CN106558708A - A kind of method for improving the carbon-based elctro-catalyst stability of fuel cell - Google Patents
A kind of method for improving the carbon-based elctro-catalyst stability of fuel cell Download PDFInfo
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- CN106558708A CN106558708A CN201611085583.8A CN201611085583A CN106558708A CN 106558708 A CN106558708 A CN 106558708A CN 201611085583 A CN201611085583 A CN 201611085583A CN 106558708 A CN106558708 A CN 106558708A
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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
- H01M4/96—Carbon-based electrodes
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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
Abstract
A kind of method for improving the carbon-based elctro-catalyst stability of fuel cell, is related to fuel cell.In the fluorine-containing or siliceous group of carbon-supported catalysts surface graft, hydrophobic carbon-supported catalysts are formed.There is protective effect to various sizes of duct, and be, by chemical bonding, to not easily run off, for a long time ducts at different levels can be protected：By chemical method on carbon-based elctro-catalyst a series of hydrophobic functional group of grafting, the hydrophobicity of catalyst can be significantly improved, the water droplet in Catalytic Layer is discharged in time, further improved stability.
Description
Technical field
The present invention relates to fuel cell, more particularly to a kind of side for improving the carbon-based elctro-catalyst stability of fuel cell
Method.
Background technology
Fuel cell as a kind of efficient, environmentally friendly energy conversion apparatus of new sustainability, by the extensive of people
Concern.But its large-scale application is still limited by the Pt catalyst of costliness, thus using cheap base metal elctro-catalyst
Remove to replace Pt catalyst for the large-scale promotion of fuel cell has very important significance.In recent years, base metal oxygen is also
The research of former elctro-catalyst [particularly metal/nitrogen/carbon (M/N/C)] makes great progress, and is applied in fuel cell,
Activation polarization region, the polarization curve of M/N/C is already close to Pt/C catalyst.As a kind of business Pt/C catalyst of substituting
Non noble metal oxygen reduction catalyst, it is necessary to have high activity and high stability concurrently.Although M/N/C catalyst shows high activity,
But the stability of M/N/C catalyst is but still very low (performance degradation of front 20h is more than 50%), does not much reach real requirement
(5000h).Thus, the stability for improving non-precious metal catalyst is the primary study direction of non-precious metal catalyst from now on.
The unstable source of carbon-based non-precious metal catalyst (M/N/C) is in 2 factors:A) active sites itself decay；B) duct
Water logging causes concentration polarization.At present, itself decay mechanism indefinite of catalyst activity position, from active sites this body structure
Go to improve the stability very blindness of catalyst, and effect on driving birds is not good.Thus, go to improve by solving the problems, such as duct water logging
In duct, the reaction environment of active sites is to improve stability simple and effective method.But for carbon-based base metal is urged
The active sites overwhelming majority of agent (M/N/C) is located at micropore, and microporous activated position is easier by little point of water, alcohol etc. than mesoporous and macropore
Son absorption.The oxygen radical of oxygen reduction reaction output simultaneously also can attack C carriers, so as to increase the hydrophilic of C carriers so that
Duct water logging phenomenon is more serious.And the micropore water logging of guard catalyst is all unable to according to prior art.Chinese patent
101237048A and document Ji, M.B.；Wei,Z.D.；Chen,S.G.；Li,L.“Ji,M.B.；Wei,Z.D.；Chen,
S.G.；Li, L.J.Phys.Chem.C 2009,113,765. " J.Phys.Chem.C 2009,113,765 disclose one kind " to be had
Sequence resists the preparation method of drowned gas perforated electrode ", its be mainly characterized by by viscosity for 5-100cp silicone oil, with volatile
Solvent mixes, and obtains silicone oil mixed liquor, is added drop-wise on Pt/C negative electrodes, produces pressure reduction by Bush's funnel, is distributed in silicone oil many
On pore electrode, so as to prepare the anti-drowned electrode of ordering.The method is that the hydrophobic silicone oil of small molecule is introduced directly into electrode to urge
Change in the duct of layer, although the hydrophobicity of macropore (20-70nm) can be increased, but there is following some shortcoming：A) to micropore without
Effect, because the methyl-silicone oil of small molecule on the contrary can be blocking microporous, as its oxygen diffusion coefficient is very low, can be caused tighter on the contrary
The concentration polarization of weight；B) methyl-silicone oil is present in duct by physical absorption, it is easy to be lost in, it is impossible to maintain a long-term stability
Property.
