CN110380067A - A kind of fuel cell membrane electrode catalyst, preparation method and application - Google Patents
A kind of fuel cell membrane electrode catalyst, preparation method and application Download PDFInfo
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- CN110380067A CN110380067A CN201910754307.3A CN201910754307A CN110380067A CN 110380067 A CN110380067 A CN 110380067A CN 201910754307 A CN201910754307 A CN 201910754307A CN 110380067 A CN110380067 A CN 110380067A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention provides a kind of fuel cell membrane electrode catalyst, preparation method and application, this method comprises: S1, transition-metal cation source compound is dissolved in the first solvent, the first solution is obtained；Organic nitrogen-containing ligand is dissolved in the second solvent, obtains the second solution；Third solvent is dispersed by porous, electrically conductive carbon material, obtains suspension；S2, it after mixing first solution with the second solution, then mixes and is adsorbed with the suspension, separated, obtain solid matter；S3, the solid matter is reacted by annealing, obtains fuel cell membrane electrode catalyst comprising porous, electrically conductive carbon carrier, and the transition metal and nitrogen that are carried in the carrier inside hole.Catalyst activity made from the method for the present invention is high, has very excellent gas-solid-liquid three phase boundary.The method of the present invention is simple, low in cost, especially suitable for high-power metal air cell and the anode of fuel cell, has good Commercial Prospect.
Description
Technical field
The present invention relates to fuel cell catalyst technical field more particularly to a kind of fuel cell membrane electrode catalyst, its
Preparation method and application.
Background technique
Fuel cell is the new green energy switching device that chemical energy is converted into electric energy, compares function with height
Rate, energy conversion efficiency, it is pollution-free many advantages, such as, it is considered to be can solve the key side of environmental pollution and energy crisis
Case, transportation and communication, unmanned plane, portable mobile power supply, in terms of all have wide application prospect.
Fuel cell is made of positive and negative two electrodes and electrolyte；Its core reaction is that the redox on positive membrane electrode is anti-
It answers, generally requires with the high performance membrane electrode catalyst haveing excellent performance.It is believed that the superiority and inferiority of fuel battery performance is in suitable journey
It is to be determined by the performance height of membrane electrode catalyst on degree.
Reasonable gas-solid-liquid three phase boundary and efficient intrinsic catalytic activity, are the inevitable requirements of such catalyst.Tradition
Membrane electrode catalyst there are three types of improved preparation method: for the rare metals catalytic active component such as Pt, Ag, generally make
Carried out with High-conductivity carbon with rare metal it is compound, i.e., it is direct by rare metal using conventional conductive black and active carbon etc.
In-situ reducing, or conductive carbon surface is deposited on to prepare efficient rare metal catalyst.For MnO2、Co3O4Deng traditional quotient
It is currently that this kind of active reaction substance and conductive carbon are directly subjected to solid-phase ball milling, or after evenly mixing for catalyst
It uses.For non-precious metal catalyst, such as period 4 transition metal, usually metal and organic matter ligand are carried out
Fumed pyrogenic obtains the active material structure compound with pyrolytic carbon in situ.
The design of above-mentioned membrane electrode catalyst material is essentially consisted in synthesis principle, as far as possible activity of raising catalyst itself
The density and degree of exposure in site, this design principle are conducive to the property that catalyst has been obtained in the test such as rotating disk electrode (r.d.e)
Energy.But when being assembled into fuel cell and carrying out high current long-time discharge test, their disadvantage is then sufficiently sudden and violent
Expose: firstly, traditional catalyst lacks Effective Regulation on electron propagation ducts, needing to increase many conductive agents to be formed
Enough electronics accesses, these conductive agents reduce the conversion zone of catalyst.Secondly, traditional catalyst does not have gas transport logical
The rational design in road and ion transport channel, building gas transport channel mainly pass through the hydrophobic polymerics such as addition polytetrafluoroethylene (PTFE)
Form network structure, on the one hand this method can significantly reduce electric conductivity, while also resulting in the drop of catalyst reaction area
It is low, it is carrying out being easy to produce water logging when high current is discharged for a long time, is seriously affecting battery life.
All in all, the main problem of existing membrane electrode catalyst influence fuel battery performance is, three phase boundary of catalyst
Face channel lacks reasonable design.Therefore, researching and developing one kind has high activity, while having the fuel cell membranes of abundant three phase boundary
Electrode catalyst is the thing being of great significance.
Summary of the invention
In view of this, the application provides a kind of fuel cell membrane electrode catalyst, preparation method and application, the application system
Standby membrane electrode catalyst has gas-solid-liquid three-phase reaction interface abundant, and activity is high, can export for fuel cell maximum
The runing time of power density and long-time stable provides strong guarantee.
