CN104716345B - Preparation method for fuel cell cathode catalyst - Google Patents
Preparation method for fuel cell cathode catalyst Download PDFInfo
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- CN104716345B CN104716345B CN201310694663.3A CN201310694663A CN104716345B CN 104716345 B CN104716345 B CN 104716345B CN 201310694663 A CN201310694663 A CN 201310694663A CN 104716345 B CN104716345 B CN 104716345B
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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
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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
- H01M4/88—Processes of manufacture
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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 invention relates to a fuel cell cathode electrocatalyst and preparation and application thereof, the porous nano structure doped catalyst comprises the active components of Se doped nano carbon or Se and N codoped nano carbon; the total mass percent content of Se atoms doped in the catalyst is 0.1%-10%, the total mass percent content of N atoms doped in the catalyst is 0%-10%, the carbon material specific surface area is 50-3000 m＜2＞ / g, and the carbon material total pore volume is 0.5-5 cm＜3＞/ g. The advantage of the invention is to disclose a metal-free fuel cell Se doped nano carbon catalyst and a preparation method and application thereof, and the preparation method is simple and easy to control and easy in scale application. The catalyst has high redox catalytic activity, selectivity and poison resistance.
Description
Technical field
The present invention relates to fuel-cell catalyst, the preparation of specifically a kind of doped nano carbon elctro-catalyst and its
Using the catalyst can be used as Proton Exchange Membrane Fuel Cells (PEMFC) and DMFC (DMFC) negative electrode electricity is urged
Agent.
Background technology
The energy is the basis of the national economic development and progress of social civilization, formed in 20th century with oil, natural gas and coal
The fossil fuels such as charcoal are the energy resource system of main body, and future society cannot have been met to efficient, cleaning, economy, safety energy system
Requirement, energy development is faced with unprecedented challenge.In order to realize the sustainable development of human society, people one for many years
Directly striving to find high efficient and reliable and environment-friendly energy utilization patterns.
Polymer-membrane fuel battery (PEFCs) includes Proton Exchange Membrane Fuel Cells (Proton Exchange
Membrane Fuel Cell, PEMFC) it is and the DMFC (DMFC) with pure hydrogen or purification reformation gas as fuel
Deng being a kind of fuel cell with perfluoro sulfonic acid membrane as electrolyte.Due to they have can room temperature quickly start, specific power and
The features such as specific energy is high, so wide having in fields such as fixed power station, electric automobile, military special type power supply and portable power supplies
Wealthy application prospect.Since 21 century, PEMFC makes great progress at aspects such as critical material, battery pack and systems.For electricity
The PEMFC of electrical automobile dynamical system has succeeded demonstrating running, is just progressively strided forward to industrialization.DMFC is due to its small volume, portable
The features such as, succeed demonstrating running in portable electric source domain.At present, wide variety of catalyst is in PEMFC and DMFC
Pt/C catalyst.The Pt consumptions of PEMFC are generally 0.5gPt kW-1, and the consumption of catalyst is significantly larger than this numerical value in DMFC,
So as to the cost for causing elctro-catalyst remains high.Meanwhile, PEFCs uses surrounding air as oxidant, with Environment Day
Become to deteriorating, air quality degradation, the catalyst poisoning problem that impurity causes in air turns into influences the important of its durability
Factor it.Meanwhile, DMFC easily penetrates into negative electrode due to methyl alcohol from anode, causes cathod catalyst to be poisoned, under battery performance
Drop..Therefore, developing low-cost platinum alternative catalysts are one of the research emphasis in current PEMFC fields.