The content of the invention
The purpose of the present invention is for (the especially carbon-based pore type catalysis of carbon-supported catalysts decay of activity in fuel cell
Agent), while the shortcomings of micropore can not being protected in being directed to prior art, is easy to run off, there is provided the one of its stability can be increased substantially
Plant the method for improving the carbon-based elctro-catalyst stability of fuel cell.
The present invention's comprises the following steps that：
In the fluorine-containing or siliceous group of carbon-supported catalysts surface graft, hydrophobic carbon-supported catalysts are formed.
The impurity adsorbed by catalyst duct in removing building-up process, after heat treatment, by clean catalyst preparation into gas
Bulk diffusion electrode (GDE), after be prepared into membrane electrode assembly (MEA) and be applied to DMFC (DMFC) and hydrogen-oxygen proton
Its stability is investigated in exchange film fuel battery (PEMFC).
The group fluorine-containing or siliceous in carbon-supported catalysts surface graft can adopt chemical method, the chemical method
Diazol grafting, photocatalysis trifluoromethylation, single fluorine substitution reaction, friedel-crafts acylation, Fu Ke can be selected according to the group of grafting
The chemical methodes such as alkylation；The fluorine-containing or siliceous group of the grafting can be the base with hydrophobic property of siliceous or fluorine
Group, the group with hydrophobic property of described siliceous or fluorine may be selected from p-trifluoromethylaniline, pentafluoroaniline, and 1,2,4,5- tetra-
One kind in fluoro- 3- aminobenzenesulfonic acids, trifluoromethyl sodium sulfite, trim,ethylchlorosilane etc.；The carbon-supported catalysts may be selected from
Pore type Fe/N/C three-way catalysts, porous type Co/N/C catalyst, porous type Pt/C catalyst and other porous types it is carbon-based
At least one of catalyst；
The impurity adsorbed by catalyst duct in the removal building-up process can be cleaned by ultrasonic using organic solvent, described to have
Machine solvent can adopt dichloromethane or isopropanol.
The present invention has protective effect to various sizes of duct, and is, by chemical bonding, to not easily run off, Neng Gouchang
Phase is protected to ducts at different levels (micropore, mesoporous, macropore)：By chemical method, on carbon-based elctro-catalyst, grafting is a series of
Hydrophobic functional group (such as fluoro-containing group, silicon-containing group), can significantly improve the hydrophobicity of catalyst, discharge the water in Catalytic Layer in time
Drop, further improves stability.
Description of the drawings
Fig. 1 is embodiment Isosorbide-5-Nitrae, 7～9 and Comparative experiment A hydrogen-oxygen fuel cell stability curve.In figure：Curve 1 is table
Hydrogen-oxygen fuel cell of the carbon-based elctro-catalyst (Fe/N/C) of face grafting p-trifluoromethyl phenyl corresponding to cathod catalyst is steady
Qualitative curve；Curve 4 is hydrogen of the carbon-based elctro-catalyst of surface graft pentafluorophenyl group corresponding to cathod catalyst (Fe/N/C)
Oxygen fuel cell stability curve；Curve 7 is the carbon-based elctro-catalyst (Fe/ of 1,2,4,5- tetra- fluoro- 3- benzenesulfonic acids root of surface graft
N/C) the hydrogen-oxygen fuel cell stability curve corresponding to cathod catalyst；Curve 8 is the carbon-based of surface graft trifluoromethyl
Elctro-catalyst is the hydrogen-oxygen fuel cell stability curve corresponding to cathod catalyst (Fe/N/C)；Curve 9 is surface graft three
The carbon-based elctro-catalyst of methylsilyl is the hydrogen-oxygen fuel cell stability curve corresponding to cathod catalyst (Fe/N/C)；Curve
A is the hydrogen-oxygen fuel cell stability curve corresponding to the Fe/N/C negative electrodes of non-grafting；
Fig. 2 is the hydrogen-oxygen fuel cell stability curve of embodiment 2,5 and contrast experiment B.In figure：Curve 2 is that surface is transferred
Connect hydrogen-oxygen fuel cell stability of the carbon-based elctro-catalyst (Co/N/C) of p-trifluoromethyl phenyl corresponding to cathod catalyst
Curve；Curve 5 is hydrogen-oxygen combustion of the carbon-based elctro-catalyst (Co/N/C) of surface graft pentafluorophenyl group corresponding to cathod catalyst
