CN109346728A - Non-precious Metal Catalysts electrode, membrane electrode and preparation method thereof - Google Patents
Non-precious Metal Catalysts electrode, membrane electrode and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention discloses a kind of Non-precious Metal Catalysts electrodes, membrane electrode and preparation method thereof, the Catalytic Layer of the electrode diffusion layer surface of the Non-precious Metal Catalysts electrode is made catalyst component be grown on or load on electrode diffusion layer by Catalytic Layer material precursor mixture and is formed by high-temperature heat treatment, Catalytic Layer material precursor mixture includes transition metal precursor, carbon source material and nitrogen source material, Catalytic Layer is the carbon-based catalyst component of the high nitridation containing transition metal of the non-platinum of porous orderly Large ratio surface, catalytic activity mostlys come from carbon, the multicomponent system of nitrogen and transition metal composition, catalysis region is with porous and high-sequential and has very hydrophobic characteristic and the conductive performances such as excellent gas and electronics, catalytic active component disposably directly can be supported or be grown in electrode diffusion layer table by the preparation method of integrated straight forming Face, saves the time, simplifies electrode manufacturing step and catalyst is avoided to waste, have the advantages that prepare it is simple, at low cost, have excellent performance.
Description
Technical field
The present invention relates to fuel cell art fields, are to be related to a kind of Non-precious Metal Catalysts electrode, membrane electrode more specifically
And preparation method thereof.
Background technique
The developed economies such as especially middle America and Japan of our times various countries increasingly increase the consumption of fossil fuel, and fossil
The reserves of fuel on earth are limited and constantly reducing, and combustion of fossil fuel bring air pollution is also got worse.
As the environmental consciousness of people gradually increases, environmental-friendly and reproducible clean energy resource and energy conversion technology gradually by
The welcome of people.As the research hotspot of new energy technology, fuel cell (fuelcells) is to be best suitable for sustainable development idea
Electrochemical energy conversion equipment, have environmental pollution small, discharge amount is low or even zero-emission, and energy conversion efficiency is high, starting
It responds rapidly to fast, has wide range of applications, be most to be hopeful and most have application prospect the advantages that system reliability and high maintainability
One of energy conversion technology.Proton Exchange Membrane Fuel Cells --- including direct alcohol fuel cell --- is that application range is most wide
Low-temperature fuel cell, core component be membrane electrode assembly zoarium.Membrane electrode assembly zoarium be by solid electrolyte film, Catalytic Layer with
And the composition such as diffusion electrode, electrode reaction, proton conducting and the electronics etc. at catalysis yin-yang the two poles of the earth are played in the fuel cell system
Effect is the decisive component for influencing proton exchange film fuel battery performance and service life and cost.In typical proton exchange
In membrane cell, hydrogen or other fuel such as methanol, ethyl alcohol, acetic acid etc. are oxidized in anode and generate proton, electronics and dioxy
Change carbon (whens reforming gas etc. using alcohol, formic acid or purifying), proton and electronics pass through solid electrolyte membrane and external circuit respectively
It is transmitted to cathode, oxygen is reduced in cathode and proton, electron reaction and generates water and heat.
