CN103566960A - Fuel-cell catalyst, as well as preparation and application thereof - Google Patents
Fuel-cell catalyst, as well as preparation and application thereof Download PDFInfo
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Abstract
The invention provides a fuel-cell catalyst, as well as preparation and application thereof. The fuel-cell catalyst is characterized in that the active components include N,N'-disalicylaldehyde ethanediamine and a transition metal salt, wherein the mass ratio of the N,N'-disalicylaldehyde ethanediamine to the transition metal in the transition metal salt is (1:1)-(1:0.015); the ratio of the weight of a carbon material to the weight sum of the N,N'-disalicylaldehyde ethanediamine and the transition metal in the transition metal salt in the active components is (40-90):(10-60). The fuel-cell catalyst disclosed by the invention can remarkably reduce the cost of a fuel cell and improve the catalytic activity.
Description
Technical field
The invention belongs to fuel cell and use non-precious metal catalyst field, particularly a kind of carbon load N, N '-bis-salicylide ethylenediamine cobalt (Co-salen/C) fuel-cell catalyst and its preparation method and application.
Background technology
Fuel cell is a kind ofly will to be present in chemical energy in fuel and oxidant and to be converted into the device of electric energy, there is the advantages such as energy conversion efficiency is high, room temperature starts fast, environmental friendliness, in fields such as military affairs, space, power plant, motor vehicle, mobile device, resident families, have a wide range of applications.The fuel cell that the PEM of wherein take is dielectric substrate claims Proton Exchange Membrane Fuel Cells (PEMFCs).Compare with other fuel cell, PEMFCs can at room temperature start fast, and can change fast power output according to load request, is the desirable substitute electric power of the most rising following electric automobile, distributing power station, stand-by power supply and portable electronics.
Yet fuel cell runs into a lot of restrictions on its commercialization road, key reason is that its anode and negative electrode effective catalyst are all that to take platinum (Pt) be that metal is main noble metal catalyst, and the expensive scarcity of resources of Pt seriously restricts its commercial scale application.Therefore, reduce the load capacity of Pt in fuel cell and the main direction that development non-precious metal catalyst becomes the current focus of attention and Low-Temperature Fuel Cell Catalysts research.On short terms, it is feasible reducing Pt carrying capacity, yet in the long run, the non-precious metal catalyst that searching can substitute Pt is better selection.When fuel cell is at alkaline medium (OH
-) many defects and the deficiency that can avoid Proton Exchange Membrane Fuel Cells to have while operating under condition.Under alkali condition, fuel (H on anode
2, methyl alcohol) oxidation and negative electrode on oxygen (O
2) reduction reaction all will become easier, the corrosion resistance of many materials in alkaline environment is much better than it in acid medium, thereby can adopt cheap non-Pt eelctro-catalyst as Ag, Ni, Co, Fe, MnO2 etc. replace expensive Pt catalyst, thereby greatly reduce the manufacturing cost of fuel cell.
At present, fuel cell mainly concentrates on [Electrochim.Acta, 41 (1996) 1689 such as transition metal oxide, sulfide, transition metal carbonyl compound and transition metal macrocyclic compound with the research of non-precious metal catalyst; J.Electrochem Soc, 141 (1994) 41; Int J Hydrogen Energy, 25 (2000) 255].And the carbon carrying transition metal N dopant material of high-temperature heat treatment is considered to most promising oxygen reduction catalyst, some of them have shown active [the Energy Environ.Sci. of hydrogen reduction approaching even higher than commercialization Pt/C catalyst, 4,3167 (2011)].Wherein transition metal central ion and containing n-donor ligand structure are considered to determine the key factor [Electrochim.Acta52,2562 (2007)] of catalyst activity.
It is a kind of with the nitrogenous aromatic compounds of nano carbon particle load and transition metal composite that Chinese patent CN10657921A reports, and the carbon nano-fiber containing transition metal and nitrogen element of Chinese patent CN102021677A report etc., all form the complex of transition metal and nitrogen, thereby shown good hydrogen reduction activity.Yet structure and the catalytic mechanism of carbon carrying transition metal and N doped catalyst are still not very clear at present, its activity is compared and is also also had certain gap with Pt catalyst.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of carbon load N, N '-bis-salicylide ethylenediamine cobalt (Co-salen/C) fuel-cell catalyst and its preparation method and application, this catalyst is non-platinum catalyst, can reduce significantly the cost of fuel cell; Preparation method is simple, and easily operation, cost are low, are suitable for suitability for industrialized production, have a good application prospect.