The present invention provides a kind of preparation method of fuel cell membrane electrode catalyst, comprising the following steps:
S1, transition-metal cation source compound is dissolved in the first solvent, obtains the first solution；
Organic nitrogen-containing ligand is dissolved in the second solvent, obtains the second solution；
Third solvent is dispersed by porous, electrically conductive carbon material, obtains suspension；
S2, it after mixing first solution with the second solution, then mixes and is adsorbed with the suspension, through separating,
Obtain solid matter；
S3, the solid matter is reacted by annealing, obtains fuel cell membrane electrode catalyst；The combustion
Expect cell membrane-electrode catalyst include porous, electrically conductive carbon carrier, and the transition metal being carried in the carrier inside hole and
Nitrogen；
First solvent and the second solvent are sub- independently selected from water, oleyl amine, hexamethylene, dimethylformamide, dimethyl
One of sulfone, methanol, ethyl alcohol and oleic acid are a variety of；The type of the third solvent is different from the first solvent and second molten
Agent.
Preferably, in the fuel cell membrane electrode catalyst, mole of these three composition primitives of transition metal, nitrogen and carbon
Than for (1~50): (1~50): 100.
Preferably, the third solvent be selected from water, ethyl alcohol, methanol, ethylene glycol, ethyl acetate, toluene, acetone, ethylenediamine,
One of triethanolamine, dimethylformamide and acetonitrile are a variety of.
Preferably, the porous, electrically conductive carbon material be selected from active carbon, conductive black, acetylene black, carbon nanotube, graphene and
One of fullerene is a variety of, and specific surface area is in 200-2000m2Between/g.
Preferably, the organic nitrogen-containing ligand is selected from 2,2- bipyridyl, diamino-pyridine, picoline, ethylpyridine, hydroxyl
One of yl pyridines, nitropyridine, Phen and dicyanodiamine are a variety of.
Preferably, the absorption is no less than half an hour realization by stirring under the conditions of -20~30 DEG C.
Preferably, the annealing includes: to be warming up to 500~1000 DEG C with 1~10 DEG C/min of heating rate and forged
It burns 0.5~5 hour, it is cooling with 1~50 DEG C/min of rate later.
Preferably, in the step S1, the substance for being dissolved in the first solvent further includes surfactant, the surfactant
Selected from polyethyleneimine, neopelex, cetyl trimethylammonium bromide, disodium ethylene diamine tetraacetate, polyethylene
Pyrrolidones, lauroyl glutamate, sodium stearyl sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol and poloxamer three block
One of copolymer is a variety of.
The present invention provides a kind of fuel cell membrane electrode catalyst, and preparation method by mentioned earlier is made；The fuel
Cell membrane-electrode catalyst is 10nm ultra micro nanocluster below or the unit point structure with atom level dispersion；The combustion
Expect that cell membrane-electrode catalyst has hydrophobicity.
In addition, the present invention, which provides catalyst as previously described, is preparing the application in fuel cell membrane electrode.
Compared with prior art, the present invention is porous by solvent optimising and adjustment using porous, electrically conductive carbon material as base material
The adsorption energy of conductive carbon material, thus efficient absorption transition metal and organic nitrogen-containing ligand；Then a step annealing processing is carried out,
By active site rivet in the internal void of carbon substrate, the catalyst material for fuel cell membrane electrode is obtained.This
There is catalyst made from inventive method hydrophobicity and biggish specific surface area to be conducive to gas transport, while have higher
Conductivity, therefore have very excellent gas-solid-liquid three phase boundary.Gained catalyst is swept in the linear volt-ampere of rotating disk electrode (r.d.e)
It retouches in curve test, it is close with extremely low reaction starting polarization potential (1.0V reference is in reversible hydrogen potential) and high carrying current
Spend (5.8mAcm-2More than), it is higher than conventional catalyst 30mV or more on take-off potential and half wave potential, and carrying current
Density will be higher by 1mAcm-2More than.This provides extremely low anode instead in the application of hydrogen-oxygen and metal fuel battery for catalyst
Overpotential is answered, the runing time that maximum power density and long-time stable can be exported for fuel cell provides strong guarantor
Card.
When membrane electrode prepared by the present invention is applied to metal-air battery, the peak value higher than market similar product can be obtained
Power density.Especially under the conditions of high current density, the stability with minimum overpotential and overlength.Meanwhile it answering
There is good hydrophobic discharge characteristic, comprehensive performance is no less than carbon paper, but price is far below the latter when for hydrogen-oxygen fuel cell.
In addition, method of the invention has process flow is simple, low in cost, yield is big, is suitable for industrialized production etc.
Feature has good Commercial Prospect especially suitable for high-power metal air cell and the anode of fuel cell.