By the development of many decades, fuel cell especially Proton Exchange Membrane Fuel Cells has obtained considerable hair
Exhibition, the either performance of fuel cell or service life are all enhanced, however are commercialized and large-scale fuel cell
Using biggish obstacle is still suffered from, wherein hindering the obstacle of Proton Exchange Membrane Fuel Cells industrialization mainly includes fuel electricity
The performance in pond still needs to larger raising, and the service life still falls short of, and the cost of battery is still too high.Fuel cell cost is wherein caused to occupy
High not lower main factor first is that still need large-scale use in the membrane electrode of Proton Exchange Membrane Fuel Cells at present expensive
Metal platinum or platinum based catalyst.Solve the problems, such as that a kind of this thinking is expensive to improve by improving the preparation method of Catalytic Layer at present
Phenomena such as metal platinum utilization reduces the usage amount of platinum, avoids water logging, to reduce cost；Such as Chinese patent (publication number
CN104979567A the film electricity of multi-level gradient type) is prepared in such a way that silk-screen printing and ultrasonic spraying process combine
Service life and the performance of membrane electrode are improved in pole.Another thinking is to develop the platinum based catalysts such as alloying or shell, with cheap mistake
It crosses metal substitute or part replaces noble metal platinum, reduce the usage amount of platinum in catalyst；Alloying or shellization simultaneously
It can promote the interaction between platinum and other metallic elements, to further increase the catalytic activity and utilization rate of platinum, reduce
Catalyst cost.Last decade, with the research and development of non-platinum catalyst, transient metal doped high nitridation or high nitrogen-containing
Carbon material show certain electro catalytic activity, in particular for the oxygen reduction reaction of fuel battery negative pole side.It is many at present
The a variety of non-platinum catalysts with preferable oxygen reduction catalytic activity of document report, such as Chinese patent (publication number
CN101657921A a kind of preparation method of non-noble metal fuel cell cathod catalyst) is disclosed, this method is especially suitable for system
Standby support type contains the carbon-supported catalysts of the N doping of transition metal.For another example the PANI-Fe-C of polyaniline package carbon carrier synthesis
Or PANI-Co-C generated after high-temperature process thermally decomposes high catalytic activity and high stability non-platinum catalyst (Science,
332,2011,443), the catalyst shown in acid medium with the comparable activity of platinum carbon catalyst, and stability is remote
Better than the latter.Although opinions vary for the catalytic mechanism of these current non-platinum catalysts, wait further to explore and clear, it is multi-party
The result of study of position shows that nitrogen-transition metal-carbon system, which has oxygen reduction reaction, can't deny catalytic activity.Although non-platinum
The catalytic performance and stability of the carbon material of the high nitridation of catalyst especially containing transition metal are also unable to reach platinum base catalysis
The level of agent, but this also for Proton Exchange Membrane Fuel Cells reduce cost and industrialized development provide a kind of new thinking and
It may.With fuel cells applications range further expansion and it is commercialized gradually spread out, especially fuel cell is in automobile
And the use further expansion of stationary electric power plant, backup power source etc., necessarily increase the demand to platinum；And on the earth platinum storage
Amount is extremely limited, and at high price, therefore the carbon material of the high nitridation of non-platinum catalyst especially containing transition metal,
Nitrogen-transition metal-carbon system gradually will necessarily more be paid attention to；It, will be gradually real with the further promotion of its performance
With change, it is expected to part and replaces even whole substitution platinum based catalysts.
The development of non-platinum catalyst at present is also limited to laboratory level mostly, and half-cell test is more.Monocell performance is surveyed
Though examination has been reported that quantity is few.Even monocell is tested, Catalytic Layer and electrode preparation also substantially replicate current platinum
Base catalyst constructs process, i.e., first prepares catalyst, then again by transfer or spray etc. modes by catalyst loading or
Transfer is fixed to formation Catalytic Layer or electrode in proton exchange membrane perhaps electrode diffusion layer.Such as Chinese patent
201611014894.5 prepare thin layer Catalytic Layer using the method for transfer, and avoid the loss of catalyst in transfer process,
Improve the utilization rate of catalyst.But these Catalytic Layers and the preparation method of electrode are more time-consuming at present, and causing can not
The loss of the catalyst avoided.
Summary of the invention
It is an object of the invention to overcome drawbacks described above in the prior art, a kind of Non-precious Metal Catalysts electrode, film are provided
Electrode and preparation method thereof.
To achieve the above object, the first aspect of the present invention provides a kind of Non-precious Metal Catalysts electrode, including electrode expands
Layer is dissipated, the surface of the electrode diffusion layer is formed with Catalytic Layer, and the Catalytic Layer is passed through by Catalytic Layer material precursor mixture
High-temperature heat treatment makes catalyst component be grown on or load on electrode diffusion layer and is formed；Wherein, the catalysis layer material forerunner
Body mixture includes the transition metal precursor, carbon source material and nitrogen source material of non-platinum group.
The material of Catalytic Layer material precursor mixture can be dissolved separately in identical or different solvent, then take institute
Need amount mixing and form, can also weigh respectively required for amount mix after again co-dissolve and form.