In order to solve the problems of the technologies described above, the invention provides a kind of fuel-cell catalyst, it is characterized in that, adopt and to comprise that the raw material of material with carbon element and active constituent makes, wherein, described active component is N, N '-bis-salicylide ethylenediamine and transition metal salt; Described N, the mass ratio of the transition metal in N '-bis-salicylide ethylenediamine and transition metal salt is 1:1～1:0.015; N in the weight of material with carbon element and active component, the ratio of the weight sum of the transition metal in N '-bis-salicylide ethylenediamine and transition metal salt is 40-90:10-60.
Preferably, described material with carbon element is at least one in Vulcan XC-72, BP2000, CNT, nano cages, carbon nano-fiber and Graphene.
Preferably, described transition metal salt is that mass ratio is cobalt salt and other transition metal salt of 1:0～1:1.
More preferably, described cobalt salt is cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate or ethyl acetate cobalt.
More preferably, described other transition metal salt is ammonium vanadate, amine molybdate, sodium tungstate or cerous nitrate.
The present invention also provides the preparation method of above-mentioned fuel-cell catalyst, it is characterized in that, concrete steps are:
The first step: in proportion material with carbon element and active component are placed in to mortar, add solvent, be fully ground to solvent evaporates complete, vacuum drying obtains catalyst precursor;
Second step: by the catalyst precursor of first step gained under inert gas atmosphere protection with the 20 ℃/min speed roasting 2～4h at 600～1000 ℃ that heats up, obtain fuel-cell catalyst.
Preferably, described solvent is water, methyl alcohol, ethanol or chloroform.
Preferably, described inert gas is argon gas or nitrogen.
The present invention also provides a kind of and has applied above-mentioned fuel-cell catalyst and prepare the method in membrane-membrane electrode for fuel cell combination, it is characterized in that, concrete steps are: fuel-cell catalyst is distributed in water, ethanol or aqueous isopropanol, obtains the ink solution of catalyst after ultrasonic; The ink solution of described catalyst is transferred on glass carbon (GC) electrode and naturally dried formation catalyst layer, again methanol solution and Nafion solution are mixed as binding agent, binding agent is dropped on the catalyst layer on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Preferably, described fuel cell is for take direct alkaline fuel cell, the hydrogen-sky (O that methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether be liquid fuel
2) alkaline fuel cell, zinc-empty battery or microbiological fuel cell.
Preferably, the mass ratio of described methanol solution and Nafion solution is 1:5-1:100.
Preferably, in described membrane-membrane electrode for fuel cell combination, the load capacity of fuel-cell catalyst is 80 μ g-1500 μ g/cm
2.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention is non-platinum catalyst, can reduce significantly the cost of fuel cell, by nitride high temperature modification activities metal, forms Co-Nx-C composite construction, improves catalytic activity;
(2) preparation method of the present invention is simple, and easily operation, cost are low, are suitable for suitability for industrialized production, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is that the fuel-cell catalyst of different temperatures is at O
2polarization curve in saturated 0.1MKOH solution (wherein: the corresponding embodiment 18 of corresponding embodiment 17, Co-salen/C-1000 of corresponding embodiment 16, Co-salen/C-900 of corresponding embodiment 15, Co-salen/C-800 of corresponding embodiment 14, Co-salen/C-600 of Co-salen/C-700); Fig. 2 is that the fuel-cell catalyst of different carrying capacity is at O
2polarization curve in saturated O.1MKOH solution (wherein: the corresponding embodiment 21 of corresponding embodiment 20, Co-salen/C-700-800 μ g/cm2 of corresponding embodiment 19, Co-salen/C-700-400 μ g/cm2 of corresponding embodiment 14, Co-salen/C-700-200 μ g/cm2 of Co-salen/C-700-80 μ g/cm2);
The specific embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.All mass percents in embodiment 1-13 are all with N in material with carbon element and active constituent, and the quality sum of the transition metal in N '-bis-salicylide ethylenediamine and transition metal salt is that benchmark draws.
Embodiment 1
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and transition metal Co salt; The mass percent of Vulcan XC-72R carbon dust is 80wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and transition metal Co salt is 20wt%, the active component of 20wt% comprises the Co of 10wt% and the N of 10wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0.0477g CoSO
47H
2o, 0.0100gN, N '-bis-salicylide ethylenediamine and 0.0800g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely, agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and transition metal Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% comprises the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.9600gVulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely, agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 3
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and transition metal Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% comprises the Co of 25wt% and the N of 15wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.1193g CoSO
47H
2o, 0.0150gN, N '-bis-salicylide ethylenediamine and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely, agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 4
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and transition metal Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% comprises the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is Co (NO
3)
26H
2o.The preparation method of described fuel-cell catalyst is: take 0.0741gCo (NO
3)
26H2O, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely, agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and transition metal Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% comprises the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is cobalt acetate.
