: the nitrogen-doped carbon modification-low platinum composite catalyst that curve 1 ~ 3 is by embodiment 1 working electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, the chloric acid aqueous solution that saturated 0.1 mol/L of oxygen is high is electrolyte, sweep speed be aging under the condition of 10 millivolts/second before, aging 2000 circle after and aging 4000 circle after hydrogen reduction linear scan curve.
Five, detailed description of the invention:
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment 1
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) dopamine in-situ polymerization with absorption iron ion
First, the ratio being 1 ︰ 0.7 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 mg/ml, by ultrasonic 10 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 hours under 30 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 by Pt and iron chloride mol ratio again and add iron chloride, stirring makes it fully adsorb iron ion in 2 hours.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 0.7 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 1, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 800 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 0.5 hour at 800 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 0.7; stir 8 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtFe alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system:
The composite catalyst taking the N doping carbon-coating modification obtained by 2 milligram of (3) step joins in 800 microliter anhydrous ethanol, after sonic oscillation is uniformly dispersed for 10 minutes, microsyringe is drawn 20 microlitres and is evenly coated in vitreous carbon rotating disk electrode (r.d.e), keeps 2 hours at 60 DEG C.As working electrode, silver/silver chloride electrode is reference electrode, platinum filament is auxiliary electrode, with the high chloro acid solution of saturated 0.1 mol/L of nitrogen for electrolyte solution, at electrochemical workstation (CHI660b, Shanghai Chen Hua instrument company) above record current density is with the situation of change of voltage, and cyclic voltammetry scan 50 encloses with activating catalyst and evaluates the electrochemical active surface of catalyst.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, the curve 1 in corresponding diagram 2.
(5) N doping carbon-coating modifies the transmission electron microscope test of ultralow platinum composite catalyst
The ultralow platinum composite catalyst transmissioning electric mirror test that the N doping carbon-coating prepared is modified obtains high-resolution-ration transmission electric-lens (TEM) photo in Fig. 1.
Embodiment 2
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) dopamine in-situ polymerization with absorption iron ion
First, the ratio being 1 ︰ 3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 hours under 0 DEG C of condition, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 by Pt and ferric nitrate mol ratio again and add ferric nitrate, stirring makes it fully adsorb iron ion in 2 hours.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 0.7 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 2, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 600 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 3 hours at 600 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 1; stir 8 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtFe alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system
Electrochemical property test is with the step 4 in embodiment 1.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, the curve 2. in corresponding diagram 2
Embodiment 3
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) in-situ polymerization of dopamine and adsorption of cobalt ion
First, the ratio being 1 ︰ 3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 2 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 24 hours under 30 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 5 by Pt and cobalt nitrate mol ratio again and add cobalt nitrate, stir and within 24 hours, make its abundant adsorption of cobalt ion.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 3 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 6, stirring was transferred in culture dish after 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 700 DEG C; the flow velocity controlling inert gas is 500 ml/min; and keep 2.5 hours at 700 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 3; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtCo alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system
Electrochemical property test is with the step 4 in embodiment 1.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, the curve 3. in corresponding diagram 2
Embodiment 4
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) in-situ polymerization of dopamine and adsorption of cobalt ion
First, the ratio being 1 ︰ 1.2 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 2 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 1 mg/ml, by ultrasonic 20 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 2 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 5 hours under 10 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 3 by Pt and cobalt chloride mol ratio again and add cobalt chloride, stir and within 6 hours, make its abundant adsorption of cobalt ion.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 1.5 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 1, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 900 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 1 hour at 900 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 1; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtCo alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system
Electrochemical property test is with the step 4 in embodiment 1.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, the curve 4. in corresponding diagram 2
Embodiment 5
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) in-situ polymerization of dopamine and absorbed Ni ion
First, the ratio being 1 ︰ 2.2 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1.5 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 1.5 mg/ml, by ultrasonic 40 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 20 hours under 20 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 4 by Pt and nickel nitrate mol ratio again and add nickel nitrate, stir and within 20 hours, make its abundant absorbed Ni ion.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 2 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 6, stirring was transferred in culture dish after 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 1000 DEG C; the flow velocity controlling inert gas is 300 ml/min; and keep 0.5 hour at 1000 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 2; stir 20 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtNi alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system
Electrochemical property test is with the step 4 in embodiment 1.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, the curve 2. in corresponding diagram 3
Embodiment 6
A preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises:
(1) in-situ polymerization of dopamine and absorbed Ni ion
First, the ratio being 1 ︰ 1.5 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.5 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1.5 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 15 hours under 5 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 2 by Pt and nickel chloride mol ratio again and add nickel chloride, stir and within 24 hours, make its abundant absorbed Ni ion.
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 3 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 4, stirring was transferred in culture dish after 20 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish.
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 800 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 1.5 hours at 800 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 3; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtNi alloy nano particle.