Preferably, all kinds of inorganic salts or organic compound of the transition metal precursor from transition metal,
It includes but is not limited to metal halide, metal acetate, metal nitrate, metal sulphite, metal carbonate, metal cyanogen
Compound, metal hydroxides, metal phosphate, metal sulfide, metal sulfate, metal sulphite, metal sulphite,
In metal phthalocyanine compound, metalloporphyrin compound any one or combinations thereof.Wherein, the transition metal includes but is not limited to iron
Fe, cobalt Co, molybdenum Mo, nickel, manganese Mn, chromium Cr, copper Cu, in zinc Zn any one or combinations thereof.
The nitrogen source material and carbon source material can be same material, be also possible to any combination of multiple material.Make
To be preferred, the carbon source material includes but is not limited to saccharin, glucose, formaldehyde, phenol, polystyrene, carbon dust, carbon nanometer
It is any one in the materials such as pipe, graphene, vinylamine (ethyleneamines), phthalocyanine, ferrosin, melamine, aniline and its derivative
Kind or combinations thereof.The nitrogen source material includes but is not limited in all kinds of organic amino compounds, inorganic amide or nitride
Any one or combinations thereof.
Preferably, the electrode diffusion layer include but is not limited to carbon paper, carbon cloth and all kinds of sheet carbon materials or other
Conductive material, the sheet carbon material can first pass through processing in advance or directly use, the pretreatment include with hydrophobic material or
Water wetted material changes the hydrophobic hydrophilic nmature of sheet carbon material, or with carbon dust, carbon nanotube, carbon ball, graphene or aoxidizes stone
In black alkene any one or combinations thereof prepare or improve diffusion layer and pore structure, wherein prepare used in diffusion layer
Adhesive includes but is not limited to polytetrafluoroethylene (PTFE) and its derivative.
Preferably, the Catalytic Layer material precursor mixture further includes catalyst structure directed agents, the catalysis
Agent structure directing agent includes template, chelating agent and pore creating material.
Preferably, the template includes but is not limited to that each molecular sieve analog, MCM-41, MCM-48, SBA15 etc. have
In sequence mesoporous material any one or combinations thereof；The chelating agent includes but is not limited to the networks such as complexones, F127, P123
In mixture and surfactant any one or combinations thereof；The pore creating material includes but is not limited to sodium chloride, zinc chloride, chlorination
Aluminium, magnesium chloride, calcium chloride, all kinds of carbonate, all kinds of nitrate, in each ammonium salts any one or combinations thereof.
The second aspect of the present invention provides a kind of preparation method of Non-precious Metal Catalysts electrode, comprising the following steps:
(1) Catalytic Layer material precursor mixture and solvent are mixed and made into mixed liquor；Wherein, before the catalysis layer material
Drive the transition metal precursor, carbon source material and nitrogen source material that body mixture includes non-platinum group；
(2) mixed liquor made from step (1) is loaded on electrode diffusion layer, and solvent is removed；
(3) by by the load electrode diffusion that has mixed liquor of step (2) processing be placed under the protection of particular atmosphere into
Row high-temperature heat treatment makes to form Catalytic Layer on electrode diffusion layer, and Non-precious Metal Catalysts electrode is made.
Preferably, the solvent but to be not limited to include water, all kinds of alcohol, all kinds of ethers, any in all kinds of ketone equal solvents
One kind or combinations thereof.
Preferably, the mixed liquor is loaded in such a way that spraying, smearing, knife are scraped or are impregnated in step (2)
Onto electrode diffusion layer；When load, environment temperature locating for electrode diffusion layer be -20~200 degrees Celsius, preferably 30~
150 degrees Celsius；In loading process, the solvent is removed by volatilization.
Preferably, the high-temperature heat treatment mode includes high-temperature roasting processing or thermally decomposes, at the high-temperature roasting
Reason or the temperature of thermal decomposition are 200~1200 degrees Celsius, preferably between 350~1000 degrees Celsius；The high-temperature roasting processing
Or be divided into 1~10 stage, preferably 1~5 stage, each section of programmed rate 0.01~50.0 degree Celsius/
Minute, preferably 0.5~10.0 degrees celsius/minute.
Preferably, the particular atmosphere includes inert atmosphere, reducing atmosphere or the atmosphere containing ammonia.