Porous carbon material is a kind of novel charcoal material with certain pore structure, because it has aboundresources, ratio high
Surface area, pore volume, high conductivity and programmable pore structure, thus it is widely used in dividing for electronics industry, gas and liquid
From fields such as, health cares.Research shows, carried out in the material such as semi-conducting material and carbon micro- (N, B etc.) doping or
Modification, thus it is possible to vary the physics of material, chemically and thermally mechanical property, so as to make it have excellent catalytic performance.Research shows,
Ru/C catalyst is easily oxidized to RuO under relatively low current potentialx, but after the modification of Se atoms is added, between Ru and Se
Chemical bonding effect prepare RuxSeyCatalyst can suppress the oxidation of Ru atoms, strengthen catalyst oxygen reduction activity and
Stability [V.Zaikovskii, K.Nagabhushana, V.Kriventsov, K.Loponov, S.Cherepanova,
R.Kvon,H.D.Kochubey,E.Savinova.Synthesis and Structural
Characterization of Se-Modified Carbon-Supported Ru Nanoparticles for the
Oxygen Reduction Reaction.The Journal of Physical Chemistry B,2006(110):6881-
6890.]。
The content of the invention
It is an object of the invention to provide a kind of fuel cell electro-catalyst and its preparation and application, to reach above-mentioned mesh
, the technical scheme of use is as follows,
One kind is used for fuel battery negative pole elctro-catalyst, and the catalyst activity component is mixing with porous nanometer structure
Miscellaneous type catalyst, comprising Se dopen Nanos carbon or Se and nitrogen co-doped nano-sized carbon；The gross mass hundred of doping Se atoms therein
Content is divided to be 0.1~10%；The gross mass percentage composition of nitrogen-atoms is 0~10%；The specific surface area of Carbon Materials is 50-
3000m2/g；Carbon Materials total pore volume is 0.5-5cm3/g。
The present invention so that carbon precursor and Se presomas are compounded to form into composite precursor under elevated pressure conditions, then by its
The Se dopen Nanos charcoal or Se and nitrogen that inert gas and/or the lower high temperature carbonization of ammonia atmosphere protection prepare loose structure are co-doped with
Miscellaneous nanocarbon catalyst.Modification by Se to Nano carbon, forms more defect active sites, to improve nano-sized carbon in Nano carbon
The catalysis activity of catalyst.
Comprise the following steps：
(1) the amount ratio that carbon precursor and solvent press material is 1 by:1~1:100 ratio mixing, heats (room temperature~95
DEG C) stirring, it is fully dissolved, form clear solution A；
(2) by the presoma containing Se containing 0.5mg/L-20mg/L Se and solvent with the amount ratio of material be 1:1~1:100
Mixture obtains B；
(3) be added to B in A by, continues to stir, and is allowed to form dispersed, obtains C；Wherein Se presomas and charcoal forerunner
The amount ratio of the material of body is 1:10~1:1000；It is preferably in a proportion of 1:5~1:100；
(4) pours into high-pressure hydrothermal reaction kettle C, and reaction 1-10h is sealed under uniform temperature and pressure, obtains D；
Wherein reaction temperature is 40-200 DEG C, and preferable temperature is 60 DEG C -160 DEG C；Reaction pressure is 0.1-3MPa, and preferred pressure range is
0.1-1.5MPa；
(5) persistently stirs D in the environment of room temperature~95 DEG C, after after moisture or organic solvent evaporating completely 60~80
DEG C drying, obtains compound E；
(6) compound E is dried burin-in process 1~7 day by, is crushed after taking-up, obtains solid powder F；
(7) charingization treatment under the conditions of 500~1200 DEG C of inert gas shieldings or under nitriding atmosphere by solid powder F
0.5~8 hour, obtain solid powder G；Preferable temperature is 700-1000 DEG C；
(8) washs mixture G, and the ball milling 1-8h under 100-1000rpm, obtains what the present invention was protected after drying
Catalyst.
Described doping type catalyst, the charcoal predecessor include it is following in one or two or more kinds：
(1) low molecular carbohydrate, including sucrose, starch, glucose, maltose, xylose, furfuryl alcohol etc. in one kind or several
Kind；
(2) organic matter of small molecule, including formaldehyde, ethylenediamine, trimethylamine, melamine, phenol, ethene, acetylene, third
One or more in alkene, benzene；
(3) high molecular polymer, including mesophase pitch, polyurethane, polypyridine, polyethylene glycol, polypyrrole, polypropylene
Nitrile, polyaniline, phenol formaldehyde resin, resorcinol formaldehyde resin, two/melamine resin, Lauxite, gelatin and life
One or more in thing albumen etc.；
Described doping type catalyst, its solvent is water, ethanol, isopropanol, acetone, N-N dimethylformamides, N-N bis-
One or two or more kinds in methylacetamide or 1-METHYLPYRROLIDONE；
Described preparation method, it is described using in inert gas or reducing atmosphere, inert gas be nitrogen, argon gas,
One kind in helium；The nitriding atmosphere is NH3/N2、NH3、CH3One kind in CN or HCN atmosphere；
Described preparation method, described Se presomas are sodium selenate, selenourea, selenic acid, potassium selenate, simple substance Se, titanium dioxide
Any one in selenium etc. or more than one mixtures；
Described fuel cell, including Proton Exchange Membrane Fuel Cells and DMFC, its negative electrode is to include
One or more of doping type catalyst in claim 1.