(4) electrochemical property test of the ultralow platinum composite catalyst of nitrogen-doped carbon in three-electrode system
Electrochemical property test is with the step 4 in embodiment 1.After surface active is carried out to catalyst, linear scan volt-ampere curve is tested in the perchloric acid solution of saturated 0.1 mol/L of oxygen, the rotating speed of rotation electrode is 1600 revs/min, sweep limits 0-1.1V (relative to standard hydrogen electrode), and sweep speed is 10 millivolts/second.Curve 1 in corresponding diagram 3.
Contrast experiment:
Contrast experiment 1
(1) preparation of business platinum carbon catalysis electrode
Taking 2 milligrams of Britain Jonhson-Matthey company trade Pt/C (platinum mass percent 40%) catalyst joins in 800 microliter anhydrous ethanol, after sonic oscillation is uniformly dispersed for 10 minutes, drawing 20 microlitres with microsyringe is evenly coated in vitreous carbon rotating disk electrode (r.d.e), keep 2 hours at 60 DEG C, controlling platinum carrying capacity is 10ug, and is uniformly coated on several times on electrode and obtains business Pt/C catalysis electrode.
(2) compare with the redox active of conventional P t/C (Jonhson-Matthey, mass percent 40%)
Adopt three-electrode system, load has the glass-carbon electrode of Pt/C catalyst to be working electrode, silver/silver chloride electrode is reference electrode, platinum filament is to electrode, with the saturated high chloro acid solution of 0.1 mole often liter of oxygen for electrolyte solution, at electrochemical workstation (CHI660b, Shanghai Chen Hua instrument company) upper record hydrogen reduction curve, hydrogen reduction linear scan scope is 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, rotating speed is 1600 revs/min, the curve 5 in corresponding diagram 2.
Contrast experiment 2
Step (1) is with step (1) in contrast test 1
(2) with the comparison of the stability of conventional P t/C (E-TEAK, mass percent 20%)
Adopt three-electrode system, load has the glass-carbon electrode electrode of Pt/C catalyst to be working electrode, silver/silver chloride electrode is reference electrode, platinum filament is to electrode, with the high chloro acid solution of saturated 0.1 mol/L of nitrogen for electrolyte solution, at electrochemical workstation (autolab, Shanghai Chen Hua instrument company) on record aging before and aging after expression activitiy, in burn-in test, cyclic voltammetry scope is 0-1.2V, sweep speed is 50 millivolts/second, 4000 circles, hydrogen reduction linear scan scope is 0-1.1V (relative to standard hydrogen electrode), sweep speed is 10 millivolts/second, rotating speed is 1600 revs/min, corresponding diagram 4.
Result of the test of the present invention:
The TEM (Fig. 1 and Fig. 2) of nitrogen-doped carbon modification-low platinum composite catalyst shows: the catalyst particle size that this method of invention is formed is uniformly dispersed, general at about 4-5nm, and in hollow structure, substantially increase the utilization rate of the middle Pt of catalyst, alloy effect and special hollow structure all add the catalytic activity of catalyst.From Fig. 2 redox curve map can find out that we make the half wave potential of catalyst compared with conventional P t/C catalyst, improve 20mv, j
kcan 0.8891 be reached under 0.9V condition, compare conventional P t/C (0.3940) catalyst and improve 3 times, namely we system catalyst there is very high oxygen reduction activity.
And as can be seen from Figure 4 and Figure 5 according to invention method catalyst be greatly improved in stability compared to traditional Pt/C catalyst.Fig. 4 shows, traditional Pt/C catalyst is after 2000 circle cyclic voltammetries, and curve 2 can find out that activity decrease is obvious, and after 4000 circle cyclic voltammetries, curve 3 can find out that activity decrease is a lot.Fig. 5 show that we make this nitrogen-doped carbon modification-low platinum composite catalyst after enclosing cyclic voltammetries through 2000 circles and 4000, activity does not all change substantially, illustrates that the catalyst that we obtain has very high stability.
Claims (8)
1. a preparation method for high activity and high stability fuel cell composite catalyst, its concrete grammar step comprises
(1) in-situ polymerization of dopamine and adsorb transition metal ions
First, the ratio being 1 ︰ 0.7 ~ 1:3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1 ~ 1:3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 ~ 2 mg/ml, by ultrasonic 10 ~ 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 ~ 1:3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 ~ 24 hours under 0 ~ 30 DEG C of condition, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 ~ 1:5 by Pt and transition metal mole ratio again and add transition metal precursor, stir and within 2 ~ 24 hours, make its abundant adsorbing metal cation,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate or silicic acid triethyl are that 1 ︰ 0.7 ~ 1:3 takes ethyl orthosilicate or silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 1 ~ 6, stirring was transferred in culture dish after 10 ~ 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace, under nitrogen or argon tube furnace is warming up to 600 ~ 1000 DEG C, the flow velocity controlling inert gas is 50 ~ 500 ml/min, and keep 0.5 ~ 3 hour at 600 ~ 1000 DEG C, after product cooling, last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 0.7 ~ 1:3, stir 8 ~ 24 hours, finally that product is centrifugal, washing, dry, low platinum-Nonmetallic Composite Structure the catalyst of the nitrogen-doped carbon coated PtM alloy nano particle of high activity and high stability is obtained after grinding.