Preferably, the preparation method is further comprising the steps of:
(4) the Non-precious Metal Catalysts electrode obtained by step (3) is successively rinsed or boiled with lye and/or acid solution, and
It is dried again after washed, to remove the residue of catalyst structure directed agents；
(5) ion conductor polymer material is applied or is impregnated into the Non-precious Metal Catalysts electrode handled by step (4)
On, enter ion conductor polymer material in the Catalytic Layer of base metal electrode.
Preferably, liquid required for the washing includes but is not limited to the acidic aqueous solutions such as hydrofluoric acid, hydroxide
The alkaline aqueous solutions such as sodium, high purity water, all kinds of alcohol, in all kinds of ketone any one or combinations thereof；The drying temperature is 30~200
Degree Celsius.
Preferably, the different zones of Catalytic Layer of the ion conductor polymer material in Non-precious Metal Catalysts electrode
Carrying capacity be uniform or non-uniform；Used ion conductor polymer material and prepare used solid when membrane electrode
Ion conductor polymer in dielectric film can be same material.It is adulterated in the solution of the ion conductor polymer material
There are hydrophobic material or water wetted material, to meet the hydrophobic or hydrophilic requirement of the different zones of Catalytic Layer.
The third aspect of the present invention provides a kind of membrane electrode, including solid electrolyte film, the solid electrolyte film
Side by hot pressing mode is equipped with the oxidizing electrode of hydrogen or load has the oxidation catalyst of hydrogen, the solid electrolyte film it is another
Side is equipped with Non-precious Metal Catalysts electrode described in above-mentioned technical proposal by hot pressing mode.
Non-precious Metal Catalysts electrode is mainly used as but is not limited to catalysis electrode, is mainly used as but is not limited to oxygen and air
Reducing electrode, it is preferential but be not limited to be used as the cathode of fuel cell and all kinds of metal air fuel cells or cell reaction
Catalysis electrode, presently disclosed Non-precious Metal Catalysts electrode are also used as the electrode of each types of fuel cells or cell reaction
Diffusion layer, for loading other catalyst or Catalytic Layer or multilayer Catalytic Layer.
Compared with prior art, the beneficial effects of the present invention are:
1, Catalytic Layer material precursor mixture is directly loaded to electrode before this by Non-precious Metal Catalysts electrode of the invention
Layer surface is spread, so that catalyst component is grown on or is loaded on electrode diffusion layer using high-temperature process and forms non-platinum catalysis
Layer, Catalytic Layer are the carbon-based catalyst component of the high nitridation containing transition metal of the non-platinum of porous orderly Large ratio surface, are urged
Change the multicomponent system that activity mostlys come from carbon, nitrogen and transition metal composition, catalysis region has porous and high-sequential
And there are very hydrophobic characteristic and the conductive performances such as excellent gas and electronics, and the water logging phenomenon of cathode side can be prevented.
2, the preparation method of integrated straight forming of the invention disposably catalytic active component directly can be supported or
It is grown in electrode diffusion layer surface, to save the time, simplify electrode manufacturing step and catalyst is avoided to waste, there is preparation
Simply, low in cost, the advantages of haveing excellent performance.
3, the present invention can reduce the cost of fuel cell electrode, to reduce the cost of Proton Exchange Membrane Fuel Cells, energy
It is enough to be combined with membrane electrode, simplify membrane electrode preparation process, improve the activity, stability and mass transfer characteristic of membrane electrode, promotees
Into the industrialized development of Proton Exchange Membrane Fuel Cells.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is that the electric field transmitting scanning electron for the Non-precious Metal Catalysts electrode that the preparation that 4 provide is implemented in present invention invention is aobvious
Micro mirror (FESEM) as a result, unsupported Catalytic Layer electrode diffusion layer surface；
Fig. 2 is that the electric field transmitting scanning electron for the Non-precious Metal Catalysts electrode that the preparation that 4 provide is implemented in present invention invention is aobvious