When catalyst as described above is used for into assembling fuel cell, shows good catalysis activity, stability and resist
Toxicity energy, thus be hopeful to substitute the elctro-catalyst during platinum turns into Proton Exchange Membrane Fuel Cells and DMFC.
The present invention is using such non-metallic catalyst as fuel-cell catalyst, and cost is very low, with good catalytic performance, and increases
Add the variation of catalyst, accelerate the process of fuel cell industrialization.With all kinds of catalyst of document report and its preparation
Method is compared, the invention has the advantages that：
1. the present invention proposes a kind of catalyst of new fuel cell and its preparation method and application.With receiving for only undoped p
Rice C catalyst is compared, and such catalyst has hydrogen reduction higher in Proton Exchange Membrane Fuel Cells and methanol fuel cell
Catalysis activity, selective and anti-NOx、SOxAnd the toxicant such as methyl alcohol poisons ability.
2. catalyst proposed by the present invention has antitoxinization performance very high.Such catalyst has excellent anti-impurity gas
Body NOx、SOxAnd the ability that methyl alcohol etc. poisons.
3. with traditional RuxSeyThe catalyst such as/C are compared, and the cost of such catalyst is very low, but its performance and its property
Can be suitable, or better than the Ru with identical Se contentsxSeyThe catalyst such as/C.
4. a kind of preparation method of new dopen Nano C catalyst is provided, i.e., Se elements is mixed in carbonization process,
Se can not only be made to be uniformly dispersed in charcoal nanostructured, the valence link formed between Se and charcoal can improve the work between Se and charcoal
Firmly, the activity and stability of catalyst are further improved.
5. catalyst low cost proposed by the present invention.With traditional Pt/C catalytic phases ratio, Main Components of the invention are Se
Or Se and nitrogen co-doped nano-sized carbon, and without any metal, these components are cheap, aboundresources, preparation process is simple,
Thus make the totle drilling cost of catalyst very low.
6. catalyst preparation process proposed by the present invention is simple, flow is few, easy to operate, environment-friendly, preparation cost is low and
It is easily formed mass production scale.
Brief description of the drawings
Fig. 1 is the polarization curves of oxygen reduction of the nanocarbon catalyst prepared according to embodiment 1 and embodiment 2.Electrolyte is molten
Liquid：0.5M H2SO4；Reference electrode：Saturated calomel electrode, to electrode：Platinum filament；Sweep speed:5mV/s, electrode rotation rate：
1600rpm；Electric potential scanning：0-1.04V vs.SHE.
Specific embodiment
Loaded catalyst as described above is used in negative electrode.The fuel cell can be polymer dielectric film fuel
Battery (PEMFC) or DMFC (DMFC).
The preparation of working electrode
By 5mg catalyst, 1ml absolute ethyl alcohols, 50 μ l 5%Nafion solution, after mixing, sonic oscillation is uniform, takes 10 μ
L mixed solutions are distributed to area for 0.1256cm2Glass carbon (GC) disk electrode surface, obtain membrane electrode after drying.
Hydrogen reduction polarization performance method of testing in Proton Exchange Membrane Fuel Cells
Oxygen is dissolved in 0.5M H2SO4Until electrolyte saturation in electrolyte, then from open-circuit voltage (OCV) with negative
The method scanned to (negative direction) measures electric current (sweep speed:5mV/s, electrode rotation rate：
1600rpm).Under the potential of the 0.6~0.8V reduced in the electrodes less than wherein most oxygen, electric current reaches material limits
Electric current.Material limits electric current is the maximum of electric current caused by being lacked by reactant.In RDE experiments, with electrode rotary speed
Rate is improved, and dissolving oxygen in the electrolyte is more provided to electrode surface, so that material limits electric current and whole potential area
Electric current in domain is improved.
Hereinafter, one or more implementation method of the invention will be described in detail with reference to following examples.So
And, these embodiments not only limit the purpose and scope of one or more implementation method of the invention.
According to the embodiment of the present invention, the catalyst activity component is the doping type catalysis with porous nanometer structure
Agent, comprising Se dopen Nanos carbon or Se and nitrogen co-doped nano-sized carbon；The gross mass percentage composition of doping Se atoms therein is
0.1~10%；The gross mass percentage composition of nitrogen-atoms is 0~10%；The specific surface area of Carbon Materials is 50-3000m2/g；Raw material of wood-charcoal
Material total pore volume is 0.5-5cm3/g.Hereinafter, the catalyst according to embodiment of the present invention will be described in detail.