Detailed description of the invention
Fig. 1 is the configuration schematic diagram of the catalyst of synthesis of the embodiment of the present invention；
Fig. 2 is the transmission electron microscope picture of catalyst prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD diagram of catalyst prepared by the embodiment of the present invention 1；
Fig. 4 is the XPS figure of catalyst prepared by the embodiment of the present invention 1；
Fig. 5 is the contact angle figure of catalyst prepared by the embodiment of the present invention 2；
Fig. 6 is the specific surface area figure of catalyst prepared by the embodiment of the present invention 3；
Fig. 7 is the transmission electron microscope picture of conventional catalyst in comparative example of the present invention；
Fig. 8 is the contact angle figure of conventional catalyst in comparative example of the present invention；
Fig. 9 is discharge curve comparison diagram when catalyst described in the embodiment of the present invention 1 and comparative example is applied.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of preparation methods of fuel cell membrane electrode catalyst, comprising the following steps:
S1, transition-metal cation source compound is dissolved in the first solvent, obtains the first solution；
Organic nitrogen-containing ligand is dissolved in the second solvent, obtains the second solution；
Third solvent is dispersed by porous, electrically conductive carbon material, obtains suspension；
S2, it after mixing first solution with the second solution, then mixes and is adsorbed with the suspension, through separating,
Obtain solid matter；
S3, the solid matter is reacted by annealing, obtains fuel cell membrane electrode catalyst；The combustion
Expect cell membrane-electrode catalyst include porous, electrically conductive carbon carrier, and the transition metal being carried in the carrier inside hole and
Nitrogen；
First solvent and the second solvent are sub- independently selected from water, oleyl amine, hexamethylene, dimethylformamide, dimethyl
One of sulfone, methanol, ethyl alcohol and oleic acid are a variety of；The type of the third solvent is different from the first solvent and second molten
Agent.
Membrane electrode catalyst material prepared by the present invention has versatility, can apply empty in hydrogen-oxygen fuel cell and metal
In the positive membrane electrode in pneumoelectric pond；The material has gas-solid-liquid three-phase reaction interface abundant and higher catalytic activity, can
Strong guarantee is provided with the runing time for exporting maximum power density and long-time stable for battery.In addition, side of the present invention
Method also have the characteristics that it is easy to operate, low in cost, be suitable for industrialized production.
The embodiment of the present invention weighs transition-metal cation source compound and organic nitrogen-containing ligand, and it is molten to be dissolved in first respectively
Agent, the second solvent, correspondence obtain the first solution and the second solution.
Wherein, transition metal is abbreviated as M in the transition-metal cation source compound, and M is preferably selected from the periodic table of elements
One of period 4 IB-VIII B race transition elements is a variety of, is further selected from iron (Fe), cobalt (Co), nickel (Ni), copper
(Cu) and one of zinc (Zn) or a variety of.The transition-metal cation source compound is mainly nitrate, metal chloride
And its one of hydrate or a variety of；The embodiment of the present invention preferably uses ferric nitrate or cobalt nitrate.The present invention is synthetically prepared tool
There is high versatility, all metallic elements in transition metal period can be achieved.First solvent is selected from water (preferably
For deionized water), oleyl amine, hexamethylene, dimethylformamide, dimethyl sulfoxide, methanol, one of ethyl alcohol and oleic acid or more
Kind, the preferably mixed solution of water and ethyl alcohol.
Transition-metal cation source compound can be added in the container for filling the first solvent for the embodiment of the present invention, preferably stir
Mixing is mixed, the first solution is obtained.In addition, being dissolved in the substance of the first solvent, it is also preferable to include surfactants；It can weigh certain
The surfactant of amount is added in the mixed solution of transition-metal cation source compound and the first solvent, continues to stir,
Obtain the first solution.The surfactant is preferably selected from polyethyleneimine, neopelex, cetyl trimethyl
Ammonium bromide, disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, lauroyl glutamate, sodium stearyl sulfate, poly alkyl alcohol
One of ethylene oxide ether sodium sulfate and poloxamer triblock copolymer are a variety of, further preferably polyethyleneimine.Institute
State surfactant main function be with increase degree of cooperation in subsequent second solvent engagement process, improve the ligand of formation
Concentration class is adsorbed to be more advantageous to carbon carrier.
Also, the organic nitrogen-containing ligand can be added in the container for filling the second solvent for the embodiment of the present invention, preferably stir
Mixing is mixed, the second solution is obtained.The organic nitrogen-containing ligand is represented by organic ligand containing N, is preferably selected from 2,2- bipyridyl, two
One of aminopyridine, picoline, ethylpyridine, pyridone, nitropyridine, Phen and dicyanodiamine are more
Kind, further preferably dicyanodiamine or 2,2- bipyridyl.Second solvent be selected from water (preferably deionized water), oleyl amine,
One of hexamethylene, dimethylformamide, dimethyl sulfoxide, methanol, ethyl alcohol and oleic acid are a variety of, preferably water.The present invention
Stirring in embodiment is technological means well known in the art, and the application has no specifically limited；Generally use magnetic force or machine
The modes such as tool stirring can accelerate dispersion, dissolution, obtain uniformly mixed solution.