Material stability test curve；Curve B is the hydrogen-oxygen fuel cell stability curve corresponding to the Co/N/C negative electrodes of non-grafting；
Fig. 3 is the DMFC stability curve of embodiment 3,6 and contrast experiment C.Curve 3 is surface graft
DMFC stability of the carbon-based elctro-catalyst (Pt/C) of p-trifluoromethyl phenyl corresponding to cathod catalyst
Curve；Curve 6 is direct methanol of the carbon-based elctro-catalyst (Pt/C) of surface graft pentafluorophenyl group corresponding to cathod catalyst
Fuel battery stability curve；Comparative experiment A is the DMFC stability corresponding to the Pt/C negative electrodes of non-grafting
Curve；
Specific embodiment
Embodiment 1
A) Fe/N/C catalyst surfaces grafting p-trifluoromethyl phenyl：P-trifluoromethylaniline is added in 250ml beakers
(5mmol), fluoboric acid (15mmol) and water (100mL), stir transparent to solution；Sodium nitrite solution is slowly added dropwise under ice-water bath
(15mmol), slowly generate diazol.Appropriate Fe/N/C catalyst and a small amount of reducing agent (sodium borohydride) are added, under ice-water bath
Stirring 2h；
B) clean Fe/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Embodiment 2
A) Co/N/C catalyst surfaces grafting p-trifluoromethyl phenyl：P-trifluoromethylaniline is added in 250ml beakers
(5mmol), fluoboric acid (15mmol) and water (100mL), stir transparent to solution；Sodium nitrite solution is slowly added dropwise under ice-water bath
(15mmol), slowly generate diazol.Appropriate Co/N/C catalyst and a small amount of reducing agent (sodium borohydride) are added, under ice-water bath
Stirring 2h；
B) clean Co/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Co/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃；
Embodiment 3
A) Pt/C catalyst surfaces grafting p-trifluoromethyl phenyl：P-trifluoromethylaniline is added in 250ml beakers
(5mmol), fluoboric acid (15mmol) and water (100mL), stir transparent to solution；Sodium nitrite solution is slowly added dropwise under ice-water bath
(15mmol), slowly generate diazol.Appropriate Pt/C catalyst and a small amount of reducing agent (sodium borohydride) are added, is stirred under ice-water bath
Mix 2h；
B) clean Pt/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；Plus
Enter isopropanol, ultrasonic 10min is filtered, and repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is positioned over
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) MEA is prepared and test：Negative electrode ink consists of-Pt/C catalyst 10mg；5wt%nafion solution 0.065mL；
Solvent normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas is prepared by the way of drop coating
Bulk diffusion electrode (GDE), the carrying capacity of final cathod catalyst is 0.4mgpt cm-2；Anode gas diffusion layer adopts business Pt/C
Catalyst or Pt-Ru/C catalyst；The gas-diffusion electrode for preparing and PEM (nafion films) hot pressing are formed
Membrane electrode (hot pressing condition is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, is tested
Condition is：Arbin methanol fuel cell test systems；Oxidant：The oxygen (100sccm) not humidified；Fuel：The methanol-water of 3M
Solution (2sccm)；Battery temperature：60℃；
Embodiment 4
A) Fe/N/C catalyst surfaces grafting pentafluorophenyl group：Pentafluoroaniline (5mmol), fluoboric acid are added in 250ml beakers
(15mmol) with water (100mL), stir transparent to solution；Sodium nitrite solution (15mmol) is slowly added dropwise under ice-water bath, slowly
Generate diazol.Appropriate Fe/N/C catalyst and a small amount of reducing agent (sodium borohydride) are added, under ice-water bath, 2h is stirred；
B) clean Fe/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Embodiment 5
A) Co/N/C catalyst surfaces grafting pentafluorophenyl group：Pentafluoroaniline (5mmol), fluoboric acid are added in 250ml beakers
(15mmol) with water (100mL), stir transparent to solution；Sodium nitrite solution (15mmol) is slowly added dropwise under ice-water bath, slowly
Generate diazol.Appropriate Co/N/C catalyst and a small amount of reducing agent (sodium borohydride) are added, under ice-water bath, 2h is stirred；