The preparation method of described fuel-cell catalyst is: take 0.0451g cobalt acetate, and 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely, agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 6
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt and W salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, transition metal Co in N '-bis-salicylide ethylenediamine and Co salt and W salt and the mass percent sum of W are 40wt%, the active component of 40wt% comprises the N of the Co of 10wt%, the W of 5wt% and 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o, W salt used is sodium tungstate.
The preparation method of described fuel-cell catalyst is: take 0.0477g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine, 0.0090g sodium tungstate and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 7
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt and Ce salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, transition metal Co in N '-bis-salicylide ethylenediamine and Co salt and Ce salt and the mass percent sum of Ce are 40wt%, the active component of 40wt% comprises the N of the Co of 10wt%, the Ce of 5wt% and 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o, Ce salt used is cerous nitrate.
The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine, 0.0150g cerous nitrate and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 8
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, in the active component of 40wt%, comprise the Co of 15wt% and the N of 25wt%, N,-bis-salicylide ethylenediamines, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 600 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-Salen/C-600 catalyst).
Embodiment 9
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent of transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, in the active component of 40wt%, comprise the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600gVulcan XC-72R carbon dust are placed in agate mortar.Add 20mi to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 800 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-Salen/C-800 catalyst).
Embodiment 10
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent of transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, in the active component of 40wt%, comprise the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600gVulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 900 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-Salen/C-900 catalyst).
Embodiment 11
, adopting and to comprise that the raw material of Vulcan XC-72R carbon dust and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt; The mass percent of Vulcan XC-72R carbon dust is 60wt%, N in active component, the mass percent of transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, in the active component of 40wt%, comprise the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g Vulcan XC-72R carbon dust are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 1000 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-Salen/C-1000 catalyst).
Embodiment 12
, adopting and to comprise that the raw material of CNT and active constituent makes, described active component is N, N ' two salicylide ethylenediamines and Co salt; The mass percent of CNT is 60wt%, N in active component, the mass percent of transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, in the active component of 40wt%, comprise the Co of 15wt% and the N of 25wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g CNT are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, catalyst precursor is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-salen/CNT-700 catalyst).
Embodiment 13
, adopting and to comprise that the raw material of Graphene and active constituent makes, described active component is N, N '-bis-salicylide ethylenediamine and Co salt; The mass percent of Graphene is 60wt%, N in active component, the mass percent of the transition metal Co in N '-bis-salicylide ethylenediamine and Co salt is 40wt%, comprises the Co of 15wt% and the N of 25wt% in the active component of 40wt%, N '-bis-salicylide ethylenediamine, wherein Co salt used is CoSO
47H
2o.
The preparation method of described fuel-cell catalyst is: take 0.0716g CoSO
47H
2o, 0.0250gN, N '-bis-salicylide ethylenediamine and 0.0600g Graphene are placed in agate mortar.Add 20ml to analyze pure methyl alcohol, be fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are wherein put into vacuum drying 1h at 60 ℃ of vacuum drying ovens, obtain catalyst precursor, the catalyst precursor of gained is placed in to quartz boat, at N
2under atmosphere protection, with 20 ℃/min heating rate, be increased to roasting reduction under 700 ℃ of conditions and process 2h, obtain needed fuel-cell catalyst (Co-salen/Graphene-700 catalyst).
Embodiment 14
Fuel-cell catalyst in the embodiment 2 of 4mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 80.8 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 15
Fuel-cell catalyst in the embodiment 8 of 4mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 80.8 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 16
Fuel-cell catalyst in the embodiment 9 of 4mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 80.8 μ g/crn
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 17
Fuel-cell catalyst in the embodiment 10 of 4mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 80.8 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 18
Fuel-cell catalyst in the embodiment 11 of 4mg is distributed in 99.7% the aqueous isopropanol of 2mi, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 80.8 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 19
Fuel-cell catalyst in the embodiment 2 of 10mg is distributed in 99.7% the aqueous isopropanol of 2mi, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using 5% Nafion solution and 99.5% methanol solution in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 202.0 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 20
Fuel-cell catalyst in the embodiment 2 of 20mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using 5% Nafion solution and 99.5% methanol solution in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 404.0 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Embodiment 21
Fuel-cell catalyst in the embodiment 2 of 40mg is distributed in 99.7% the aqueous isopropanol of 2ml, under ultrasonication, obtains catalyst solution.With micropipette rifle, pipetting the above-mentioned catalyst solution of 10 μ l, to transfer to a diameter be 0.2475cm
2gC electrode on, naturally dry formation catalyst layer.Using the methanol solution of 5% Nafion solution and 99.5% in mass ratio 1:100 mix as binding agent, get a binding agent and drop on the catalyst layer on glass carbon (GC) electrode, naturally dry.The load capacity of fuel-cell catalyst is 808.1 μ g/cm
2, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
In traditional three-electrode system, use the chemical property of the membrane electrode joint body in Rotation ring disk electrode technology (RDE) test implementation example 14-21.Electrolyte is 0.1M KOH, and working electrode is the membrane electrode joint body in embodiment 14-21, and reference electrode is saturated calomel electrode, to electrode, is Pt silk electrode.Polarization curve under room temperature is as Fig. 1, shown in Fig. 2.