Porous adsorbing medium containing C can be carried out ultrasonic disperse by the embodiment of the present invention in third solvent, obtain suspension.
The porous adsorbing medium containing C is porous, electrically conductive carbon material, with micropore abundant and mesoporous, conduction with higher
Property and excellent hydrophobic property.Specifically, the porous, electrically conductive carbon material can be selected from active carbon, conductive black, acetylene black, carbon
One of nanotube, graphene and fullerene are a variety of, preferably conductive black or acetylene black；Specific surface area is in 200-
2000m2Between/g, preferably 1000-2000m2/g.The water contact angle of the porous, electrically conductive carbon material is greater than 100 degree, can be
Oneself preparation, can also use commercially available commercial product.
In the present invention, the type of the third solvent is all different with the first solvent, the second solvent；The third solvent
Be preferably selected from water, ethyl alcohol, methanol, ethylene glycol, ethyl acetate, toluene, acetone, ethylenediamine, triethanolamine, dimethylformamide and
One of acetonitrile is a variety of, more preferably ethylene glycol.The embodiment of the present invention is molten by porous, electrically conductive carbon material addition third
In agent, it is ultrasonically treated after preferably stirring, to obtain evenly dispersed suspension.
The embodiment of the present invention mixes above-mentioned first solution with the second solution, then mixes with the suspension.It is described outstanding
Turbid can be prepared simultaneously with the first solution, the second solution, can also prepare again after the first solution is mixed with the second solution, this
Application has no specifically limited.The embodiment of the present invention can pour into the mixed liquor of the first solution and the second solution in the suspension,
It is preferred that mixing, adsorbing under agitation.
For the present invention mainly using the strategy of absorption confinement synthesis, selection has abundant micropore and mesoporous High-conductivity carbon substrate
Material, by the adsorption energy of the carbon-based bottom material of solvent optimising and adjustment, thus efficient absorption metal and organic nitrogen-containing ligand.Its
In, effective absorption key of ligand is the type selection for ligand used in metal and the regulation for solvent polarity.Institute
It states organic nitrogen-containing ligand and mainly selects multiple tooth and monodentate, and there is abundant lewis base co-ordinating functionality, it can be with metal shape
At the organic ligand or high molecular material of close coupling.For solvent polarity regulation there are two purpose, one is to metal
And its ligand dispersed regulation in a solvent, metal and its ligand dispersion size in a solvent and state directly determine to adsorb
Number, whether solvent polarity and conductive substrates polarity match a possibility that directly determining absorption.
In an embodiment of the present invention, the concentration ratio of first solution, the second solution and suspension meets: obtained
In fuel cell membrane electrode catalyst, transition metal (M), nitrogen (N) and carbon (C) these three composition primitives molar ratios be (1~
50): (1~50): 100, preferably (1~20): (1~30): 100.Specifically, the absorption passes through under the conditions of -20~30 DEG C
Stirring is more than to realize half an hour.The mixture that the embodiment of the present invention obtains absorption is separated by solid-liquid separation, it is preferred to use centrifugation point
From mode；It takes solid phase to be washed, dried again, obtains dry solid matter.Wherein, the temperature and time when absorption
And the drying after absorption is preferably regulated and controled.For example, the temperature of the absorption at 30 degree between minus 20 degrees, preferably
It is -10~10 DEG C, further preferably -5~0 DEG C；Time between 0.5h to 48 hours, can for 1~for 24 hours or 2~12h.Institute
Stating drying can be using modes such as common dryness in the sun, vacuum drying, freeze-drying, supercritical drying, spray drying；The present invention
It carries out draining processing preferably by freeze drier.
It drains after obtaining solid matter, the embodiment of the present invention makes annealing treatment it by tube furnace, and reaction is fired
Expect cell membrane-electrode catalyst.
