CN105355936B - A kind of preparation method being catalyzed carbon paper - Google Patents
A kind of preparation method being catalyzed carbon paper Download PDFInfo
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- CN105355936B CN105355936B CN201510906490.6A CN201510906490A CN105355936B CN 105355936 B CN105355936 B CN 105355936B CN 201510906490 A CN201510906490 A CN 201510906490A CN 105355936 B CN105355936 B CN 105355936B
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- carbon paper
- graphene
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- source gas
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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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
Abstract
A kind of preparation method being catalyzed carbon paper, belongs to fuel cell catalyst material and diffusion layer field.Graphene oxide solution is placed in electrolytic cell by the present invention, using carbon paper as working electrode, after being passed through -2.0V~-1.7V DC voltage 0.5~8 hour, graphene oxide is reduced to graphene, graphene coated is prepared with vapor deposition technique after dry on carbon paper and is catalyzed carbon paper.Catalysis carbon paper prepared by the present invention not only possesses the performance of the original carbon paper of diffusion layer, and imparts carbon paper oxygen reduction catalytic activity and good wear-resisting anti-rotten characteristic.
Description
Technical field
The invention patent belongs to fuel cell carbon paper and catalysis material field.
Background technique
Fuel cell power generation is the 4th class generation technology after waterpower, firepower, nuclear energy power generation, it be it is a kind of without
Burning will be stored in the efficiently (50%- of the chemical energy in fuel and oxidant directly in a manner of electrochemical reaction under isothermal conditions
70%) and with the power generator that is environmentally friendly converted into electric energy.Various fuel electricity fuel cells (Fuel Cell) are as a kind of
High-energy density, high energy conversion rate, environment-friendly type power supply device and receive the whole world and widely pay close attention to.The expansion of fuel cell
Dissipating layer (main component is carbon paper) is the critical component in (PEMFC) Proton Exchange Membrane Fuel Cells, plays multi-functional, right
The structure and performance of fuel cell have important influence.The mechanical strength of diffusion layer (carbon paper) determines it in cell assembling processes
In deformation, influence the consistency of battery mass transfer, heat transfer, current density etc. in the process of running.Proton exchange membrane at present
Fuel cell mainly uses noble metal platinum to make catalyst, and high cost limits its industrial application, although fuel cell
Performance promoted and promoted with material property, but due to expensive structural material and high platinum black dosage, hinder PEMFC into one
Step development, manned space flight power supply hereafter have selected alkaline fuel cell, so that the development of 20 years subsequent PEMFC is in
Dead state.
With the progress of scientific research, the appearance of grapheme material, many problems have been instantly obtained very good solution.Graphite
It is also most hard nano material that alkene, which is most thin in the world,；Thermal coefficient is up to 5300W/ (mK), is higher than carbon nanotube and Buddha's warrior attendant
Stone, its electron mobility is more than 15000cm under room temperature2/ (Vs), but it is higher than carbon nanotubes or silicon crystal, and resistivity is about
10-6Ω cm, it is lower than copper or silver, it is the smallest material of world resistivity.However since graphene does not have band gap, so that its
Electrical conductance cannot be controlled completely as traditional semiconductor, and graphene surface is smooth and inert, be unfavorable for and its
His material it is compound, to hinder the application of graphene.In recent years, researcher makes great efforts to explore the side for improving graphene property
Method, wherein graphene nitrating, sulphur play key effect in terms of the application field for expanding graphene, and graphene doping can be beaten
It opens band gap and adjusts conduction type, change the electronic structure of graphene, the free carrier density of graphene is improved, to mention
The electric conductivity and stability of high graphene.In addition, introducing nitrogen atom structure in the carbon grid of graphene, stone can be increased
The active sites of black alkene adsorption metallic, to enhance the interaction of metallic and graphene as fuel cell oxygen
Reducing catalyst fuel battery negative pole is usually an ORR process.Nitrating and sulfur graphite alkene not only itself have catalytic oxidation-reduction
The ability of reaction is also used as carrier loaded base metal and participates in oxygen reduction reaction, can generate more better than nitrogen-doped graphene
The catalytic performance of oxygen reduction reaction.
But so far, lose the report for merging fuel cell catalyst layer and diffusion layer with doped forms.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods for being catalyzed carbon paper.With nitrating/sulfur graphite alkene, carbon paper, knot are coated
It closes the original Catalytic Layer of fuel cell to be integrated with diffusion layer, expands Catalytic Layer range.
