CN105355936A - Preparation method of catalytic carbon paper - Google Patents

Preparation method of catalytic carbon paper Download PDF

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Publication number
CN105355936A
CN105355936A CN201510906490.6A CN201510906490A CN105355936A CN 105355936 A CN105355936 A CN 105355936A CN 201510906490 A CN201510906490 A CN 201510906490A CN 105355936 A CN105355936 A CN 105355936A
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Prior art keywords
carbon paper
preparation
graphene
graphene oxide
source gas
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CN201510906490.6A
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CN105355936B (en
Inventor
粱伊丽
伍小波
谢志勇
黄启忠
李宏斌
杨飘飘
孙敏
刘艳
李向辉
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Central South University
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Central South University
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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

The invention provides a preparation method of catalytic carbon paper and belongs to the field of fuel cell catalytic materials and diffusion layers. According to the preparation method, a graphene oxide solution is placed into an electrolytic bath, the carbon paper serves as a work electrode, a direction current voltage ranging from -2.0V to -1.7 V is introduced, after 0.5-8 hours pass, graphene oxide is reduced into grapheme, the carbon paper is wrapped with the grapheme, and after drying is conducted, the catalytic carbon paper is prepared through a gas deposition method. The catalytic carbon paper prepared from the method has performance of original carbon paper of a diffusion layer, and oxygen reduction catalytic activity and good wear resistance and corrosion properties are given to the carbon paper.

