CN103566960B - A kind of fuel-cell catalyst and preparation thereof and application - Google Patents

A kind of fuel-cell catalyst and preparation thereof and application Download PDF

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CN103566960B
CN103566960B CN201310525872.5A CN201310525872A CN103566960B CN 103566960 B CN103566960 B CN 103566960B CN 201310525872 A CN201310525872 A CN 201310525872A CN 103566960 B CN103566960 B CN 103566960B
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fuel
catalyst
cell
transition metal
salicylide
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CN103566960A (en
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乔锦丽
徐攀
李亚楠
菅赛赛
徐丽
张恩光
陈淑丽
汤俏薇
杨焜
雷涛
敖蓓
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Donghua University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention provides a kind of fuel-cell catalyst and preparation thereof and application. Described fuel-cell catalyst is characterized in that, wherein, described active component is N, N '-two salicylide ethylenediamine and transition metal salt; The mass ratio of the transition metal in described N, N '-two salicylide ethylenediamine and transition metal salt is 1:1��1:0.015; In the weight of material with carbon element and active component, the ratio of the weight sum of the transition metal in N, N '-two salicylide ethylenediamine and transition metal salt is 40-90:10-60. The present invention can reduce the cost of fuel cell significantly, carries high catalytic activity.

Description

A kind of fuel-cell catalyst and preparation thereof and application
Technical field
The invention belongs to fuel cell non-precious metal catalyst field, particularly to a kind of carbon load N, N '-two salicylide ethylenediamine cobalt (Co-salen/C) fuel-cell catalyst and its preparation method and application.
Background technology
Fuel cell is the device that a kind of chemical energy that will be present in fuel and oxidant is converted into electric energy, there is energy conversion efficiency height, the advantage such as room temperature quickly starts, environmental friendliness, have a wide range of applications in military affairs, space, power plant, motor vehicles, the mobile field such as equipment, residential households. The fuel cell being wherein dielectric substrate with PEM claims Proton Exchange Membrane Fuel Cells (PEMFCs). Compared with other fuel cell, PEMFCs can at room temperature quickly start, and can quickly change 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.
But fuel cell runs into a lot of restriction on its commercialization road, it is the noble metal catalyst of metal based on platinum (Pt) that key reason is in that its anode and negative electrode effective catalyst are all, and the expensive scarcity of resources of Pt seriously restricts the application of its commercial scale. Therefore, the load capacity and the development non-precious metal catalyst that reduce Pt in fuel cell become the current focus of attention and the Main way of Low-Temperature Fuel Cell Catalysts research. On short terms, it is feasible for reducing Pt carrying capacity, but in the long run, finding the non-precious metal catalyst that can substitute Pt is then better selection.When fuel cell is at alkaline medium (OH-) many defects and deficiency that Proton Exchange Membrane Fuel Cells has can be avoided under condition during operation. Under alkali condition, fuel (H on anode2, methanol) oxidation and negative electrode on oxygen (O2) reduction reaction all will become easier to, many materials corrosion resistance in alkaline environment is much better than it in acid medium, thus cheap non-Pt eelctro-catalyst such as Ag can be adopted, Ni, Co, Fe, MnO2 etc. replace the Pt catalyst of costliness, thus being substantially reduced the manufacturing cost of fuel cell.
At present, the research of fuel cell non-precious metal catalyst focus primarily upon transition metal oxide, sulfide, transition metal carbonyl compound and transition metal macrocyclic compound etc. [Electrochim.Acta, 41 (1996) 1689; J.ElectrochemSoc, 141 (1994) 41; IntJHydrogenEnergy, 25 (2000) 255]. And the carbon carrying transition metal N dopant material of high-temperature heat treatment is considered as most promising oxygen reduction catalyst, some of them have shown close to the oxygen reduction activity [EnergyEnviron.Sci. even above commercialization Pt/C catalyst, 4,3167 (2011)]. Wherein transition metal centre ion and containing n-donor ligand structure are considered as the key factor [Electrochim.Acta52,2562 (2007)] determining catalyst activity.
The one of Chinese patent CN10657921A report is with the nitrogenous aromatic compounds of nano carbon particle load and transition metal composite, and the carbon nano-fiber etc. containing transition metal and nitrogen element of Chinese patent CN102021677A report, all define the coordination compound of transition metal and nitrogen, thus showing good oxygen reduction activity. But, current carbon carrying transition metal is still not very clear with the structure of N doped catalyst and catalytic mechanism, and its activity also also has certain gap compared with Pt catalyst.