Specific preparation process of the invention is as follows:
A, the preparation of graphene oxide: using natural scale graphite as raw material, using the concentrated sulfuric acid, sodium nitrate, potassium permanganate as oxygen
Agent prepares graphite oxide solution using Hummers method；
B, the cladding of carbon paper: the made graphene oxide solution of step A is placed in electrolytic cell, using carbon paper as working electrode,
After being passed through -2.0V~-1.7V DC voltage 0.5~8 hour, graphene oxide is reduced to graphene, and graphene coated is in charcoal
On paper；
C, it is dried: carbon paper made in step B being put and is dried in a vacuum drying oven；
D, it is catalyzed the preparation of carbon paper: right under vapor deposition technique with nitrogen source and sulphur source gas by carbon paper obtained by above-mentioned step C
Carbon paper carries out the doping of nitrogen and sulphur, obtains catalysis carbon paper, and wherein the volume ratio of nitrogen source gas and sulphur source gas is 1:1~3:1.
Carbon paper described in step B is fiber carbon paper, and carbon paper passes through 2000-3000 DEG C of high-temperature process before cladding, to mention
Its high degree of graphitization.
In step B, first graphene oxide is put into alcohol before cladding and is ultrasonically treated 2-3 hours.
In step C, the temperature of vacuum drying treatment is 40-80 DEG C, and drying time is 24-48 hours.
In step D, nitrogen source gas is ammonia, and sulphur source gas is hydrogen sulfide.Doping time is 2-12 hours, temperature 700-
1200℃。
The catalysis carbon paper prepared using the method for the present invention is beaten so that nitrogen-atoms and sulphur atom and carbon atom form covalent bond
It opens band gap and adjusts conduction type, change the electronic structure of graphene, the free carrier density of graphene is improved, to mention
The electric conductivity and stability of high graphene.
Catalysis carbon paper prepared by the present invention imparts the new function-catalysis of common carbon paper (diffusion layer), in conjunction with fuel
Battery diffusion layer and Catalytic Layer are in one, so that the expansion of Catalytic Layer range, effectively improves catalytic performance, while not influencing diffusion layer
Original performance.New catalytic carbon paper not only possesses the performance of the original carbon paper of diffusion layer, and imparts the new hydrogen reduction of carbon paper and urge
Change activity and good wear-resisting anti-rotten characteristic.
Detailed description of the invention
Fig. 1 is present invention catalysis carbon paper scanning figure；
Fig. 2 is the cyclic voltammetry curve figure for being catalyzed carbon paper.
Specific embodiment
Embodiment 1
Using natural scale graphite as raw material, using the concentrated sulfuric acid, sodium nitrate, potassium permanganate as oxidant, using Hummers legal system
Made graphene oxide solution is put into alcohol and is ultrasonically treated 2 hours, is then placed in electrolytic cell by standby graphite oxide solution,
Use the fiber carbon paper of 2800 DEG C of high-temperature process for working electrode, after being passed through DC voltage 2 hours of -1.8V, graphene oxide
It is reduced to graphene, graphene coated is on carbon paper；Made carbon paper is put in vacuum drying after 50 DEG C 24 hours dry；It will be upper
Gained carbon paper is stated, the doping of nitrogen and sulphur is carried out to carbon paper under vapor deposition technique with nitrogen source and sulphur source gas, at 800 DEG C, 2 hours
After obtain catalysis carbon paper, wherein the volume ratio of ammonia and hydrogen sulfide gas be 1:2.Gained, which is catalyzed carbon paper, has good hydrogen reduction
Catalytic activity, open circuit potential is 0.60V vs RHE, as shown in books 1 and Fig. 2.
Embodiment 2
Using natural scale graphite as raw material, using the concentrated sulfuric acid, sodium nitrate, potassium permanganate as oxidant, using Hummers legal system
Made graphene oxide solution is put into alcohol and is ultrasonically treated 2 hours, is then placed in electrolytic cell by standby graphite oxide solution,
Use the fiber carbon paper of 2500 DEG C of high-temperature process for working electrode, after being passed through DC voltage 3 hours of -1.75V, graphene oxide
It is reduced to graphene, graphene coated is on carbon paper；Made carbon paper is put in vacuum drying after 50 DEG C 24 hours dry；It will be upper
Gained carbon paper is stated, the doping of nitrogen and sulphur is carried out to carbon paper under vapor deposition technique with nitrogen source and sulphur source gas, at 700 DEG C, 2 hours
After obtain catalysis carbon paper, wherein the volume ratio of ammonia and hydrogen sulfide gas be 1:1.Gained, which is catalyzed carbon paper, has good hydrogen reduction
Catalytic activity, open circuit potential are 0.58V vs RHE.
