CN106910902A - A kind of fuel cell oxygen reduction catalyst and preparation method thereof - Google Patents
A kind of fuel cell oxygen reduction catalyst and preparation method thereof Download PDFInfo
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- CN106910902A CN106910902A CN201710045207.4A CN201710045207A CN106910902A CN 106910902 A CN106910902 A CN 106910902A CN 201710045207 A CN201710045207 A CN 201710045207A CN 106910902 A CN106910902 A CN 106910902A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention provides a kind of fuel cell oxygen reduction catalyst and preparation method thereof, the preparation of methods described including graphene oxide aqueous dispersions, the preparation of manganese basigamy compound and under gas with various atmosphere high-temperature roasting obtain different products, the method of the present invention is raw materials used cheap and easy to get, it is simple and efficient to handle, energy consumption is small, to equipment without particular/special requirement, it is additional low in the pollution of the environment, splendid hydrogen reduction catalytic performance is shown by controlling manganese base oxidation state species, has good application prospect in fuel cell field.Also, in product prepared by the present invention, MnO and Mn2O3Mixed state metal oxide and MnO, are club shaped structure, can be combined closely with Graphene, and specific surface area is big, electro-catalysis efficiency high.
Description
Technical field
The present invention relates to field of fuel cell technology, more particularly to a kind of fuel cell oxygen reduction catalyst and its preparation side
Method.
Background technology
With the increasingly depleted of fossil energy, and in use to the pollution of environment, to develop as early as possible cleaning, can
The requirement of the renewable sources of energy is more and more urgent.Fuel cell is a kind of efficient green clean energy resource conversion system of current great potential
System, is the 4th class generation technology after firepower, waterpower and nuclear energy power generation, is a kind of by fuel（Hydrogen, natural gas, alcohols
Deng）With oxidant（Oxygen）The chemical energy of reaction, by electrochemical reaction without by burning, being directly translated into electric energy
Electrochemical reaction appts.
Cathodic oxygen reduction（ORR）It is limitation Proton Exchange Membrane Fuel Cells（PEMFC）And DMFC
（DMFC）The key factor of performance.At present, it is believed that ORR mainly occurs by two kinds of approach, i.e., the electronics of tetrahydrochysene four is complete
The partial reduction of the process and the electronics of dihydro two of reduction generation water generates the process of hydrogen peroxide.
Nowadays it is Pt/C catalyst using wider fuel battery cathod catalyst, carbon material is simple, easy due to preparing
In mass producing and having good chemical property, mechanical stability, fuel-cell catalyst carrier is widely used for by people.
2004, British scientist was found that by a kind of tightly packed carbonaceous green wood into bi-dimensional cellular shape lattice structure of single layer of carbon atom
Material-Graphene (graphene).Graphene is the highly important new material of a class, with specific surface area is big, electric conductivity and is led
Critical nature and the architectural features such as hot excellent and unique ultra-thin graphite plane structure.The electro-chemical activity of metal oxide
Depending on the size and shape of nano material, nanostructured has bigger specific surface area and more activated centres, in electrification
Learning just has activity higher in reacting.
But, because Pt electrodes have, high cost, durability be low, resource shortage, and the easily shortcoming of poisoning, seriously constrains
Fuel cell large-scale application and commercialized development.Therefore it is badly in need of cheap, durable, the efficient and stable non-platinum base negative electrode oxygen of exploitation also
Raw catalyst.
The content of the invention
The present invention is in view of the shortcomings of the prior art, there is provided a kind of fuel cell oxygen reduction catalyst and preparation method thereof, system
For the graphene-supported material modified fuel cell oxygen reduction catalyst of Mn bases for going out, with efficient, low price, environment-friendly spy
Point.
The present invention is achieved through the following technical solutions, there is provided a kind of fuel cell oxygen reduction catalyst, is work with MnO
Property center or with MnO and Mn2O3It is activated centre.