Micro mirror (FESEM) is as a result, Non-precious Metal Catalysts electrode surface；
Fig. 3 is transmission electron microscope (TEM) knot for the base metal electrode surface material that the preparation that 4 provide is implemented in present invention invention
Fruit.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
Prepare carbon catalysis (MoCo-N-C) electrode of the high nitridation of the cobalt molybdenum doping of carbon paper load
20.0 grams of sodium chloride are dissolved in 100 ml deionized waters, and 9.0 grams of pentaethylene hexamines are then added dropwise inward
(Pentaethylenehexamine), after stirring one hour, 15.0 grams of MCM-41 and two hours of ultrasonic disperse is added, are obtained
To the ultra-fine slurries of MCM-41.30 milliliters of ethyl alcohol dissolve 2.2 grams of cobalt chloride (CoCl2·6H2) and 1.6 grams of ammonium molybdate ((NH O4)6Mo7O24·4H2O), it is added to above-mentioned MCM-41 slurries after mixing, and is stirred overnight.Mixture is steamed in 50 degrees Celsius of rotations
Sticky paste after the most of solvent of hair removal is uniformly applied on 80 millimeters × 50 millimeters of carbon paper diffusion layer, and is freezed
It is dry to remove remaining solvent.Then carbon paper is placed in tube furnace and leads to high pure nitrogen temperature programming heat treatment: is Celsius with rate 1
Degree/min from room temperature rise to 300 degrees Celsius keep 2.5 hours；Then it is small 750 degrees Celsius of holdings 3 to be risen to 2 degrees celsius/minutes
When.Nitrogen protection drops to room temperature, successively uses sodium hydrate aqueous solution (10 mol/L), aqueous sulfuric acid (1 mol/L), second
Alcohol solution (1/3V/V) washing by soaking for several times, then again in an oven 120 degrees Celsius be dried overnight, obtain Non-precious Metal Catalysts
Electrode.With the alcohol water mixed solution (5.0%wt) of spray gun spraying Nafion to prepared Catalytic Layer side and at 75 degrees Celsius
With solvent flashing, Nafion carrying capacity is 0.2 milli gram/cm within dry two hours.
A piece of processed Nafion membrane (N211) is taken, side places above-mentioned obtained Non-precious Metal Catalysts electrode and is used as oxygen
Gas reducing electrode (cuts next part), and previously prepared pallium-on-carbon electrode (0.1 milli gram/cm platinum) is placed in the other side
As oxidation of hydrogen electrode, 135 degrees Celsius of hot pressing, 120 seconds obtained membrane electrodes.
Embodiment 2
Prepare carbon catalysis (Co-N-C) electrode of the high nitridation of the cobalt N doping of carbon paper load
In the exemplary embodiments of Non-precious Metal Catalysts electrode for preparing cobalt N doping, 2.1 grams of cobalt chloride (CoCl2·
6H2O) it is used as cobalt source, 4.4 grams of pentaethylene hexamines (Pentaethylenehexamine) are used as nitrogen source and carbon source material, and 0.5 gram
Graphene is used as carbon source material.Pentaethylene hexamine is dissolved into 50 milliliters of sodium chloride (12.0 grams) aqueous solution first, stirring half
Hour to be uniformly mixed, is then added 2.5 grams of grindings in advance and dried MCM41 ultrasonic disperse half an hour, stirs half an hour；
Hereafter graphene is added in above-mentioned solution, the fully dispersed rear aqueous solution (50 milliliters) that cobalt chloride is added dropwise is stirred by ultrasonic and stirred
It mixes overnight.Through Rotary Evaporators in 50 degrees Celsius of dry removal moisture, then it is freeze-dried collection black powder.With 50 milliliters of second
Alcohol-isopropyl alcohol mixture (1/1V/V) is sprayed directly into ultrasonic flush coater with laminar microporous diffuser after being uniformly dispersed again
On carbon paper, spraying area is 40 millimeters × 40 millimeters.Then by above-mentioned sample be placed in the tube furnace for be connected with high pure nitrogen by
It is heat-treated according to following procedure heating: rising to 300 degrees Celsius from room temperature with 1 degrees celsius/minute of rate and kept for 2.5 hours；Then
750 degrees Celsius are risen to 2 degrees celsius/minutes to be kept for 3 hours.Nitrogen protection drops to room temperature, successively uses potassium hydroxide aqueous solution
(10.0 mol/L), aqueous sulfuric acid (1 mol/L), ethanol water (1/3V/V) washing by soaking for several times, are then drying again
It is dried overnight for 120 degrees Celsius in case, the carbon catalysis electrode of cobalt nitrogen codope is made.