Embodiment 1
It is 1 by the amount ratio that phenolic resin and ethanol press material:2 ratio mixing, heats 40 DEG C of stirrings, makes it fully molten
Solution, forms clear solution A；By containing 10mg/L Se containing selenourea and water with the amount ratio of material be 1:2 mixtures obtain B；By B
It is added in A, continues to stir, be allowed to form dispersed, obtains C；Wherein carbon precursor with containing Se presomas material amount
Than being 10：1；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；It is wherein anti-
It is 140 DEG C to answer temperature；Reaction pressure is 0.2MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in 60 DEG C of environment of room temperature, are treated
In 80 DEG C of dryings after moisture or organic solvent evaporating completely, compound E is obtained；Compound E is dried into burin-in process 7 days, is taken out
After crush, obtain solid powder F；The charingization place under the conditions of 800 DEG C of inert gas shieldings or under nitriding atmosphere by solid powder F
Reason 2 hours, obtains solid powder G；By mixture G washings, and the ball milling 4h under 400rpm, the present invention is obtained after drying and is protected
Catalyst.
Embodiment 2
It is 1 by the amount ratio that phenolic resin and ethanol press material:2 ratio mixing, heats 40 DEG C of stirrings, makes it fully molten
Solution, forms clear solution A；By containing 10mg/L Se containing selenourea and water with the amount ratio of material be 1:2 mixtures obtain B；By B
It is added in A, continues to stir, be allowed to form dispersed, obtains C；Wherein carbon precursor with containing Se presomas material amount
Than being 10：2；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；It is wherein anti-
It is 140 DEG C to answer temperature；Reaction pressure is 0.2MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in the environment of room temperature~95 DEG C,
After, in 80 DEG C of dryings, obtaining compound E after moisture or organic solvent evaporating completely；Compound E is dried into burin-in process 7 days, is taken
Crushed after going out, obtain solid powder F；The charingization under the conditions of 800 DEG C of inert gas shieldings or under nitriding atmosphere by solid powder F
Treatment 2 hours, obtains solid powder G；By mixture G washings, and the ball milling 4h under 400rpm, the present invention is obtained after drying and is protected
The catalyst of shield.
Embodiment 3
It is 1 by the amount ratio that melamine resin and water press material:2 ratio mixing, heats 95 DEG C of stirrings, it is fully dissolved,
Form clear solution A；By containing 10mg/L Se containing selenourea and water with the amount ratio of material be 1:3 mixtures obtain B；B is added
To in A, continue to stir, be allowed to form dispersed, obtain C；Wherein carbon precursor is with the amount ratio of the material containing Se presomas
10：2；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；Wherein react temperature
Spend is 140 DEG C；Reaction pressure is 0.2MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in the environment of room temperature~95 DEG C, water is treated
Point or organic solvent evaporating completely after in 80 DEG C of dryings, obtain compound E；Compound E is dried into burin-in process 7 days, after taking-up
Crush, obtain solid powder F；The charingization treatment under the conditions of 900 DEG C of inert gas shieldings or under nitriding atmosphere by solid powder F
2 hours, obtain solid powder G；By mixture G washings, and ball milling 2h at 600 rpm, obtain what the present invention was protected after drying
Catalyst.
Embodiment 4
It is 1 by the amount ratio that sucrose and water press material:3 ratio mixing, heats 40 DEG C of stirrings, it is fully dissolved, and is formed
Clear solution A；By containing 5mg/L Se containing selenourea and water with the amount ratio of material be 1:1 mixture obtains B；B is added to A
In, continue to stir, it is allowed to form dispersed, obtain C；Wherein carbon precursor and the amount ratio of the material of sodium selenate is 10：1；By C
Pour into high-pressure hydrothermal reaction kettle, reaction 2h is sealed under uniform temperature and pressure, obtain D；Wherein reaction temperature is 160
℃；Reaction pressure is 0.3MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in 60 DEG C of environment, moisture or organic solvent is treated
After evaporating completely, in 80 DEG C of dryings, compound E is obtained；Compound E is dried into burin-in process 7 days, is crushed after taking-up, consolidate
Body powder F；Solid powder F is processed 2 hours in 800 DEG C of charingizations under the conditions of N2 gas shields or under nitriding atmosphere, is obtained
Solid powder G；By mixture G washings, and the ball milling 4h under 400rpm, the catalyst that the present invention is protected is obtained after drying.