Annealing is the heat treatment process of a kind of pair of material, is that metal material is heated slowly to certain temperature, is kept
Enough time, it is then cooling with Reasonable Speed.Annealing includes: with 1~10 DEG C/min of liter described in the embodiment of the present invention
Warm rate is warming up to 500~1000 DEG C and calcines 0.5~5 hour, cooling with 1~50 DEG C/min of rate later.Wherein, described
The time of heat treatment process and temperature are also highly important parameter, and the temperature of heat treatment (mainly fumed pyrogenic) cannot mistake
Height, can not be too low, and main function is the formation of active site and forms strong coupling with substrate, to be conducive to
The stabilization and swift electron of active site are conducted.In embodiments herein, the temperature of the calcining (pyrolysis) is in 500-900
DEG C to be optimal, the time is optimal from 0.5h-2h.The rate of the cooling is preferably 10~30 DEG C/min, more preferably 15~25
DEG C/min.The embodiment of the present invention is heat-treated under particular atmosphere, and particular atmosphere selection can be inert atmosphere such as (argon gas, nitrogen
Gas), it is also possible to the reducing atmospheres such as ammonia, hydrogen sulfide, can also be air, oxygen.
The annealing includes a step and multi-step heat treatment technology；The embodiment of the present invention carries out a step rapid thermal treatment
(stove is first mainly warming up to specific temperature, reactive material is directly placed into reaction, then directly take out cooling process,
In quickly refer to that rate of temperature fall is fast), by active site rivet carbon substrate micropore and it is mesoporous in, obtain for fuel cell
The oxygen reduction catalyst (abbreviation fuel cell membrane electrode catalyst) of membrane electrode comprising porous, electrically conductive carbon carrier, and load
Transition metal and nitrogen in the carrier inside hole.Catalyst prepared by the present invention have high active site exposure with
And gas-solid-liquid three phase boundary abundant, have both high conductivity, high gas transport, macroion transmittability.This kind of catalyst simultaneously
It is easily dispersed and prepares slurry, be suitable for the film-forming methods such as spraying, roll-in, hot pressing, the membrane electrode prepared as material is in fuel
High power density and extremely long service life are shown on battery.
The embodiment of the invention provides a kind of fuel cell membrane electrode catalyst, and preparation method by mentioned earlier is made；
Its general formula is MaNbCc, M indicates that transition metal element, N indicate nitrogen, and C indicates that carbon, a:b:c indicate each composition primitive
Molar ratio.In the general formula, M is preferably selected from the one or more of period 4 IB-VIIIB, more preferably Fe, Co, Ni, Cu and Zn
One of or it is a variety of.Also, the oxygen reduction catalyst formula MaNbCcIn, each molar ratio a:b:c for forming primitive can be (1
~50): (1~50): 100, preferably (1~20): (1~30): 100.
Referring to the configuration schematic diagram for the catalyst that Fig. 1, Fig. 1 are synthesis of the embodiment of the present invention.In the embodiment of the present application, institute
Fuel cell membrane electrode catalyst is stated using porous, electrically conductive carbon material as conductive carrier；The carrier is preferably active carbon, conduction
One of carbon black, acetylene black, carbon nanotube, graphene and fullerene are a variety of, and specific surface area is required in 200-2000m2/g
Between.Also, load has transition metal M and nitrogen N in the conductive carrier internal void.The present invention is by the reaction zone of active site
Domain has carried out effective regulation, and conductive carbon surface is all exposed to traditional catalyst and is easy to be flooded difference, of the present invention
Active catalyst sites are predominantly located in the hole inside conductive carbon.
Fuel cell membrane electrode catalyst described in the embodiment of the present invention has hydrophobicity；It mainly includes 10nm below super
Micro-nano cluster or the unit point structure dispersed with atom level, the particle size of catalyst carrier are generally 10 nanometer -200
Nanometer, is conducive to make full use of reaction site, enhances its reactivity.The fuel cell membrane electrode catalyst has hydrophobicity
Be conducive to gas transport with high conductivity, and great specific surface area, therefore there is very excellent gas-solid-liquid three-phase
Interface.
In addition, the present invention, which provides catalyst as previously described, is preparing the application in fuel cell membrane electrode.It will be described
Catalyst is applied to rotating disk electrode (r.d.e), and after tested, with extremely low reaction starting polarization potential, (1.0V reference is in reversible hydrogen
Current potential) and high limiting current density (5.8mAcm-2More than), it is higher than Conventional catalytic on take-off potential and half wave potential
Agent 30mV or more.Also, its limiting current density will be higher by 1mAcm-2More than, this is catalyst in hydrogen-oxygen and metal fuel electricity
The application in pond provides extremely low anode reaction overpotential etc..
Specifically, the catalyst can be used for preparing the positive membrane electrode of metal-air battery and hydrogen-oxygen fuel cell.It is logical
The fuel cell membrane electrode material for crossing the preparation of previously described method, peak power density in metal-air battery can be with
Reach 250mW/cm2More than, 600mW/cm is reached in hydrogen-oxygen fuel cell2More than, 100mAcm-2Current density, service life
Much larger than 100 hours.