Mn oxides have preferable catalytic oxidation-reduction performance, in the oxide of mixed valence, due to the oxygen of different valence state
Compound coexists, and so as to promote the electro transfer of oxygen reduction reaction, is strengthened performance, shows more excellent performance.Stone
Black alkene loads MnO, Mn2O3Mixed state oxide or MnO fuel cell oxygen reduction catalysts, because it has certain stability
And flexibility, therefore, nanometer grade thickness on a macroscopic level is hopeful to be more widely used in fuel cell.
The present invention also provides a kind of preparation method of fuel cell oxygen reduction catalyst, comprises the following steps：
S101：Prepare graphene oxide aqueous dispersions；
S102：Prepare manganese basigamy compound：It is 1 according to mass ratio by manganese sulfate and potassium permanganate:2.5 ratio wiring solution-forming, and
Add 30-50ml graphene oxide aqueous dispersions to stir, 10-12h is reacted under the conditions of 140 DEG C and obtains sediment, then
By sediment washing, dry, obtain manganese basigamy compound；
S103：The manganese basigamy compound is reduced into 4h under 550-600 DEG C of hydrogen or ammonia atmosphere, fuel cell oxygen is obtained also
Raw catalyst product.
The method that the present invention is provided is supported on Graphene with manganese sulfate and potassium permanganate as raw material, and control ratio is obtained
Manganese basigamy compound, and then under reducing atmosphere（Hydrogen or ammonia）Reduced, can be obtained under the conditions of hydrogen reducing MnO and
Mn2O3Mixed state metal oxide, and ammonia atmosphere reduction obtains MnO compounds.Under normal circumstances, the purpose of ammonia roasting is
For nitrating, and the present invention is then using ammonia as reducing gas；The present invention compared with prior art, prepares the original thing of MnO
Material is different, the MnO and Mn for preparing2O3Mixed state metal oxide and MnO, are club shaped structure, and can be tight with Graphene
With reference to.
Preferably, in the step S102, the method for obtaining sediment is：Uniform mixture will be mixed, reactor will be added
In, reactor is then put into temperature and is set as reacting 10-12h in 140 DEG C of baking oven.Used as optimal, the reaction time is 12h.
Preferably, in the step S103, when reducing atmosphere is ammonia, obtains the Graphene with MnO as activated centre and bear
Carry the material modified fuel cell oxygen reduction catalyst product of Mn bases.
Preferably, in the step S103, when reducing atmosphere is hydrogen, obtain with MnO and Mn2O3It is the stone in activated centre
Black alkene loads the material modified fuel cell oxygen reduction catalyst product of Mn bases.
Preferably, in the step S101, prepare graphene oxide aqueous dispersions method and comprise the following steps：
S1011：3g graphite powders, 15g potassium permanganate and the 114g concentrated sulfuric acids are stirred into 12h in ice-water bath, viscous brown thing is obtained；
The concentrated sulfuric acid herein is effective mass, i.e., the quality of the pure concentrated sulfuric acid, if for example, being that 98%, density is with concentration
1.836g/cm3The concentrated sulfuric acid then need add about 64ml.
S1012：By in viscous brown thing addition 200mL ultra-pure waters, the dioxygen that 15mL concentration is 30% is then added dropwise
Water, centrifuge washing is carried out after stirring 30min at 30 DEG C, obtains graphene oxide aqueous dispersions.
Add hydrogen peroxide by the foreign ion cleaning in viscous brown thing, then separate solid liquid phase thing using centrifuge
Matter, it is also possible to be first centrifuged, then cleaned with solvent and be mixed in sediment（That is viscous brown thing）In foreign ion, or
Washed in centrifugal process.
Preferably, in the step S1012, the condition of centrifuge washing is：Rotating speed 9000r/min, centrifuge washing 6 times, often
Secondary 5min.