Embodiment 3
Prepare base metal carbon catalysis (Co-N-C) electrode of the cobalt nitrogen codope of carbon paper support
In the typical case of Non-precious Metal Catalysts electrode for preparing cobalt nitrogen codope, pentaethylene hexamine
(Pentaethylenehexamine) it is used as carbon source and nitrogen source, cobalt nitrate (Co (NO3)2·6H2O) it is used as cobalt source.First
1.9 grams of pentaethylene hexamines are dissolved into 50 milliliters of water, stir 0.5 hour to be uniformly mixed；Then 2.3 grams of grindings in advance are added
With dried MCM-41, sonic oscillation and stirring makes it be uniformly dispersed and be kept stirring in 2 hours；Hereafter by 2.3 grams of polyethylene
Pyrrolidones (PVP) is dissolved in 50 milliliters of water, and 1.5 grams of cobalt nitrates and 1.6 grams of zinc nitrate (Zn (NO are added3)2·6H2O), surpass
Sound oscillation and stirring make three uniformly mixed for one hour；Then the aqueous solution containing cobalt nitrate, zinc nitrate and PVP is slowly added dropwise
Into the slurries containing pentaethylene hexamine, it is stirred at room temperature 12 hours.Mixed serum after being sufficiently mixed infiltration uses rotary evaporation
Instrument removes moisture at 50 c, then it is freeze-dried obtain black powder sample, twice dispersing to ethyl alcohol-ethylene glycol mixing
It in solvent (3/1V/V), is then sprayed on the carbon paper with laminar microporous diffuser through ultrasound, spraying area is 30 millimeters × 30 millis
Rice, spraying area temperature are 80 degrees Celsius.After drying and removing organic solvent, to carbon paper in tube furnace under high pure nitrogen protection
The sample of load is heat-treated.450 degrees Celsius are risen to by room temperature with the heating rate of 2 degrees celsius/minutes first when heat treatment
Then heat preservation 2 hours is warming up to 1050 degrees Celsius with same heating rate and keeps the temperature 3 hours, last cooled to room temperature,
Obtain the Non-precious Metal Catalysts layer of carbon paper load.Gained Non-precious Metal Catalysts electrode successively uses sodium hydroxide solution, and (10.0 rub
You/liter), sulfuric acid solution (1.0 mol/L), ethanol water (1/3V/V) washing is multiple, finally by the base metal after washing
The catalysis electrode 200 DEG C water thermal activations in concentrated ammonia solution (28%wt) again, in 80 degrees Celsius of dryings after filtration washing
The base metal carbon catalysis electrode of cobalt nitrogen codope is made in 12h.
Embodiment 4
Prepare iron cobalt-nitrogen-doping base metal carbon catalysis (FeCo-N-C) electrode of carbon paper support
In the typical case of base metal carbon catalysis electrode for preparing iron cobalt N doping, melamine be used as carbon source and
Nitrogen source, ferric nitrate (Fe (NO3)3·9(H2)) and cobalt nitrate (Co (NO O3)2·6H2O) it is used as the presoma of iron cobalt.First will
6.5 grams of melamines are dissolved into 50 milliliters of water, stir 0.5 hour to be uniformly mixed；Then 4.5 grams of grindings in advance are added and do
The MCM48 of dry mistake, sonic oscillation and stirring make it be uniformly dispersed and be kept stirring in 2 hours；Hereafter by 2.5 grams of polyvinyl pyrroles
Alkanone (PVP) is dissolved in 50 milliliters of water, and 1.5 grams of cobalt nitrates, 2.1 grams of ferric nitrates and 3.0 grams of zinc nitrate (Zn (NO are added3)2·
6H2O), sonic oscillation and stirring make three uniformly mixed for one hour；Then it will contain the water-soluble of cobalt nitrate, zinc nitrate and PVP
Liquid is slowly dropped in the slurries containing pentaethylene hexamine, is stirred at room temperature 12 hours.Mixed serum after being sufficiently mixed infiltration makes
Moisture is removed at 50 c with Rotary Evaporators, then freeze-dried obtains black powder sample, twice dispersing to ethyl alcohol-
In isopropyl alcohol mixed solvent (2/1V/V), then sprayed on the carbon paper with laminar microporous diffuser through ultrasound, spraying area 60
Millimeter × 30 millimeters, spraying area temperature are 80 degrees Celsius.After drying and removing organic solvent, in tubular type under high pure nitrogen protection
The sample of carbon paper load is heat-treated in furnace.It is risen to first with the heating rate of 2 degrees celsius/minutes by room temperature when heat treatment
400 degrees Celsius keep the temperature 2 hours, are then warming up to 1050 degrees Celsius with same heating rate and keep the temperature 3 hours, last naturally cold
But to room temperature, the Non-precious Metal Catalysts layer of carbon paper load is obtained.Gained Non-precious Metal Catalysts electrode successively uses sodium hydroxide molten
Liquid (10 mol/L), sulfuric acid solution (1 mol/L), ethanol water (1/3V/V) washing repeatedly, finally will be non-after washing
The precious metal catalyst electrode 200 DEG C water thermal activations in concentrated ammonia solution (28%wt) again, in 80 degrees Celsius after filtration washing
It is 12 hours dry, the base metal carbon catalysis electrode of iron cobalt N doping is made.