When membrane electrode prepared by the present invention is applied on metal-air battery, the peak higher than market similar product can be obtained
It is worth power density.Especially under the conditions of high current density, the stability with minimum overpotential and overlength.Meanwhile
There is good hydrophobic discharge characteristic, after comprehensive performance is no less than carbon paper, but price is far below when applied to hydrogen-oxygen fuel cell
Person.The features such as method of the invention has process flow simple, and low in cost, yield is big, is suitable for industrialized production, it is especially suitable
For high-power metal air cell and the anode of fuel cell, there is good Commercial Prospect.
For a further understanding of the application, fuel cell membrane electrode provided by the present application is catalyzed below with reference to embodiment
Agent, preparation method and application are specifically described.It is understood that these embodiments are with technical solution of the present invention
Premised under implemented, the detailed implementation method and specific operation process are given, only be further illustrate the present invention
Feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following implementation
Example.
Meanwhile in the case where no in addition explanation, various source chemicals and equipment involved in present specification
It is purchased from market and directly uses.
Embodiment 1
0.5g ferric nitrate is weighed, is added and fills 30mL deionized water and 10mL ethyl alcohol, in the beaker that volume is 100mL, use
Magnetic stirrer 5 minutes；Weigh 0.1g polyethyleneimine (Aladdin company, M.W.600,99%, article No. E107007-
25g, following embodiment are identical) it is added in above-mentioned mixed solution, continue to stir, obtains the first solution after ten minutes.
4g dicyanodiamine is weighed, is added and fills 100mL deionized water, in the beaker that volume is 500mL, use magnetic agitation
After device stirs 30min, the second solution is obtained.First solution is poured into wherein, heating stirring 1h is continued, obtains the first solution and the
The mixed solution of two solution.
200mL ethylene glycol is added in 4g conductive black BP2000 (being produced by Cabot Co., Ltd, the U.S., can directly buy)
In, it after magnetic stirrer 10min, is ultrasonically treated using supersonic cleaning machine, after 30min, is obtained evenly dispersed
Suspension.
The mixed solution of first solution and the second solution is poured into above-mentioned suspension, using ice bath, in 0 degrees celsius
Lower stirring 4h.Then, supercentrifuge is used to the mixture that absorption obtains, carries out the centrifuge separation of 1600rpm/min, used
After deionized water and ethyl alcohol respectively carry out 1 washing, carries out draining processing using freeze drier, obtain solid matter.
By the solid matter by tube furnace (argon atmosphere, following embodiment are identical), 1 is carried out under the conditions of 900 degree
Hour calcining, wherein heating rate is 5 degree per minute, and annealing rate of temperature fall per minute, obtains the hydrogen reduction catalysis for 20 degree
Agent.
Obtained catalyst structure signal is as shown in Figure 1；Its pattern is as shown in Fig. 2, Fig. 2 is the system of the embodiment of the present invention 1
The transmission electron microscope photo of standby catalyst.Obtained material sample is partial size between 5 nanometers -200 microns, has porous knot
The catalyst of structure, square resistance are lower than 1 Ω ﹒ cm.Square resistance test method: being tested using ST-21 type square resistance,
Electrode film is cut out into the square for 2x2cm, with a thickness of 0.6 centimetre, using four probes center and nearby symmetrical 4
Point, is touched, and is applied voltage, is obtained the parameters such as current resistor, square resistance is calculated according to formula.
Resulting sample is identified and tested and analyzed, XRD and XPS result is respectively referring to Fig. 3 and Fig. 4；Determine gained
Sample be porous Fe of uniform sizeaNbCcCatalyst.Wherein, Fe and N molar ratio is the two adduction and carbon between 3.5 to 5
Molar ratio be 1:10-50.
Fig. 3 is X-ray diffraction pattern (XRD), illustrates that the catalyst of synthesis there is no iron particle and its compound, master
Wanting existing is carbon peak, illustrates that the active material of iron is dispersed in carbon-coating well.Fig. 4 is x-ray photoelectron spectroscopy
Scheme (XPS), illustrates active material FeaNbCcMiddle iron mainly exists in the form of Fe2+ to 3+, and Fe particle is not present；Explanation forms
Preferable Fe-N coordination.
Embodiment 2
0.5g cobalt nitrate is weighed, is added and fills 30mL deionized water and 10mL ethyl alcohol, in the beaker that volume is 100mL, use
Magnetic stirrer 5 minutes；It weighs 0.1g polyethyleneimine to be added in above-mentioned mixed solution, continues to stir, 10 minutes
After obtain the first solution.
1g 2 is weighed, 2- bipyridyl is added and fills 100mL deionized water, in the beaker that volume is 500mL, uses magnetic force
After blender stirs 30min, the second solution is obtained.First solution is poured into wherein, continues heating stirring 1h, obtains the first solution
With the mixed solution of the second solution.