Description

A kind of preparation method of catalysis carbon paper
Technical field
Patent of the present invention belongs to fuel cell carbon paper and catalysis material field.
Background technology
Fuel cell power generation is the 4th class generation technology after waterpower, firepower, nuclear energy power generation, it is a kind of without burning, under isothermal conditions direct with electrochemical reaction mode by the chemical energy be stored in fuel and oxidant efficient (50%-70%) and with the Blast Furnace Top Gas Recovery Turbine Unit (TRT) being environmentally friendly converted into electric energy.Various fuel electricity fuel cell (FuelCell) as a kind of high-energy-density, high energy conversion rate, environment-friendly type supply unit and receive the whole world and pay close attention to widely.The diffusion layer (main component is carbon paper) of fuel cell is the critical component in (PEMFC) Proton Exchange Membrane Fuel Cells, plays multi-functional, has important impact to the stuctures and properties of fuel cell.The mechanical strength of diffusion layer (carbon paper) determines its deformation in cell assembling processes, affects the consistency of battery in running in mass transfer, heat transfer, current density etc.Current Proton Exchange Membrane Fuel Cells mainly adopts noble metal platinum to make catalyst, high cost limits its commercial application, although the performance of fuel cell promotes with material property and promotes, but due to structural material and the high platinum black consumption of costliness, hinder further developing of PEMFC, after this manned space flight power supply have selected alkaline fuel cell, so that the development of 20 years PEMFC subsequently stays cool.
Along with the progress of scientific research, the appearance of grapheme material, many problems obtain good solution at once.Graphene is the thinnest in the world is also the hardest nano material; Conductive coefficient is up to 5300W/ (mK), and higher than carbon nano-tube and diamond, under normal temperature, its electron mobility is more than 15000cm 2/ (Vs), again than CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10 -6Ω cm, than copper or silver lower, be the material that world resistivity is minimum.But there is no band gap due to Graphene, its electrical conductance can not be controlled completely as traditional semiconductor, and graphenic surface is smooth and in inertia, be unfavorable for the compound with other materials, thus hinder the application of Graphene.In recent years, researcher makes great efforts to explore the method improving Graphene character, wherein Graphene nitrating, sulphur play key effect in the application expanding Graphene, Graphene adulterates, can band gap be opened and adjust conduction type, change the electronic structure of Graphene, improve the free carrier density of Graphene, thus improve electric conductivity and the stability of Graphene.In addition, nitrogen atom structure is introduced in the carbon grid of Graphene, can increase the active sites of graphenic surface adsorbing metal particles, thus the interaction of enhancing metallic and Graphene is as a fuel cell oxygen reduction catalyst fuel battery negative pole normally ORR process.Nitrating and sulfur graphite alkene not only itself have the ability that catalytic oxidation-reduction reacts, and can also participate in oxygen reduction reaction, can produce the catalytic performance of oxygen reduction reaction more better than nitrating Graphene as carrier loaded base metal.
But so far, lose the report merging fuel cell catalyst layer and diffusion layer with doped forms.
Summary of the invention
The object of this invention is to provide a kind of preparation method of catalysis carbon paper.With nitrating/sulfur graphite alkene, coated carbon paper, is integrated in conjunction with the original Catalytic Layer of fuel cell and diffusion layer, expands Catalytic Layer scope.
Concrete preparation process of the present invention is as follows:
The preparation of A, graphene oxide: with natural scale graphite for raw material, with the concentrated sulfuric acid, sodium nitrate, potassium permanganate for oxidant, adopts Hummers legal system for graphite oxide solution;
B, carbon paper coated: inserting in electrolysis tank by made for steps A graphene oxide solution, take carbon paper as work electrode, and pass into the direct voltage of-2.0V ~-1.7V after 0.5 ~ 8 hour, graphene oxide is reduced to Graphene, and graphene coated is on carbon paper;
C, dry process: carbon paper made in step B is put in vacuum drying chamber dry;
The preparation of D, catalysis carbon paper: by above-mentioned step C gained carbon paper, carbon paper is carried out to the doping of nitrogen and sulphur with nitrogenous source and sulphur source gas under vapor deposition technique, obtain catalysis carbon paper, 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, carbon paper before coated through 2000-3000 DEG C of high-temperature process, to improve its degree of graphitization.
In step B, before coated, first graphene oxide is put into alcohol ultrasonic process 2-3 hour.
In step C, the temperature of vacuum drying treatment is 40-80 DEG C, and drying time is 24-48 hour.
In step D, nitrogen source gas is ammonia, and sulphur source gas is hydrogen sulfide.Doping time is 2-12 hour, and temperature is 700-1200 DEG C.
Adopt catalysis carbon paper prepared by the inventive method, make nitrogen-atoms and sulphur atom and carbon atom form covalent bond, open band gap and adjust conduction type, change the electronic structure of Graphene, improve the free carrier density of Graphene, thus improve electric conductivity and the stability of 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 in one, make Catalytic Layer expanded range, effectively improve catalytic performance, do not affect the original performance of diffusion layer simultaneously.New catalytic carbon paper not only has the performance of the original carbon paper of diffusion layer, and imparts the new oxygen reduction catalytic activity of carbon paper and good wear-resisting anti-rotten characteristic.
Accompanying drawing explanation
Fig. 1 is catalysis carbon paper scintigram of the present invention;
Fig. 2 is the cyclic voltammetry curve figure of catalysis carbon paper.
Embodiment
Embodiment 1
With natural scale graphite for raw material, with the concentrated sulfuric acid, sodium nitrate, potassium permanganate for oxidant, adopt Hummers legal system for graphite oxide solution, made graphene oxide solution is put into the ultrasonic process of alcohol 2 hours, then insert in electrolysis tank, the fiber carbon paper adopting 2800 DEG C of high-temperature process is work electrode, passes into the direct voltage of-1.8V after 2 hours, graphene oxide is reduced to Graphene, and graphene coated is on carbon paper; Made carbon paper is put in vacuumize 50 DEG C of dryings after 24 hours; By above-mentioned gained carbon paper, carbon paper is carried out to the doping of nitrogen and sulphur with nitrogenous source and sulphur source gas under vapor deposition technique, at 800 DEG C, obtain catalysis carbon paper after 2 hours, wherein the volume ratio of ammonia and hydrogen sulfide gas is 1:2.Gained catalysis carbon paper has good oxygen reduction catalytic activity, and Open Circuit Potential is 0.60VvsRHE, as shown in books 1 and Fig. 2.
Embodiment 2
With natural scale graphite for raw material, with the concentrated sulfuric acid, sodium nitrate, potassium permanganate for oxidant, adopt Hummers legal system for graphite oxide solution, made graphene oxide solution is put into the ultrasonic process of alcohol 2 hours, then insert in electrolysis tank, the fiber carbon paper adopting 2500 DEG C of high-temperature process is work electrode, passes into the direct voltage of-1.75V after 3 hours, graphene oxide is reduced to Graphene, and graphene coated is on carbon paper; Made carbon paper is put in vacuumize 50 DEG C of dryings after 24 hours; By above-mentioned gained carbon paper, carbon paper is carried out to the doping of nitrogen and sulphur with nitrogenous source and sulphur source gas under vapor deposition technique, at 700 DEG C, obtain catalysis carbon paper after 2 hours, wherein the volume ratio of ammonia and hydrogen sulfide gas is 1:1.Gained catalysis carbon paper has good oxygen reduction catalytic activity, and Open Circuit Potential is 0.58VvsRHE.
Embodiment 3
With natural scale graphite for raw material, with the concentrated sulfuric acid, sodium nitrate, potassium permanganate for oxidant, adopt Hummers legal system for graphite oxide solution, made graphene oxide solution is put into the ultrasonic process of alcohol 2.5 hours, then insert in electrolysis tank, the fiber carbon paper adopting 2480 DEG C of high-temperature process is work electrode, passes into the direct voltage of-1.7V after 2.5 hours, graphene oxide is reduced to Graphene, and graphene coated is on carbon paper; Made carbon paper is put in vacuumize 60 DEG C of dryings after 26 hours; By above-mentioned gained carbon paper, carbon paper is carried out to the doping of nitrogen and sulphur with nitrogenous source and sulphur source gas under vapor deposition technique, at 750 DEG C, obtain catalysis carbon paper after 1.5 hours, wherein the volume ratio of ammonia and hydrogen sulfide gas is 1:1.Gained catalysis carbon paper has good oxygen reduction catalytic activity, and Open Circuit Potential is 0.61VvsRHE.