Summary of the invention
The technical problem to be solved is to provide a kind of carbon load N, N '-two salicylide ethylenediamine cobalt (Co-salen/C) fuel-cell catalyst and its preparation method and application, this catalyst is non-platinum catalyst, it is possible to the significant cost reducing fuel cell; Preparation method is simple, it is easy to operation, cost low, be suitable for industrialized production, have a good application prospect.
In order to solve above-mentioned technical problem, the invention provides a kind of fuel-cell catalyst, it is characterised in that adopting the raw material including material with carbon element and active constituent to make, wherein, described active component is N, N '-two salicylide ethylenediamine and transition metal salt; The mass ratio of the transition metal in described N, N '-two salicylide ethylenediamine and transition metal salt is 1:1��1:0.015; In the weight of material with carbon element and active component, the ratio of the weight sum of the transition metal in N, N '-two salicylide ethylenediamine and transition metal salt is 40-90:10-60.
Preferably, described material with carbon element is at least one in VulcanXC-72, BP2000, CNT, nano cages, carbon nano-fiber and Graphene.
Preferably, described transition metal salt is mass ratio is the cobalt salt of 1:0��1:1 and other transition metal salt.
It is highly preferred that described cobalt salt is cobaltous sulfate, cobalt nitrate, cobaltous chloride, cobalt acetate or ethyl acetate cobalt.
It is highly preferred that other transition metal salt described is ammonium vanadate, amine molybdate, sodium tungstate or cerous nitrate.
The preparation method that present invention also offers above-mentioned fuel-cell catalyst, it is characterised in that concretely comprise the following steps:
The first step: be placed in mortar by material with carbon element and active component in proportion, adds solvent, is fully ground to solvent volatilization completely, and vacuum drying obtains catalyst precursor;
Second step: the catalyst precursor of first step gained is heated up roasting 2��4h at 600��1000 DEG C with 20 DEG C/min speed under inert gas atmosphere is protected, obtains fuel-cell catalyst.
Preferably, described solvent is water, methanol, ethanol or chloroform.
Preferably, described noble gas is argon or nitrogen.
Present invention also offers and a kind of apply above-mentioned fuel-cell catalyst and prepare the method in membrane-membrane electrode for fuel cell coalition, it is characterized in that, concretely comprise the following steps: fuel-cell catalyst is distributed in water, ethanol or aqueous isopropanol, after ultrasonic, obtains the ink solution of catalyst; The ink solution of described catalyst is transferred to glass carbon (GC) electrode dries formation catalyst layer naturally, 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 coalition.
Preferably, described fuel cell be with methanol, ethanol, propanol, glycerol or dimethyl ether be liquid fuel direct alkaline fuel cell, hydrogen-sky (O2) alkaline fuel cell, zinc-sky battery or microbiological fuel cell.
Preferably, described methanol solution and the mass ratio of Nafion solution are 1:5-1:100.
Preferably, in described membrane-membrane electrode for fuel cell coalition, the load capacity of fuel-cell catalyst is 80 �� g-1500 �� g/cm2��
Compared with prior art, the invention has the beneficial effects as follows:
(1) present invention is non-platinum catalyst, it is possible to the significant cost reducing fuel cell, forms Co-Nx-C composite construction by nitride high temperature modification activities metal, carries high catalytic activity;
(2) preparation method of the present invention is simple, it is easy to operation, cost low, be suitable for industrialized production, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is that the fuel-cell catalyst of different temperatures is at O2Polarization curve (wherein: Co-salen/C-700 correspondence embodiment 14, Co-salen/C-600 correspondence embodiment 15, Co-salen/C-800 correspondence embodiment 16, Co-salen/C-900 correspondence embodiment 17, Co-salen/C-1000 correspondence embodiment 18) in saturated 0.1MKOH solution; Fig. 2 is that the fuel-cell catalyst of different carrying capacity is at O2Polarization curve (wherein: Co-salen/C-700-80 �� g/cm2 correspondence embodiment 14, Co-salen/C-700-200 �� g/cm2 correspondence embodiment 19, Co-salen/C-700-400 �� g/cm2 correspondence embodiment 20, Co-salen/C-700-800 �� g/cm2 correspondence embodiment 21) in saturated 0.1MKOH solution;
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, it is described in detail below. All mass percents in embodiment 1-13 all draw in reference count for the quality sum of N, N '-two salicylide ethylenediamine in material with carbon element and active constituent and the transition metal in transition metal salt.