2g conductive black EC-600JD (Japanese lion princes and dukes department) is added in 200mL ethylene glycol, magnetic stirrer is used
It after 10min, is ultrasonically treated using supersonic cleaning machine, after 30min, obtains evenly dispersed suspension.
The mixed solution of first solution and the second solution is poured into above-mentioned suspension, using ice bath, in 0 degrees celsius
Lower stirring 4h.Then, supercentrifuge is used to the mixture that absorption obtains, carries out the centrifuge separation of 1600rpm/min, used
After deionized water and ethyl alcohol respectively carry out 1 washing, carries out draining processing using freeze drier, obtain solid matter.
It by the solid matter by tube furnace, carries out calcining for 1 hour under the conditions of 800 degree, wherein heating rate is 5 degree
Per minute, annealing rate of temperature fall is 20 degree per minute, obtains the oxygen reduction catalyst.
Resulting sample is identified and tested and analyzed, determines that resulting sample is porous C o of uniform sizeaNbCcIt urges
Agent.The catalyst primitive ratio is same as Example 1, and in the ratio of especially Co and N, the two molar ratio is 1:4 or so.
To resulting sample carry out contact angle test, specifically used Germany's Dataphysics OCA25 contact angle measurement,
Catalyst is subjected to tabletting, is pressed into smooth 2x2cm film, water droplet is injected at film surface using micro liquid inlet device, uses high speed
Video camera shooting, uses included analysis software the Fitting Calculation contact angle.As a result as shown in figure 5, its water contact angle is 111.1 °, it is
Hydrophobic material.
Embodiment 3
0.5g ferric nitrate is weighed, is added and fills 30mL deionized water and 10mL ethyl alcohol, in the beaker that volume is 100mL, use
Magnetic stirrer 5 minutes, obtain the first solution.
4g dicyanodiamine is weighed, is added and fills 100mL deionized water, in the beaker that volume is 500mL, use magnetic agitation
After device stirs 30min, the second solution is obtained.First solution is poured into wherein, heating stirring 1h is continued, obtains the first solution and the
The mixed solution of two solution.
4g conductive black XC-72R (Cabot Co., Ltd, the U.S.) is added in 200mL ethylene glycol, magnetic stirrer is used
It after 10min, is ultrasonically treated using supersonic cleaning machine, after 30min, obtains evenly dispersed suspension.
The mixed solution of first solution and the second solution is poured into above-mentioned suspension, using ice bath, in 0 degrees celsius
Lower stirring 4h.Then, supercentrifuge is used to the mixture that absorption obtains, carries out the centrifuge separation of 1600rpm/min, used
After deionized water and ethyl alcohol respectively carry out 1 washing, carries out draining processing using freeze drier, obtain solid matter.
It by the solid matter by tube furnace, carries out calcining for 1 hour under the conditions of 900 degree, wherein heating rate is 5 degree
Per minute, annealing rate of temperature fall is 20 degree per minute, obtains the oxygen reduction catalyst.
Resulting sample is identified and tested and analyzed, determines that resulting sample is porous Fe of uniform sizeaNbCcIt urges
Agent.
Using Merck & Co., Inc, U.S. specific-surface area detection instrument, 100mg powder is taken, carries out the test of nitrogen adsorption desorption, tests institute
The specific surface area of the sample obtained, as a result (ordinate is that every gram of substance is adsorbed or is desorbed under certain condition in Fig. 6 as shown in Figure 6
Gas (N2) volume, abscissa be than pressure P/P0, P is the true pressure of gas, P0For saturation of gas at a temperature of measurement
Steam pressure), specific surface area 1200m2/g。
Comparative example
With catalyst MnO2As a comparison, contrast sample is bought from Guangzhou nano chemical technology Co., Ltd.
The catalyst morphology is as shown in fig. 7, Fig. 7 is the transmission electron microscope photo of catalyst in comparative example of the present invention.It can from Fig. 7
See, is mainly the crystallization block that diameter is 50-100nm.To resulting sample carry out contact angle test, as a result as shown in figure 8,
Its water contact angle is 63.4 °.
Fig. 9 is discharge curve comparison diagram when catalyst described in the embodiment of the present invention 1 and comparative example is applied, and ordinate is
Current density (milliampere is every square centimeter), abscissa are current potential (voltage is relative to reversible hydrogen electrode).As seen from Figure 9, MnO2It urges
There is a big difference with synthesized catalyst for the take-off potential of agent, half wave potential and limiting current density, and take-off potential represents
Catalyst latent active, the application synthetic catalyst ratio MnO2The high nearly 200mV of catalyst illustrates the catalyst tool of the application synthesis
There is higher reactivity.Meanwhile the present invention by active site confinement in carbon structure duct, also increase its conductivity and object
Matter transport capability, thus the carrying current and half wave potential performance that are greatly improved.