Embodiment 3
Using natural scale graphite as raw material, using the concentrated sulfuric acid, sodium nitrate, potassium permanganate as oxidant, using Hummers legal system
Standby graphite oxide solution, made graphene oxide solution is put into alcohol and is ultrasonically treated 2.5 hours, electrolytic cell is then placed in
In, it uses the fiber carbon paper of 2480 DEG C of high-temperature process for working electrode, after being passed through DC voltage 2.5 hours of -1.7V, aoxidizes stone
Black alkene is reduced to graphene, and graphene coated is on carbon paper；Made carbon paper is put in vacuum drying after 60 DEG C 26 hours dry；
By above-mentioned gained carbon paper, the doping of nitrogen and sulphur is carried out to carbon paper under vapor deposition technique with nitrogen source and sulphur source gas, at 750 DEG C,
Catalysis carbon paper is obtained after 1.5 hours, wherein the volume ratio of ammonia and hydrogen sulfide gas is 1:1.Gained, which is catalyzed carbon paper, to be had well
Oxygen reduction catalytic activity, open circuit potential be 0.61V vs RHE.
Claims (4)
1. a kind of preparation method for being catalyzed carbon paper, it is characterised in that:
A, the preparation of graphene oxide: using natural scale graphite as raw material, using the concentrated sulfuric acid, sodium nitrate, potassium permanganate as oxidant,
Graphene oxide solution is prepared using Hummers method；
B, the cladding of carbon paper: the made graphene oxide solution of step A is placed in electrolytic cell, using carbon paper as working electrode, be passed through-
After 2.0V~-1.7V DC voltage 0.5~8 hour, graphene oxide is reduced to graphene, and graphene coated is on carbon paper；
The carbon paper is fiber carbon paper, and carbon paper passes through 2000-3000 DEG C of high-temperature process before cladding, improves carbon paper degree of graphitization；
C, it is dried: the carbon paper of graphene coated made in step B being put and is dried in a vacuum drying oven；
D, it is catalyzed the preparation of carbon paper: heavy with gas using nitrogen source gas and sulphur source gas as gas source by carbon paper obtained by above-mentioned step C
Area method carries out the doping of nitrogen and sulphur to carbon paper, and depositing temperature is 800~1000 DEG C, and sedimentation time is 1~12 hour, is catalyzed
Carbon paper, wherein the volume ratio of nitrogen source gas and sulphur source gas is 1:1~3:1.
2. being catalyzed the preparation method of carbon paper according to claim 1, it is characterised in that: in step B, will first aoxidize stone before cladding
Black alkene is put into alcohol and is ultrasonically treated 2-3 hours.
3. according to the method described in claim 1, the temperature of vacuum drying treatment is 40-80 DEG C it is characterized by: in step C,
Drying time is 24-48 hours.
4. being catalyzed the preparation method of carbon paper according to claim 1, it is characterised in that: in step D, nitrogen source gas is ammonia,
Sulphur source gas is hydrogen sulfide.
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| CN107342428B (en) * | 2017-06-08 | 2020-02-07 | 中国科学技术大学 | Method for enhancing microbial extracellular electron transfer in microbial electrochemical system |
| CN108110223A (en) * | 2017-12-18 | 2018-06-01 | 北京鼎能开源电池科技股份有限公司 | A kind of graphene cathode pole piece and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104192830A (en) * | 2014-05-20 | 2014-12-10 | 江苏欧力特能源科技有限公司 | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192830A (en) * | 2014-05-20 | 2014-12-10 | 江苏欧力特能源科技有限公司 | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method |
Non-Patent Citations (1)
| Title |
|---|
| Drew C. Higgins at al."Oxygen Reduction on Graphene−Carbon Nanotube Composites Doped Sequentially with Nitrogen and Sulfur".《ACS Catal.》.2014,第4卷第2734-2740页. |
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