Centrifuge washing is to be separated solid phase and liquid phase substance, is carried out using centrifuge, and the rotating speed of centrifuge is set to
9000r/min, adds solidliquid mixture for the first time, opens centrifuge, and 5min is centrifuged, and centrifuge is precipitated thing after stopping
Matter, then to solvent is added in the deposit for obtaining, then opens centrifuge 5min second, after stopping centrifuge,
Only surplus sediment in centrifuge, then to adding solvent, then third time to open centrifuge in the sediment for obtaining, by that analogy,
For centrifuge washing six times, 5min is centrifuged every time.
Technical scheme provided in an embodiment of the present invention can include following beneficial effect：
The present invention provides a kind of fuel cell oxygen reduction catalyst and preparation method thereof, and methods described includes graphene oxide moisture
The preparation of dispersion liquid, the preparation of manganese basigamy compound and under gas with various atmosphere high-temperature roasting obtain different products, side of the invention
Method is raw materials used cheap and easy to get, simple and efficient to handle, and energy consumption is small, to equipment without particular/special requirement, adds low in the pollution of the environment, by control
Manganese base oxidation state species processed shows splendid hydrogen reduction catalytic performance, has good application prospect in fuel cell field.
Also, in product prepared by the present invention, MnO and Mn2O3Mixed state metal oxide and MnO, are club shaped structure, energy and stone
Black alkene is combined closely, and specific surface area is big, electro-catalysis efficiency high.
Brief description of the drawings
For clearer the explanation embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it is clear that, to those skilled in the art, not
On the premise of paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is that a kind of flow of the preparation method of fuel cell oxygen reduction catalyst provided in an embodiment of the present invention is illustrated
Figure.
Fig. 2 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 1
The X ray diffracting spectrum of agent.
Fig. 3 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 1
The scanning electron microscope (SEM) photograph of agent.
Fig. 4 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 1
Agent difference in 0.1MKOH solution sweeps speed（5、10、20、50、100mVs-1）Under cyclic voltammetry curve figure（CV curves）.
A kind of graphene-supported material modified fuel cell oxygen reduction catalyst of Mn bases prepared by Fig. 5 embodiment of the present invention 1
In the 0.1mol L of oxygen saturation-1Rotating circular disk curve map in KOH solution.
Fig. 6 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 2
The X ray diffracting spectrum of agent.
Fig. 7 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 2
The scanning electron microscope (SEM) photograph of agent.
Fig. 8 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 2
Agent difference in 0.1MKOH solution sweeps speed（5、10、20、50、100mVs-1）Under cyclic voltammetry curve figure（CV curves）.
Fig. 9 is the material modified fuel cell oxygen reduction catalysis of a kind of graphene-supported Mn bases prepared by the embodiment of the present invention 2
Agent is in the 0.1mol L in oxygen saturation-1Rotating circular disk curve in KOH solution.
Specific embodiment
In order that those skilled in the art more fully understand the technical scheme in the present invention, below in conjunction with of the invention real
The accompanying drawing in example is applied, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, art technology
The every other embodiment that personnel are obtained under the premise of creative work is not made, should all belong to protection model of the invention
Enclose.
Referring to Fig. 1, a kind of preparation method of fuel cell oxygen reduction catalyst provided in an embodiment of the present invention is shown
Schematic flow sheet.Following embodiments are based on the method flow shown in Fig. 1.
Graphene oxide aqueous dispersions being prepared first, graphite powder being prepared using improved Hummers methods, preparation process is as follows：
By 3g graphite powders（325 mesh）, 15g potassium permanganate and the concentrated sulfuric acid that 64ml concentration is 98% 12h is stirred in ice-water bath, obtain palm fibre
Color dope, this viscous brown thing is slowly added in 200mL ultra-pure waters, is then slowly added dropwise the dioxygen that 15mL concentration is 30%
Water, stirs 30min at 30 DEG C, and then by 9000r/min centrifuge washings 6 times, each 5min adds distillation after centrifuge washing
In water, the graphene oxide aqueous dispersions of 6g/L are finally made into.Following embodiments use the graphene oxide of above-mentioned preparation
Aqueous dispersions.