Claims (5)

1. a preparation method for catalysis carbon paper, is characterized in that:
The preparation of A, graphene oxide: with natural scale graphite for raw material, with the concentrated sulfuric acid, sodium nitrate, potassium permanganate for oxidant, adopts Hummers legal system for graphene oxide solution;
B, carbon paper coated: inserting in electrolysis tank by made for steps A graphene oxide solution, take carbon paper as work electrode, and pass into the direct voltage of-2.0V ~-1.7V after 0.5 ~ 8 hour, graphene oxide is reduced to Graphene, and graphene coated is on carbon paper;
C, dry process: the carbon paper of graphene coated made in step B is put in vacuum drying chamber dry;
The preparation of D, catalysis carbon paper: by above-mentioned step C gained carbon paper, with nitrogen source gas and sulphur source gas for source of the gas, with vapor deposition technique, carbon paper is carried out to the doping of nitrogen and sulphur, depositing temperature is 800 ~ 1000 DEG C, sedimentation time is 1 ~ 12 hour, obtain catalysis carbon paper, wherein the volume ratio of nitrogen source gas and sulphur source gas is 1:1 ~ 3:1.
2. the preparation method of catalysis carbon paper according to claim 1, is characterized in that: the carbon paper described in step B is fiber carbon paper, and carbon paper through 2000-3000 DEG C of high-temperature process, improves carbon paper degree of graphitization before coated.
3. the preparation method of catalysis carbon paper according to claim 1, is characterized in that: in step B, first graphene oxide is put into alcohol ultrasonic process 2-3 hour before coated.
4. method according to claim 1, is characterized in that: in step C, and the temperature of vacuum drying treatment is 40-80 DEG C, and drying time is 24-48 hour.
5. the preparation method of catalysis carbon paper according to claim 1, it is characterized in that: in step D, nitrogen source gas is ammonia, and sulphur source gas is hydrogen sulfide.
CN201510906490.6A 2015-12-09 2015-12-09 A kind of preparation method being catalyzed carbon paper Expired - Fee Related CN105355936B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107342428A (en) * 2017-06-08 2017-11-10 中国科学技术大学 A kind of method of the extracellular electron transmission of enhancement microbiological in microorganism 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)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
DREW C. HIGGINS AT AL: ""Oxygen Reduction on Graphene−Carbon Nanotube Composites Doped Sequentially with Nitrogen and Sulfur"", 《ACS CATAL.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107342428A (en) * 2017-06-08 2017-11-10 中国科学技术大学 A kind of method of the extracellular electron transmission of enhancement microbiological in microorganism electrochemical system
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

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