From Fig. 1, Fig. 2 can find, the fuel-cell catalyst of preparing in the present invention has higher activity and stability.At 700 ℃, prepared fuel-cell catalyst shows best catalytic activity.The gas-diffusion electrode of preparing with it is at 0.1M KOH electrolyte solution and saturated O
2under atmosphere, 0.08V (with respect to standard hydrogen electrode) can produce obvious hydrogen reduction electric current, and half wave potential is at-0.02V, and greatest limit diffusion current density is 3.4mAcm
-2.In addition, when Co-salen/C carrying capacity is at 808.1 μ g/cm
2time, at 0.12V (with respect to standard hydrogen electrode), can produce obvious hydrogen reduction electric current, half wave potential is 0.055V, the about 35mV that shuffled, greatest limit dissufion current has increased 25%.
Claims (10)
1. a fuel-cell catalyst, is characterized in that, adopts and to comprise that the raw material of material with carbon element and active constituent makes, and wherein, described active component is N, N '-bis-salicylide ethylenediamine and transition metal salt; Described N, the mass ratio of the transition metal in N '-bis-salicylide ethylenediamine and transition metal salt is 1:1～1:0.015; N in the weight of material with carbon element and active component, the ratio of the weight sum of the transition metal in N '-bis-salicylide ethylenediamine and transition metal salt is 40-90:10-60.
2. fuel-cell catalyst as claimed in claim 1, is characterized in that, described material with carbon element is at least one in Vulcan XC-72, BP2000, CNT, nano cages, carbon nano-fiber and Graphene.
3. fuel-cell catalyst as claimed in claim 1, is characterized in that, described slaine is that mass ratio is cobalt salt and the transition metal salt of 1:0～1:1.
4. fuel-cell catalyst as claimed in claim 3, is characterized in that, described cobalt salt is cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate or ethyl acetate cobalt.
5. fuel-cell catalyst as claimed in claim 3, is characterized in that, described transition metal salt is ammonium vanadate, amine molybdate, sodium tungstate or cerous nitrate.
6. the preparation method of the fuel-cell catalyst described in any one in claim 1-5, is characterized in that, concrete steps are:
The first step: in proportion material with carbon element and active component are placed in to mortar, add solvent, be fully ground to solvent evaporates complete, vacuum drying obtains catalyst precursor;
Second step: by the catalyst precursor of first step gained under inert gas atmosphere protection with the 20 ℃/min speed roasting 2～4h at 600～1000 ℃ that heats up, obtain fuel-cell catalyst.
7. the preparation method of fuel-cell catalyst as claimed in claim 6, is characterized in that, described solvent is water, methyl alcohol, ethanol or chloroform.
8. the preparation method of fuel-cell catalyst as claimed in claim 6, is characterized in that, described inert gas is argon gas or nitrogen.
9. an application rights requires the fuel-cell catalyst described in any one in 1-5 to prepare the method in membrane-membrane electrode for fuel cell combination, it is characterized in that, concrete steps are: fuel-cell catalyst is distributed in water, ethanol or aqueous isopropanol, obtains catalyst solution after ultrasonic; Described catalyst solution is transferred on glass-carbon electrode, naturally dry formation catalyst layer, methanol solution and Nafion solution are mixed as binding agent, binding agent is dropped on the catalyst layer on glass-carbon electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
10. fuel-cell catalyst as claimed in claim 9 is prepared the method in membrane-membrane electrode for fuel cell combination, it is characterized in that, described fuel cell is for take direct alkaline fuel cell, hydrogen-empty alkaline fuel cell, zinc-empty battery or the microbiological fuel cell that methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether be liquid fuel.
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