Embodiment 5
It is 1 by the amount ratio that polyurethane and ethanol press material:4 ratio mixing, heats 70 DEG C of stirrings, it is fully dissolved,
Form clear solution A；By the selenic acid containing 10mg/L Se and water with the amount ratio of material be 1:2 mixtures obtain B；B is added to
In A, continue to stir, be allowed to form dispersed, obtain C；Wherein carbon precursor and the amount ratio of the material containing Se presomas is 10：
3；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；Wherein reaction temperature is
140℃；Reaction pressure is 0.2MPa；D is taken out and is put into five mouthfuls of flasks and is persistently stirred in the environment of room temperature~95 DEG C, treat moisture or
In 80 DEG C of dryings after organic solvent evaporating completely, compound E is obtained；Compound E is dried into burin-in process 7 days, is crushed after taking-up,
Obtain solid powder F；By solid powder F, charingization treatment 2 is small under the conditions of 800 DEG C of inert gas shieldings or under nitriding atmosphere
When, obtain solid powder G；By mixture G washings, and ball milling 5h at 300 rpm, obtain that the present invention protected after drying urges
Agent.
Embodiment 6
It is 1 by the amount ratio that ethylenediamine and ethanol press material:2 ratio mixing, heats 50 DEG C of stirrings, it is fully dissolved,
Form clear solution A；By containing 10mg/L Se containing selenourea and water with the amount ratio of material be 1:2 mixtures obtain B；B is added
To in A, continue to stir, be allowed to form dispersed, obtain C；Wherein carbon precursor is with the amount ratio of the material containing Se presomas
10：2；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；Wherein react temperature
Spend is 140 DEG C；Reaction pressure is 0.2MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in the environment of room temperature~95 DEG C, water is treated
Point or organic solvent evaporating completely after in 80 DEG C of dryings, obtain compound E；Compound E is dried into burin-in process 7 days, after taking-up
Crush, obtain solid powder F；The charingization treatment under the conditions of 800 DEG C of inert gas shieldings or under nitriding atmosphere by solid powder F
2 hours, obtain solid powder G；By mixture G washings, and the ball milling 4h under 400rpm, obtain what the present invention was protected after drying
Catalyst.
Embodiment 7
It is 1 by the amount ratio that polyaniline and ethanol press material:2 ratio mixing, heating stirring makes it fully dissolve, is formed
Clear solution A；By containing 20mg/L Se containing selenourea and water with the amount ratio of material be 1:4 mixtures obtain B；B is added to A
In, continue to stir, it is allowed to form dispersed, obtain C；Wherein carbon precursor and the amount ratio of the material containing Se presomas is 10：
1；C is poured into high-pressure hydrothermal reaction kettle, reaction 4h is sealed under uniform temperature and pressure, obtain D；Wherein reaction temperature is
80℃；Reaction pressure is 0.6MPa；D taking-ups are put into five mouthfuls of flasks persistently to be stirred in 65 DEG C of environment, moisture or organic molten is treated
In 80 DEG C of dryings after agent evaporating completely, compound E is obtained；Compound E is dried into burin-in process 7 days, is crushed after taking-up, consolidate
Body powder F；By solid powder F, charingization is processed 2 hours under the conditions of 800 DEG C of inert gas shieldings or under nitriding atmosphere, is obtained
Solid powder G；By mixture G washings, and the ball milling 4h under 400rpm, the catalyst that the present invention is protected is obtained after drying.
Claims (7)
1. a kind of preparation method of fuel battery negative pole elctro-catalyst, it is characterised in that：The catalyst activity component be with
The doping type catalyst of porous nanometer structure, comprising Se dopen Nanos carbon or Se and nitrogen co-doped nano-sized carbon；In catalyst
The gross mass percentage composition of doping Se atoms is 0.1~10%；The gross mass percentage composition of nitrogen-atoms is 0~10%；Carbon Materials
Specific surface area be 50-3000m2/g；Carbon Materials total pore volume is 0.5-5cm3/g；Electrocatalyst for cathode is comprised the following steps：
(1) the amount ratio that carbon precursor and solvent press material is 1 by:1~1:100 ratio mixing, heating is stirred at room temperature~95 DEG C
Mix, it is fully dissolved, form clear solution A；
(2) by the presoma containing Se containing 0.5mg/L-20mg/L Se and solvent with the amount ratio of material be 1:1~1:100 mixing
Thing obtains B；
(3) B is added in A, continues to stir, be allowed to form dispersed, obtain C；Wherein Se and the material containing carbon precursor
Amount ratio be 1:10~1:1000；
(4) pours into high-pressure hydrothermal reaction kettle C, and reaction 1-10h is sealed under uniform temperature and pressure, obtains D；It is wherein anti-
It is 40-200 DEG C to answer temperature；Reaction pressure is 0.1-3MPa；
(5) persistently stirs D in the environment of room temperature~95 DEG C, after dry at 60~80 DEG C after moisture or organic solvent evaporating completely
It is dry, obtain compound E；
(6) compound E is dried burin-in process 1~7 day by, is crushed after taking-up, obtains solid powder F；
(7) by solid powder F under the conditions of 500~1200 DEG C of inert gas shieldings or under nitriding atmosphere charingization treatment 0.5~
8 hours, obtain solid powder G；
(8) washs mixture G, and the ball milling 1-8h under 100-1000rpm, and catalyst is obtained after drying.