Compared with platinum base Catalytic Layer, Catalytic Layer prepared by catalysis electrode of the invention is complete non-noble metal nitrating
Carbon material, 1/10th of cost less than platinum base catalysis layer material, and be catalyzed layer material or catalyst is in fuel cell
The shared highest part of cost, accounts for 40% or so at present, so can significantly be dropped using catalysis electrode disclosed in this invention
The cost of low membrane electrode or even fuel cell entirety.This can be greatly promoted the commercial applications of fuel cell.On the other hand
Preparation method disclosed in this invention, simple process is direct, and product has the porous structure of high-sequential, and has preferable dredge
Water characteristic, the gas conduction and draining being very beneficial in electrode reaction, fuel cell caused by avoiding due to mass transfer
Performance degradation can improve the service life of Proton Exchange Membrane Fuel Cells significantly, this is also very beneficial for the production of fuel cell
Industry.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (17)
1. a kind of Non-precious Metal Catalysts electrode, which is characterized in that including electrode diffusion layer, the surface of the electrode diffusion layer is formed
There is Catalytic Layer, the Catalytic Layer makes catalyst component be grown on or bear by Catalytic Layer material precursor mixture by high-temperature heat treatment
It is downloaded on electrode diffusion layer and is formed；Wherein, the Catalytic Layer material precursor mixture include non-platinum group transition metal before
Drive body, carbon source material and nitrogen source material.
2. Non-precious Metal Catalysts electrode according to claim 1, which is characterized in that the transition metal precursor from
All kinds of inorganic salts or organic compound of transition metal comprising metal halide, metal acetate, metal nitrate, metal
Nitrite, metal carbonate, metal cyanides, metal hydroxides, metal phosphate, metal sulfide, metal sulfate,
Metal sulphite, metal sulphite, metal phthalocyanine compound, in metalloporphyrin compound any one or combinations thereof.
3. Non-precious Metal Catalysts electrode according to claim 2, which is characterized in that the transition metal includes iron Fe, cobalt
Co, molybdenum Mo, nickel, manganese Mn, chromium Cr, copper Cu, in zinc Zn any one or combinations thereof.
4. Non-precious Metal Catalysts electrode according to claim 1, which is characterized in that the carbon source material includes saccharin, Portugal
Grape sugar, formaldehyde, phenol, polystyrene, carbon dust, carbon nanotube, graphene, vinylamine (ethyleneamines), phthalocyanine, ferrosin, trimerization
In cyanamide, aniline and its derivatives any one or combinations thereof.
5. Non-precious Metal Catalysts electrode according to claim 1, which is characterized in that the nitrogen source material includes all kinds of organic
In amino-compound, inorganic amide or nitride any one or combinations thereof.
6. Non-precious Metal Catalysts electrode according to claim 1, which is characterized in that the electrode diffusion layer includes each such sheets
Shape carbon material, the sheet carbon material can first pass through processing in advance or directly use, the pretreatment include with hydrophobic material or
Water wetted material changes the hydrophobic hydrophilic nmature of sheet carbon material, or with carbon dust, carbon nanotube, carbon ball, graphene, graphite oxide
In alkene any one or combinations thereof prepare or improve diffusion layer and pore structure, wherein prepare and glued used in diffusion layer
Mixture includes polytetrafluoroethylene (PTFE) and its derivative.