Embodiment 1
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and transition metal Co salt; The mass percent of VulcanXC-72R carbon dust is 80wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and transition metal Co salt is 20wt%, the active component of 20wt% includes the N of Co and the 10wt% of 10wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O.The preparation method of described fuel-cell catalyst is: weigh 0.0.0477gCoSO4��7H2O, 0.0100gN, N '-two salicylide ethylenediamine and 0.0800gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely, agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 2
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and transition metal Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% includes the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.9600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely, agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 3
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and transition metal Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% includes the N of Co and the 15wt% of 25wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.1193gCoSO4��7H2O, 0.0150gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely, agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 4
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and transition metal Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% includes the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is Co (NO3)2��6H2O.The preparation method of described fuel-cell catalyst is: weigh 0.0741gCo (NO3)26H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely, agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 5
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and transition metal Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and transition metal Co salt is 40wt%, the active component of 40wt% includes the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is cobalt acetate.
The preparation method of described fuel-cell catalyst is: weighing 0.0451g cobalt acetate, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely, agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 6
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt and W salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co and the W in N '-two salicylide ethylenediamine and Co salt and W salt is 40wt%, the active component of 40wt% includes the N of W and the 25wt% of Co, 5wt% of 10wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O, W salt used is sodium tungstate.
The preparation method of described fuel-cell catalyst is: weigh 0.0477gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine, 0.0090g sodium tungstate and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 7
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt and Ce salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of transition metal Co and the Ce in N '-two salicylide ethylenediamine and Co salt and Ce salt is 40wt%, the active component of 40wt% includes the N of Ce and the 25wt% of Co, 5wt% of 10wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O, Ce salt used is cerous nitrate.
The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine, 0.0150g cerous nitrate and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain fuel-cell catalyst (Co-Salen/C-700 catalyst).
Embodiment 8
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent sum of the transition metal Co in N '-two salicylide ethylenediamine and Co salt is 40wt%, the active component of 40wt% comprises the N of Co and the 25wt% of 15wt%, N,-two salicylide ethylenediamines, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 600 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-Salen/C-600 catalyst).
Embodiment 9
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent of the transition metal Co in N '-two salicylide ethylenediamine and Co salt is 40wt%, the active component of 40wt% comprises the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20mi analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 800 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-Salen/C-800 catalyst).
Embodiment 10
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent of the transition metal Co in N '-two salicylide ethylenediamine and Co salt is 40wt%, the active component of 40wt% comprises the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O.The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 900 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-Salen/C-900 catalyst).
Embodiment 11
A kind of fuel-cell catalyst, adopts the raw material including VulcanXC-72R carbon dust and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt; The mass percent of VulcanXC-72R carbon dust is 60wt%, N in active component, the mass percent of the transition metal Co in N '-two salicylide ethylenediamine and Co salt is 40wt%, the active component of 40wt% comprises the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600gVulcanXC-72R carbon dust are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 1000 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-Salen/C-1000 catalyst).
Embodiment 12
A kind of fuel-cell catalyst, adopts the raw material including CNT and active constituent to make, and described active component is N, N ' two salicylide ethylenediamine and Co salt; The mass percent of CNT is 60wt%, N in active component, the mass percent of the transition metal Co in N '-two salicylide ethylenediamine and Co salt is 40wt%, the active component of 40wt% comprises the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O. The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600g CNT are placed in agate mortar. Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, catalyst precursor is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-salen/CNT-700 catalyst).
Embodiment 13
A kind of fuel-cell catalyst, adopts the raw material including Graphene and active constituent to make, and described active component is N, N '-two salicylide ethylenediamine and Co salt; The mass percent of Graphene is 60wt%, active component comprises in the active component that mass percent is 40wt%, 40wt% of the transition metal Co in N, N '-two salicylide ethylenediamine and Co salt the N of Co and the 25wt% of 15wt%, N '-two salicylide ethylenediamine, wherein Co salt used is CoSO4��7H2O��
The preparation method of described fuel-cell catalyst is: weigh 0.0716gCoSO4��7H2O, 0.0250gN, N '-two salicylide ethylenediamine and 0.0600g Graphene are placed in agate mortar.Add 20ml analytical pure methanol, be fully ground to methanol volatilization completely. Agate mortar and mixture therein are put in vacuum drying oven vacuum drying 1h at 60 DEG C, obtains catalyst precursor, the catalyst precursor of gained is placed in quartz boat, at N2Under atmosphere protection, it is increased under 700 DEG C of conditions roasting reduction with 20 DEG C/min heating rate and processes 2h, obtain required fuel-cell catalyst (Co-salen/Graphene-700 catalyst).