Embodiment 1
Take the MnSO of 0.2g4·H2The KMnO of O, 0.5g4With 30mL graphene oxides（6g/L）Aqueous dispersions add 15mL go from
Stirred in sub- water, mixed solution is placed in 50mL reactors, be put into baking oven, oven temperature is adjusted into 140 DEG C keeps 10
Hour, thing is precipitated, then sediment is washed with deionized, dried at 85 DEG C after washing, obtain manganese basigamy compound；
In being reduced under hydrogen atmosphere, 550 DEG C of roastings obtain one kind for 4 hours with MnO and Mn to the manganese basigamy compound that will be obtained again2O3It is activity
The graphene-supported material modified fuel cell oxygen reduction catalyst of Mn bases at center, is designated as MnxOy- RGO catalyst, wherein using RGO
Represent redox graphene.
Referring to Fig. 2, a kind of graphene-supported material modified fuel of Mn bases prepared by the method for the present embodiment offer is shown
The X ray diffracting spectrum of battery oxygen reduction catalyst, by Jade software analysis can obtain on Graphene load material be
MnO and Mn2O3, because Graphene is single layer structure, so the characteristic diffraction peak without Graphene in Fig. 2.
Referring to Fig. 3, a kind of graphene-supported material modified fuel of Mn bases prepared by the method for the present embodiment offer is shown
The scanning electron microscope (SEM) photograph of battery oxygen reduction catalyst, from the figure 3, it may be seen that obtained mixed valence oxide M nO and Mn2O3It is bar-shaped
Structure, average grain diameter is 4 μm, is conducive to the carrying out of oxygen reduction reaction.
Catalyst obtained in the present embodiment is carried out into performance test as follows, cyclic voltammetric as shown in Figure 4 is obtained
Rotating circular disk curve map shown in curve map and Fig. 5：
By in MnxOy-RGO catalyst modification to electrode.By glass-carbon electrode before test（Diameter 3mm）At following steps
Reason：First with the Al of 50nm2O3Powder film is polished, and is then cleaned with ethanol, ultra-pure water respectively（In ultrasonic instrument）, dry in the air in atmosphere
It is dry.
Preparing for working electrode is as follows：Take 5mg catalyst and add 450 μ L ultra-pure waters, it is 5% to add 50 μ L mass fractions
In Nafion solution, ultrasonic disperse 1 hour takes the μ L of above-mentioned catalyst solution 5 on glass-carbon electrode, in air with micropipette rifle
In dry.Rotating disk electrode (r.d.e)（Diameter 5mm）By same processing method, then take 10 μ L and drop in electrode surface, in air
In dry.
Referring to Fig. 4, a kind of graphene-supported material modified fuel of Mn bases prepared by the method for the present embodiment offer is shown
Battery oxygen reduction catalyst difference in the KOH solution of 0.1M sweeps speed（5、10、20、50、100mVs-1）Under cyclic voltammetry curve
Figure（CV curves）.As shown in Figure 4, during scanning, MnxOy- RGO starts appearance near -0.2V, and peak position is set to -0.2V to -0.4V,
Density peak value is -0.9mAcm-2。
Actual conditions is as follows：With CHI660d type electrochemical workstations（Shanghai Chen Hua Instrument Ltd.）Carry out electrochemistry
Property is tested, and prepared catalyst is coated on glass-carbon electrode as working electrode, and Hg/HgO electrodes and Pt electrodes are used as ginseng
Than electrode and auxiliary electrode, test obtains cyclic voltammogram in 0.1M potassium hydroxide solutions（CV schemes）.