7. Non-precious Metal Catalysts electrode according to claim 1, which is characterized in that the Catalytic Layer material precursor mixing
Object further includes catalyst structure directed agents, and the catalyst structure directed agents include template, chelating agent and pore creating material.
8. Non-precious Metal Catalysts electrode according to claim 7, which is characterized in that the template includes all kinds of molecules
Sieve, in ordered mesoporous material any one or combinations thereof；The chelating agent includes complexing agent, any one in surfactant
Kind or combinations thereof；The pore creating material includes sodium chloride, zinc chloride, aluminium chloride, magnesium chloride, calcium chloride, all kinds of carbonate, all kinds of nitre
In hydrochlorate, each ammonium salts any one or combinations thereof.
9. the preparation method of Non-precious Metal Catalysts electrode described in a kind of any one of claim 1~6, which is characterized in that
The following steps are included:
(1) Catalytic Layer material precursor mixture and solvent are mixed and made into mixed liquor；Wherein, the Catalytic Layer material precursor
Mixture includes the transition metal precursor, carbon source material and nitrogen source material of non-platinum group；
(2) mixed liquor made from step (1) is loaded on electrode diffusion layer, and solvent is removed；
(3) electrode diffusion for having mixed liquor by the load of step (2) processing is placed under the protection of particular atmosphere and carries out height
Warm processing, makes to form Catalytic Layer on electrode diffusion layer, and Non-precious Metal Catalysts electrode is made.
10. the preparation method of Non-precious Metal Catalysts electrode according to claim 9, which is characterized in that the solvent includes
Water, all kinds of alcohol, all kinds of ethers, in all kinds of ketone any one or combinations thereof.
11. the preparation method of Non-precious Metal Catalysts electrode according to claim 9, which is characterized in that in step (2),
The mixed liquor is loaded on electrode diffusion layer in such a way that spraying, smearing, knife are scraped or are impregnated；When load, electrode expands
Dissipating environment temperature locating for layer is -20~200 degrees Celsius；In loading process, the solvent is removed by volatilization.
12. the preparation method of Non-precious Metal Catalysts electrode according to claim 9, which is characterized in that at the high warm
Reason mode includes high-temperature roasting processing or thermal decomposition, and the high-temperature roasting processing or the temperature thermally decomposed are 200~1200 Celsius
Degree；The high-temperature roasting processing is divided into 1~10 stage, and each section of programmed rate is Celsius 0.01~50.0
Degree/min.
13. the preparation method of Non-precious Metal Catalysts electrode according to claim 9, which is characterized in that the particular atmosphere
Including inert atmosphere, reducing atmosphere or contain the atmosphere of ammonia.
14. the preparation method of Non-precious Metal Catalysts electrode according to claim 9, which is characterized in that further comprising the steps of:
(4) it is successively rinsed with lye and/or acid solution or boils the Non-precious Metal Catalysts electrode obtained by step (3), and through washing
It is dried again after washing, to remove the residue of catalyst structure directed agents；
(5) ion conductor polymer material is applied or is impregnated on the Non-precious Metal Catalysts electrode by step (4) processing, made
Ion conductor polymer material enters in the Catalytic Layer of base metal electrode.
15. the preparation method of Non-precious Metal Catalysts electrode according to claim 14, which is characterized in that required for the washing
Liquid include acidic aqueous solution, alkaline aqueous solution, high purity water, all kinds of alcohol, in all kinds of ketone any one or combinations thereof；It is described dry
Dry temperature is 30~200 degrees Celsius.
16. the preparation method of Non-precious Metal Catalysts electrode according to claim 14, which is characterized in that the ion conductor polymerization
Object material is uniform or non-uniform in the carrying capacity of the different zones of the Catalytic Layer of Non-precious Metal Catalysts electrode；The ion is led
Doped with hydrophobic material or water wetted material in the solution of body polymer material, with meet Catalytic Layer different zones it is hydrophobic or close
Water requirement.
17. a kind of membrane electrode, which is characterized in that including solid electrolyte film, the side of the solid electrolyte film is equipped with hydrogen
Oxidizing electrode or load have the oxidation catalyst of hydrogen, and the other side of the solid electrolyte film is equipped with any in claim 1~8
Non-precious Metal Catalysts electrode described in one.
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