Embodiment 14
Fuel-cell catalyst in the embodiment 2 of 4mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 80.8 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 15
Fuel-cell catalyst in the embodiment 8 of 4mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 80.8 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 16
Fuel-cell catalyst in the embodiment 9 of 4mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 80.8 �� g/crn2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 17
Fuel-cell catalyst in the embodiment 10 of 4mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 80.8 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 18
Fuel-cell catalyst in the embodiment 11 of 4mg is distributed in the aqueous isopropanol of 99.7% of 2mi, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer.Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 80.8 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 19
Fuel-cell catalyst in the embodiment 2 of 10mg is distributed in the aqueous isopropanol of 99.7% of 2mi, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and 99.5% methanol solution 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 202.0 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 20
Fuel-cell catalyst in the embodiment 2 of 20mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and 99.5% methanol solution 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 404.0 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
Embodiment 21
Fuel-cell catalyst in the embodiment 2 of 40mg is distributed in the aqueous isopropanol of 99.7% of 2ml, under ultrasonication, obtains catalyst solution. Pipetting the 10 above-mentioned catalyst solutions of �� l with micropipette rifle, to transfer to a diameter be 0.2475cm2GC electrode on, naturally dry formation catalyst layer. Nafion solution and the methanol solution of 99.5% 1:100 in mass ratio using 5% mix as binding agent, take on the catalyst layer that a binding agent drops on glass carbon (GC) electrode, naturally dry. The load capacity of fuel-cell catalyst is 808.1 �� g/cm2, naturally dry, obtain membrane-membrane electrode for fuel cell coalition.
The chemical property of the membrane electrode joint body in utilization Rotation ring disk electrode technology (RDE) testing example 14-21 in traditional three-electrode system. Electrolyte is 0.1MKOH, and working electrode is the membrane electrode joint body in embodiment 14-21, and reference electrode is saturated calomel electrode, is Pt silk electrode to electrode. Polarization curve under room temperature is such as shown in Fig. 1, Fig. 2.
From Fig. 1, Fig. 2 it is found that the fuel-cell catalyst prepared in the present invention has higher activity and stability. Fuel-cell catalyst prepared at 700 DEG C shows the catalysis activity of the best. With its gas-diffusion electrode prepared at 0.1MKOH electrolyte solution and saturated O2Under atmosphere, 0.08V (relative to standard hydrogen electrode) can produce obvious hydrogen reduction electric current, and half wave potential is at-0.02V, and maximum limit diffusion current density is 3.4mAcm-2. Additionally, when Co-salen/C carrying capacity is at 808.1 �� g/cm2Time, obvious hydrogen reduction electric current can be produced at 0.12V (relative to standard hydrogen electrode), half wave potential is 0.055V, and shuffled about 35mV, and maximum limit dissufion current increases 25%.

Claims (7)

1. a fuel-cell catalyst, it is characterised in that adopting the raw material including material with carbon element and active constituent to make, wherein, described active component is N, N '-two salicylide ethylenediamine and transition metal salt; The mass ratio of the transition metal in described N, N '-two salicylide ethylenediamine and transition metal salt is 1:0.6 ~ 1:0.015; In the weight of material with carbon element and active component, the ratio of the weight sum of the transition metal in N, N '-two salicylide ethylenediamine and transition metal salt is 40:60.
2. fuel-cell catalyst as claimed in claim 1, it is characterised in that described material with carbon element is at least one in VulcanXC-72, BP2000, CNT, nano cages, carbon nano-fiber and Graphene.
3. fuel-cell catalyst as claimed in claim 1, it is characterised in that described transition metal salt is mass ratio is cobalt salt and other transition metal salt of 1:0 ~ 1:1.
4. fuel-cell catalyst as claimed in claim 3, it is characterised in that described cobalt salt is cobaltous sulfate, cobalt nitrate, cobaltous chloride, cobalt acetate or ethyl acetate cobalt.
5. fuel-cell catalyst as claimed in claim 3, it is characterised in that described transition metal salt is ammonium vanadate, amine molybdate, sodium tungstate or cerous nitrate.
6. the method in membrane-membrane electrode for fuel cell coalition prepared by the fuel-cell catalyst applied according to any one of claim 1-5, it is characterized in that, concretely comprise the following steps: fuel-cell catalyst is distributed in water, ethanol or aqueous isopropanol, after ultrasonic, obtains catalyst solution; 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 coalition.
7. the method in membrane-membrane electrode for fuel cell coalition prepared by fuel-cell catalyst as claimed in claim 6, it is characterized in that, direct alkaline fuel cell, hydrogen-sky alkaline fuel cell, zinc-sky battery or the microbiological fuel cell that described fuel cell is is liquid fuel with methanol, ethanol, propanol, glycerol or dimethyl ether.
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