2. the preparation method of electrocatalyst for cathode according to claim 1, it is characterised in that：The charcoal predecessor include with
One or two or more kinds in lower：
(1) one or more in low molecular carbohydrate, including sucrose, starch, glucose, maltose, xylose, furfuryl alcohol；
(2) organic matter of small molecule, including formaldehyde, ethylenediamine, trimethylamine, melamine, phenol, ethene, acetylene, propylene, benzene
In one or more；
(3) high molecular polymer, including it is mesophase pitch, polyurethane, polypyridine, polyethylene glycol, polypyrrole, polyacrylonitrile, poly-
Aniline, phenol formaldehyde resin, resorcinol formaldehyde resin, two/melamine resin, Lauxite, gelatin and biological egg
One or more in white.
3. the preparation method of electrocatalyst for cathode according to claim 1, it is characterised in that solvent is water, ethanol, isopropyl
One or two or more kinds in alcohol, acetone, N-N dimethylformamides, N-N dimethylacetylamides or 1-METHYLPYRROLIDONE.
4. the preparation method of electrocatalyst for cathode according to claim 1, it is characterised in that：Using in inert gas or nitrogen
When changing atmosphere, inert gas is the one kind in nitrogen, argon gas, helium；The nitriding atmosphere is NH3/N2、NH3、CH3CN or HCN
One kind in atmosphere.
5. the preparation method of electrocatalyst for cathode according to claim 1, it is characterised in that：Described Se presomas are selenium
One or two or more kinds mixture in sour sodium, selenourea, selenic acid, potassium selenate, simple substance Se, selenium dioxide.
6. electrocatalyst for cathode preparation method according to claim 1, it is characterised in that：The catalyst is urged as negative electrode
Agent is applied in Proton Exchange Membrane Fuel Cells or DMFC.
7. according to the preparation method of the cathod catalyst described in claim 1, it is characterised in that：
Se and the amount ratio of the material containing carbon precursor are 1 in step (3):10~1:100；
Step (4) reaction temperature is 60 DEG C -160 DEG C；Reaction pressure is 0.1-1.5MPa；
Solid powder F charing process temperature is 700-1000 DEG C in step (7).
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| CN109888211B (en) * | 2019-01-30 | 2021-01-15 | 厦门大学 | Protein-based nitrogen-doped carbon/metal nanoparticle composite material and preparation method thereof |
| CN111063868B (en) * | 2019-07-30 | 2021-07-13 | 厦门理工学院 | Self-supporting carbon-selenium material and preparation method and application thereof |
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| CN102078816A (en) * | 2010-12-23 | 2011-06-01 | 西北师范大学 | Selenium/carbon compound material, preparation of selenium/carbon compound material and application of selenium/carbon compound material in fuel-cell catalyst preparation |
| CN103143391A (en) * | 2013-03-12 | 2013-06-12 | 西南大学 | Preparation method of three-dimensional graphene/porphyrin compounded oxygen reduction electrocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102078816A (en) * | 2010-12-23 | 2011-06-01 | 西北师范大学 | Selenium/carbon compound material, preparation of selenium/carbon compound material and application of selenium/carbon compound material in fuel-cell catalyst preparation |
| CN103143391A (en) * | 2013-03-12 | 2013-06-12 | 西南大学 | Preparation method of three-dimensional graphene/porphyrin compounded oxygen reduction electrocatalyst |
Non-Patent Citations (1)
| Title |
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| "Sulfur-Doped graphene as an efficient metal-free cathode catalyst for oxygen reduction";Zhi Yang等;《Acs nano.》;20111227;第6卷(第1期);第205-211页 * |
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