As seen from the above embodiment, catalyst made from the method for the present invention has hydrophobicity and biggish specific surface area
Be conducive to gas transport, while conductivity with higher, therefore there is very excellent gas-solid-liquid three phase boundary.Rotating circular disk
What electrode was applicable in is the rotating disk electrode (r.d.e) test macro of Pine company, the U.S., and catalyst is supported in rotating disk electrode (r.d.e),
By 1600 revs/min of rotary test, the insufficient influence factor of oxygen supply is removed, thus the sheet of more convenient Study of Catalyst
Sign activity.Pipeline purging voltammetric scan curve sweeps to 0.1V with respect to reversible hydrogen electrode from 1.1V, can preferably measure the sheet of catalyst
Sign activity.Gained catalyst originates polarization in the linear voltammetric scan curve test of rotating disk electrode (r.d.e), with extremely low reaction
Current potential (1.0V reference is in reversible hydrogen potential) and high limiting current density (5.8mAcm-2More than), in take-off potential and half-wave
It is higher than conventional catalyst 30mV or more on current potential, and limiting current density will be higher by 1mAcm-2More than.This exists for catalyst
The application of hydrogen-oxygen and metal fuel battery provides extremely low anode reaction overpotential, can export maximum function for fuel cell
The runing time of rate density and long-time stable provides strong guarantee.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (10)
1. a kind of preparation method of fuel cell membrane electrode catalyst, comprising the following steps:
S1, transition-metal cation source compound is dissolved in the first solvent, obtains the first solution；
Organic nitrogen-containing ligand is dissolved in the second solvent, obtains the second solution；
Third solvent is dispersed by porous, electrically conductive carbon material, obtains suspension；
S2, it after mixing first solution with the second solution, then mixes and is adsorbed with the suspension, separated, obtained
Solid matter；
S3, the solid matter is reacted by annealing, obtains fuel cell membrane electrode catalyst；The fuel electricity
Pond membrane electrode catalyst includes porous, electrically conductive carbon carrier, and the transition metal and nitrogen that are carried in the carrier inside hole；
First solvent and the second solvent are independently selected from water, oleyl amine, hexamethylene, dimethylformamide, dimethyl sulfoxide, first
One of alcohol, ethyl alcohol and oleic acid are a variety of；The type of the third solvent is different from the first solvent and the second solvent.
2. preparation method according to claim 1, which is characterized in that in the fuel cell membrane electrode catalyst, transition
The molar ratio of these three composition primitives of metal, nitrogen and carbon is (1~50): (1~50): 100.
3. preparation method according to claim 1, which is characterized in that the third solvent is selected from water, ethyl alcohol, methanol, second
One of glycol, ethyl acetate, toluene, acetone, ethylenediamine, triethanolamine, dimethylformamide and acetonitrile are a variety of.
4. preparation method according to claim 1, which is characterized in that the porous, electrically conductive carbon material is selected from active carbon, leads
One of electric carbon black, acetylene black, carbon nanotube, graphene and fullerene are a variety of, and specific surface area is in 200-2000m2/ g it
Between.
5. preparation method according to any one of claims 1 to 4, which is characterized in that the organic nitrogen-containing ligand is selected from
2,2- bipyridyl, diamino-pyridine, picoline, ethylpyridine, pyridone, nitropyridine, Phen and dicyanodiamine
One of or it is a variety of.
6. preparation method according to claim 5, which is characterized in that the absorption under the conditions of -20~30 DEG C by stirring
No less than half an hour is realized.
7. preparation method according to claim 6, which is characterized in that the annealing includes: with 1~10 DEG C/min
Heating rate, be warming up to 500~1000 DEG C and calcine 0.5~5 hour, it is cooling with 1~50 DEG C/min of rate later.
8. preparation method according to claim 5, which is characterized in that in the step S1, be dissolved in the substance of the first solvent
It further include surfactant, the surfactant is selected from polyethyleneimine, neopelex, cetyl trimethyl
Ammonium bromide, disodium ethylene diamine tetraacetate, polyvinylpyrrolidone, lauroyl glutamate, sodium stearyl sulfate, poly alkyl alcohol
One of ethylene oxide ether sodium sulfate and poloxamer triblock copolymer are a variety of.
9. a kind of fuel cell membrane electrode catalyst, which is characterized in that by preparation side according to any one of claims 1 to 8
Method is made；The fuel cell membrane electrode catalyst is 10nm ultra micro nanocluster below or the list with atom level dispersion
Site structure；The fuel cell membrane electrode catalyst has hydrophobicity.
10. the catalyst obtained such as preparation method according to any one of claims 1 to 8 or catalysis as claimed in claim 9
Agent is preparing the application in fuel cell membrane electrode.
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