Referring to Fig. 5, a kind of graphene-supported material modified fuel of Mn bases prepared by the method for the present embodiment offer is shown
0.1mol L of the battery oxygen reduction catalyst in oxygen saturation-1Rotating circular disk curve map in KOH solution, calculates for urging
Agent MnxOy- RGO shifts electron number n at -0.45, -0.47, -0.49, -0.5V and is respectively 3.22,3.39,3.43,3.45.
Embodiment 2
Take the MnSO of 0.2g4·H2The KMnO of O, 0.5g4With 50mL graphene oxide aqueous dispersions（6g/L）Add 15mL go from
Stirred in sub- water, mixed solution is placed in 50mL reactors, be put into baking oven, kept for 12 hours at 140 DEG C, sunk
Starch, then washs sediment, then is dried at 80 DEG C, obtains manganese basigamy compound；The manganese basigamy compound that will be obtained is in ammonia
Lower 600 DEG C of atmosphere is calcined 4 hours, obtains a kind of graphene-supported material modified fuel cell of Mn bases with MnO as activated centre
Oxygen reduction catalyst, is designated as MnO-RGO catalyst, wherein representing redox graphene with RGO.
Referring to Fig. 6, the material modified fuel electricity of graphene-supported Mn bases that the method for the present embodiment offer is prepared is shown
The X ray diffracting spectrum of pond oxygen reduction catalyst, by Jade software analysis can obtain on Graphene load material be
MnO, because Graphene is individual layer, so XRD cannot obtain diffraction maximum.
Referring to Fig. 7, the material modified fuel electricity of graphene-supported Mn bases that the method for the present embodiment offer is prepared is shown
The scanning electron microscope (SEM) photograph of pond oxygen reduction catalyst, observation Fig. 7 understands that MnO is club shaped structure for major part, and average grain diameter is 4 μm, from
It can be seen that Graphene is attached on MnO in individual layer shape in figure.
Catalyst obtained in the present embodiment is carried out into performance test as follows, cyclic voltammetric as shown in Figure 8 is obtained
Rotating circular disk curve map shown in curve map and Fig. 9：：
By in MnO-RGO catalyst modification to electrode.By glass-carbon electrode before test（Diameter 3mm）Processed by following steps：First
With the Al of 50nm2O3Powder film is polished, and is then cleaned with ethanol, ultra-pure water respectively（In ultrasonic instrument）, dry in atmosphere.
Preparing for working electrode is as follows：Take 5mg catalyst and add 450 μ L ultra-pure waters, it is 5% to add 50 μ L mass fractions
In Nafion solution, ultrasonic disperse 1 hour takes the μ L of above-mentioned catalyst solution 5 on glass-carbon electrode, in air with micropipette rifle
In dry.Rotating disk electrode (r.d.e)（Diameter 5mm）By same processing method, then take 10 μ L and drop in electrode surface, in air
In dry.
Referring to Fig. 8, the material modified fuel electricity of graphene-supported Mn bases that the method for the present embodiment offer is prepared is shown
Oxygen reduction catalyst difference in the KOH solution of 0.1M in pond sweeps speed（5、10、20、50、100mVs-1）Under cyclic voltammetry curve figure
（CV curves）.During scanning, MnO-RGO catalyst starts appearance near -0.3V, and peak position is set to -0.3V to -0.5V, and electric current is close
Degree peak value is -0.6mAcm-2。
Actual conditions is as follows：With CHI660d type electrochemical workstations（Shanghai Chen Hua Instrument Ltd.）Carry out electrochemistry
Property is tested, and prepared catalyst is coated on glass-carbon electrode as working electrode, and Hg/HgO electrodes and Pt electrodes are used as ginseng
Than electrode and auxiliary electrode, test obtains cyclic voltammogram in 0.1M potassium hydroxide solutions（CV schemes）.
Referring to Fig. 9, the material modified fuel cell oxygen of graphene-supported Mn bases that the method for the present embodiment is prepared is shown
0.1mol L of the reducing catalyst in oxygen saturation-1Rotating circular disk curve in KOH solution, calculates for catalyst MnO-
RGO shifts electron number n at -0.45, -0.47, -0.49, -0.5V and is respectively 2.00,2.09,2.18,2.19.