2. according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that described transition metal precursor be iron chloride, ferric nitrate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride one of them.
3., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) dopamine in-situ polymerization with absorption iron ion
First, the ratio being 1 ︰ 0.7 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 mg/ml, by ultrasonic 10 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 hours under 30 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 by Pt and iron chloride mol ratio again and add iron chloride, stirring makes it fully adsorb iron ion in 2 hours,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 0.7 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 1, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 800 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 0.5 hour at 800 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 0.7; stir 8 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtFe alloy nano particle.
4., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) dopamine in-situ polymerization with absorption iron ion
First, the ratio being 1 ︰ 3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.1 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 2 hours under 0 DEG C of condition, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 1 by Pt and ferric nitrate mol ratio again and add ferric nitrate, stirring makes it fully adsorb iron ion in 2 hours,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 0.7 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 2, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 600 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 3 hours at 600 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 1; stir 8 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtFe alloy nano particle.
5., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) in-situ polymerization of dopamine and adsorption of cobalt ion
First, the ratio being 1 ︰ 3 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 2 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 3 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 24 hours under 30 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 5 by Pt and cobalt nitrate mol ratio again and add cobalt nitrate, stir and within 24 hours, make its abundant adsorption of cobalt ion,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of ethyl orthosilicate are that 1 ︰ 3 takes ethyl orthosilicate and added in sample prepared by step (1), the pH value regulating solution is 6, stirring was transferred in culture dish after 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 700 DEG C; the flow velocity controlling inert gas is 500 ml/min; and keep 2.5 hours at 700 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 3; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtCo alloy nano particle.
6., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) in-situ polymerization of dopamine and adsorption of cobalt ion
First, the ratio being 1 ︰ 1.2 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 2 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 1 mg/ml, by ultrasonic 20 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 2 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 5 hours under 10 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 3 by Pt and cobalt chloride mol ratio again and add cobalt chloride, stir and within 6 hours, make its abundant adsorption of cobalt ion,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 1.5 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 1, stirring was transferred in culture dish after 10 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 900 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 1 hour at 900 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 1; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtCo alloy nano particle.
7., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) in-situ polymerization of dopamine and absorbed Ni ion
First, the ratio being 1 ︰ 2.2 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 1.5 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 1.5 mg/ml, by ultrasonic 40 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 20 hours under 20 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 4 by Pt and nickel nitrate mol ratio again and add nickel nitrate, stir and within 20 hours, make its abundant absorbed Ni ion,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 2 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 6, stirring was transferred in culture dish after 30 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 1000 DEG C; the flow velocity controlling inert gas is 300 ml/min; and keep 0.5 hour at 1000 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 2; stir 20 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtNi alloy nano particle.
8., according to the preparation method of a kind of high activity and high stability fuel cell composite catalyst according to claim 1, it is characterized in that step (1) ~ (3) of concrete preparation method:
(1) in-situ polymerization of dopamine and absorbed Ni ion
First, the ratio being 1 ︰ 1.5 in mass ratio in Pt/C catalyst and dopamine takes Pt/C catalyst and dopamine, and then be that the mixed solution of 1 ︰ 3 is as solvent using the volume ratio of ethanol and water, control solution concentration, the mass concentration of Pt/C catalyst is made to be 0.5 mg/ml, by ultrasonic 60 minutes of obtained solution, make Pt/C catalyst dispersed, the ratio being 1 ︰ 1.5 in the mass ratio of Tris-HCl and dopamine again adds Tris-HCl buffer solution, polymerization is stirred 15 hours under 5 DEG C of conditions, by the deionized water centrifuge washing several of the sample after stirring, be respectively 1 ︰ 2 by Pt and nickel chloride mol ratio again and add nickel chloride, stir and within 24 hours, make its abundant absorbed Ni ion,
(2) encapsulation of polymer and confinement
The sample prepared by step (1) and the mass ratio of silicic acid triethyl are that 1 ︰ 3 takes silicic acid triethyl and added in sample prepared by step (1), the pH value regulating solution is 4, stirring was transferred in culture dish after 20 minutes, it is made to be hydrolyzed formation silica in acid condition,, weigh and transferred in magnetic Noah's ark for subsequent use after drying until catalyst in culture dish;
(3) nitrogen-doped carbon modifies the preparation of Pt based alloy catalyst
The product that step (2) obtains is placed in tube furnace; under nitrogen or argon tube furnace is warming up to 800 DEG C; the flow velocity controlling inert gas is 50 ml/min; and keep 1.5 hours at 800 DEG C; after product cooling; last again sample to be placed in the cup of polytetrafluoroethylene (PTFE) in the ratio mixing that the volume ratio of distilled water and hydrofluoric acid is 1 ︰ 3; stir 24 hours, after finally product is centrifugal, washing, dry, grinding, obtain the low platinum-Nonmetallic Composite Structure catalyst of nitrogen-doped carbon coated PtNi alloy nano particle.
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