B) clean Co/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Co/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃；
Embodiment 6
A) Pt/C catalyst surfaces face grafting pentafluorophenyl group：Pentafluoroaniline (5mmol), fluoboric acid are added in 250ml beakers
(15mmol) with water (100mL), stir transparent to solution；Sodium nitrite solution (15mmol) is slowly added dropwise under ice-water bath, slowly
Generate diazol.Appropriate Pt/C catalyst and a small amount of reducing agent (sodium borohydride) are added, under ice-water bath, 2h is stirred；
B) clean Pt/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；Plus
Enter isopropanol, ultrasonic 10min is filtered, and repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is positioned over
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) MEA is prepared and test：Negative electrode ink consists of-Pt/C catalyst 10mg；5wt%nafion solution 0.065mL；
Solvent normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas is prepared by the way of drop coating
Bulk diffusion electrode (GDE), the carrying capacity of final cathod catalyst is 0.4mgpt cm-2；Anode gas diffusion layer adopts business Pt-
Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (hot pressing bar
Part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：Arbin
Methanol fuel cell test system；Oxidant：The oxygen (100sccm) not humidified；Fuel：The methanol aqueous solution (2sccm) of 3M；
Battery temperature：60℃；
Embodiment 7
A) 1,2,4,5- tetra- fluoro- 3- sulfonic groups phenyl of Fe/N/C catalyst surfaces grafting：Add in 250ml beakers to 1,2,
4,5- tetrafluoro benzenesulfonic acids (5mmol), fluoboric acid (15mmol) and water (100mL), stir transparent to solution；Slowly drip under ice-water bath
Plus sodium nitrite solution (15mmol), slowly generate diazol.Add appropriate Fe/N/C catalyst and a small amount of reducing agent (boron hydrogen
Change sodium), 2h is stirred under ice-water bath；
B) clean Fe/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃；
Embodiment 8
A) Fe/N/C catalyst surfaces grafting trifluoromethyl：Trifluoromethyl sulfonate is added in 250ml round-bottomed flasks
(5mmol), 10ml acetone and 50mg Fe/N/C catalysis, flow back under nitrogen and illumination 12h；
B) clean Fe/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Embodiment 9
A) Fe/N/C catalyst surfaces grafting trimethyl silicon substrate：In 250ml beakers add trim,ethylchlorosilane (5mmol),
Excessive aluminum chloride and absolute ether (100mL), are eventually adding appropriate Fe/N/C catalyst, stir a few hours under ice-water bath；
B) clean Fe/N/C catalyst:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；
Isopropanol, ultrasonic 10min is added to filter, repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is placed
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Comparative experiment A
A) the Fe/N/C catalyst of non-grafting is selected as blank control group；
B) repeated washing process:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；Add
Isopropanol, ultrasonic 10min are filtered, and repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is positioned over
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Fe/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Contrast experiment B
A) the Co/N/C catalyst of non-grafting is selected as blank control group；
B) repeated washing process:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；Add
Isopropanol, ultrasonic 10min are filtered, and repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is positioned over
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Co/N/C catalyst 25mg；5wt%nafion solution 0.55mL；Solvent
Normal propyl alcohol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas expansion is prepared by the way of drop coating
Scattered electrode (GDE), the carrying capacity of final cathod catalyst is 5mg cm-2；Anode gas diffusion layer adopt business Pt/C catalyst or
Person's Pt-Ru/C catalyst；By the gas-diffusion electrode for preparing with PEM (nafion films) hot pressing into membrane electrode (heat
Press strip part is 135 DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：
Scribner hydrogen-oxygen fuel cell test systems, oxidant：100% humidification oxygen (100sccm)；Fuel：100% humidification hydrogen
(80sccm)；Battery temperature：80℃.