Certainly, described above is also not limited to the example above, technical characteristic of the present invention without description can by or
Realized using prior art, will not be repeated here；Above example and accompanying drawing are merely to illustrate technical scheme not
It is limitation of the present invention, reference has preferred embodiment been described in detail to the present invention, the ordinary skill people of this area
Member should be appreciated that change, remodeling, the addition that those skilled in the art are made in essential scope of the invention
Or replace without departure from spirit of the invention, should also belong to claims of the invention.
Claims (7)
1. a kind of fuel cell oxygen reduction catalyst, it is characterised in that with MnO as activated centre or with MnO and Mn2O3It is work
Property center.
2. a kind of preparation method of fuel cell oxygen reduction catalyst, comprises the following steps：
S101：Prepare graphene oxide aqueous dispersions；
Characterized in that, methods described also comprises the following steps：
S102：Prepare manganese basigamy compound：It is 1 according to mass ratio by manganese sulfate and potassium permanganate:2.5 ratio wiring solution-forming, and
Add 30-50ml graphene oxide aqueous dispersions to stir, 10-12h is reacted under the conditions of 140 DEG C and obtains sediment, then
By sediment washing, dry, obtain manganese basigamy compound；
S103：The manganese basigamy compound is reduced into 4h under 550-600 DEG C of hydrogen or ammonia atmosphere, fuel cell oxygen is obtained also
Raw catalyst product.
3. a kind of preparation method of fuel cell oxygen reduction catalyst according to claim 2, it is characterised in that the step
In rapid S102, the method for obtaining sediment is：Uniform mixture will be mixed, will be added in reactor, reactor will then be put into temperature
Degree is set as reacting 10-12h in 140 DEG C of baking oven.
4. a kind of preparation method of fuel cell oxygen reduction catalyst according to claim 3, it is characterised in that the step
In rapid S103, when reducing atmosphere is ammonia, the graphene-supported material modified fuel cell of Mn bases with MnO as activated centre is obtained
Oxygen reduction catalyst product.
5. a kind of preparation method of fuel cell oxygen reduction catalyst according to claim 3, it is characterised in that the step
In rapid S103, when reducing atmosphere is hydrogen, obtain with MnO and Mn2O3It is the graphene-supported material modified combustion of Mn bases in activated centre
Material battery oxygen reduction catalyst product.
6. a kind of preparation method of the fuel cell oxygen reduction catalyst according to claim any one of 2-5, its feature exists
In in the step S101, the method for preparing graphene oxide aqueous dispersions comprises the following steps：
S1011：3g graphite powders, 15g potassium permanganate and the 114g concentrated sulfuric acids are stirred into 12h in ice-water bath, viscous brown thing is obtained；
S1012：By in viscous brown thing addition 200mL ultra-pure waters, the hydrogen peroxide that 15mL concentration is 30% is then added dropwise,
Centrifuge washing is carried out after stirring 30min at 30 DEG C, graphene oxide aqueous dispersions are obtained.
7. a kind of preparation method of fuel cell oxygen reduction catalyst according to claim 6, it is characterised in that the step
In rapid S1012, the condition of centrifuge washing is：Rotating speed 9000r/min, centrifuge washing 6 times, each 5min.
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|---|---|---|---|---|
| CN108649241A (en) * | 2018-06-01 | 2018-10-12 | 济南大学 | The fuel cell oxygen reduction catalyst and preparation method thereof of nitrogen-doped graphene load C oCx/FeCo@C |
| CN108649241B (en) * | 2018-06-01 | 2021-03-09 | 济南大学 | Nitrogen-doped graphene-loaded CoCx/FeCo @ C fuel cell oxygen reduction catalyst and preparation method thereof |
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