Contrast experiment C
A) the Pt/C catalyst of non-grafting is selected as blank control group；
B) repeated washing process:By catalyst dissolution in dichloromethane, ultrasonic 10min is filtered, and repetition is secondary；Add
Isopropanol, ultrasonic 10min are filtered, and repetition is secondary；Water is added, ultrasonic 10min, repetition are secondary；The catalyst for obtaining is positioned over
10h is vacuum dried at 200 DEG C, the catalyst after grafting is obtained；
C) prepared by MEA：Negative electrode ink consists of-Pt/C catalyst 10mg；5wt%nafion solution 0.065mL；Solvent is just
Propanol 1mL；Negative electrode ink is placed on under the conditions of ice-water bath ultrasound to dispersed；Gas diffusion is prepared by the way of drop coating
Electrode (GDE), the carrying capacity of final cathod catalyst is 0.4mgpt cm-2；Anode gas diffusion layer is catalyzed using business Pt-Ru/C
Agent；By the gas-diffusion electrode for preparing, into membrane electrode, (hot pressing condition is 135 with PEM (nafion films) hot pressing
DEG C, 3MPa, 2min)；The membrane electrode assembly packed battery for preparing is carried out into monocell test, test condition is：Arbin methanol fuels
Battery test system；Oxidant：The oxygen (100sccm) not humidified；Fuel：The methanol aqueous solution (2sccm) of 3M；Battery temperature
Degree：60℃.
The present invention is by chemical method in a series of hydrophobic functional group of carbon-based elctro-catalyst surface graft (as containing fluorine-based
Group, silicon-containing group), the hydrophobicity of catalyst can be significantly improved, all kinds of ducts (micropore, mesoporous, macropore) of Catalytic Layer are discharged in time
In water droplet, thus increase substantially stability.
Claims (7)
1. a kind of method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in which comprises the following steps that：
In the fluorine-containing or siliceous group of carbon-supported catalysts surface graft, hydrophobic carbon-supported catalysts are formed.
2. a kind of as claimed in claim 1 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
Chemical method, group of the chemical method according to grafting are adopted in the fluorine-containing or siliceous group of carbon-supported catalysts surface graft
Select diazol grafting, photocatalysis trifluoromethylation, single fluorine substitution reaction, friedel-crafts acylation, Friedel-Crafts chemical method.
3. a kind of as claimed in claim 1 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
The fluorine-containing or siliceous group of grafting is siliceous or the group with hydrophobic property of fluorine.
4. a kind of as claimed in claim 1 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
The group with hydrophobic property of siliceous or fluorine is selected from p-trifluoromethylaniline, pentafluoroaniline, 1,2,4,5- tetra- fluoro- 3- amino
Benzenesulfonic acid, trifluoromethyl sodium sulfite, the one kind in trim,ethylchlorosilane.
5. a kind of as claimed in claim 1 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
Carbon-supported catalysts be selected from pore type Fe/N/C three-way catalysts, porous type Co/N/C catalyst, porous type Pt/C catalyst and
At least one of other porous type carbon-supported catalysts.
6. a kind of as claimed in claim 1 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
The impurity adsorbed by catalyst duct in removing building-up process is cleaned by ultrasonic using organic solvent.
7. a kind of as claimed in claim 6 method for improving the carbon-based elctro-catalyst stability of fuel cell, it is characterised in that described
Organic solvent adopts dichloromethane or isopropanol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975332A (en) * | 2019-12-23 | 2020-04-10 | 中国石油大学(华东) | Carbon fiber felt modification method for oil-water separation |
| CN113632265A (en) * | 2019-04-09 | 2021-11-09 | 凸版印刷株式会社 | Membrane electrode assembly and solid polymer fuel cell |
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|---|---|---|---|---|
| CN1373910A (en) * | 1999-10-12 | 2002-10-09 | 卡伯特公司 | Gas diffusion electrodes contg. modified carbon products |
| US20050233183A1 (en) * | 2004-03-15 | 2005-10-20 | Hampden-Smith Mark J | Modified carbon products, their use in electrocatalysts and electrode layers and similar devices and methods relating to the same |
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2016
- 2016-11-30 CN CN201611085583.8A patent/CN106558708A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373910A (en) * | 1999-10-12 | 2002-10-09 | 卡伯特公司 | Gas diffusion electrodes contg. modified carbon products |
| US20050233183A1 (en) * | 2004-03-15 | 2005-10-20 | Hampden-Smith Mark J | Modified carbon products, their use in electrocatalysts and electrode layers and similar devices and methods relating to the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113632265A (en) * | 2019-04-09 | 2021-11-09 | 凸版印刷株式会社 | Membrane electrode assembly and solid polymer fuel cell |
| CN110975332A (en) * | 2019-12-23 | 2020-04-10 | 中国石油大学(华东) | Carbon fiber felt modification method for oil-water separation |
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