CN109935846A - A kind of fuel cell electro-catalyst carrier and preparation method thereof - Google Patents
A kind of fuel cell electro-catalyst carrier and preparation method thereof Download PDFInfo
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- CN109935846A CN109935846A CN201711349480.2A CN201711349480A CN109935846A CN 109935846 A CN109935846 A CN 109935846A CN 201711349480 A CN201711349480 A CN 201711349480A CN 109935846 A CN109935846 A CN 109935846A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of fuel cell electro-catalyst carriers and preparation method thereof.The electro-catalyst carrier is functionalization carbon black/graphene composite material, preparation method includes the following steps: carrying out functional modification to carbon black with cationic polymer first keeps its positively charged, then functionalization carbon black/graphene oxide multilevel structure is formed by electrostatic self-assembled with negatively charged graphene oxide, graphene oxide therein is most reduced to graphene through the methods of chemistry, electrochemistry afterwards, to further increase the electric conductivity of composite material.This preparation method is simple and easy to do, low in cost, use easy to spread.The study found that composite material prepared by the present invention has three-dimensional porous structure, biggish specific surface area, good electric conductivity, and it is easier to capture and evenly dispersed nano metal particles.Electro-chemical test shows the active high and stable performance advantage of elctro-catalyst prepared using the functionalization carbon black/graphene composite material as carrier.
Description
Technical field
The invention belongs to fuel cell fields, and in particular to a kind of functionalization carbon black/graphene composite wood of three-dimensional structure
The preparation of material and application as fuel cell electro-catalyst carrier.
Background technique
Fuel cell is a kind of power generator that the chemical energy being stored in fuel and oxidant is converted into electric energy,
With energy conversion efficiency height, start quick, advantages of environment protection, is expected to large-scale application and is produced in vehicle, portable electronic
The fields such as product and dispersion power plant, research have caused the great attention of national governments.
Elctro-catalyst is the critical material of fuel cell, and active and stability directly affects performance and the longevity of fuel cell
Life.And carrier then plays a crucial role the performance of catalyst.Carrier is the polymolecularity and stability of metallic
Possibility is provided, to improve the utilization rate of catalyst, activity and stability.Following item should be met as catalyst carrier
Part: (1) good electric conductivity, in favor of charge transmission；(2) biggish specific surface area so as to dispersed actives, is improved and is lived
Property object utilization rate；(3) stronger support-catalyst interaction, for improving catalytic efficiency, the loss of less catalyst；
(4) pore structure abundant improves three-phase reaction interface so that the reactant in electrolyte is contacted with catalyst；(5) stronger anti-
Corrosive power, to improve chemical stability of the catalyst in reaction medium.Graphene is by sp2The two dimension of carbon atom bonding composition
Structural body, having biggish specific surface area, (theoretical specific surface area is up to 2620m2g-1), good electrical conductance, excellent chemistry is surely
It is qualitative and be easy to the advantages that being surface modified, it is a kind of ideal catalyst carrier, is opened up to improve the performance of fuel cell
New direction.However, graphene still remains many problems as the research of catalyst carrier.For example, graphene sheet layer it
Between in reduction or drying process because irreversible reunion may occur for Van der Waals force, or even graphite knot can be piled into again
Structure, can not only destroy the high-ratio surface of graphene, but also be unfavorable for the dispersion that graphene carries platinum slurry；Graphene is prepared in early period
Process introduces a large amount of fault of construction, reduces the electric conductivity of graphene, influences the electron transport rate during electro-catalysis.
To solve the above problems, researcher introduces electrical-conductive nanometer material as spacer, a side in graphene film interlayer
Face prevents the stacking of graphene film, and interconnect to form hole with graphene by the way that conductive material is embedded in graphene film interlayer
Hole structure；On the other hand, by the nano combined fault of construction for repairing graphene, the conductivity of complex carrier is improved.It is so far
Only, many carbon materials have all been used as spacer, effectively prevent the stacking again of graphene.Wherein, pass through chemical vapor deposition
Carbon nanotube is embedded in graphene sheet layer by product method can be effectively synthesized carbon nano tube/graphene compound, but the preparation
Process is complicated, at high cost, limit this kind of graphene complex large-scale application (Z.Lei, L. Lu and X.S.Zhao,
Energy Environ.Sci.,2012,5,6391–6399.).Carbon black, as a kind of cheap, with superior electrical conductivity carbon
Material is a kind of ideal graphene zone isolation object.Lee et al. has reported the carbon black/stone synthesized under a kind of ultrasonication
Black alkene compound, with its support Pt nanoparticle can effectively improve catalyst stability (Y.J.Li, Y.J.Li, E.Zhu,
T.Mclouth, C.Y.Chiu,X.Q.Huang and Y.Huang,J.Am.Chem.Soc.,2012,134, 12326–
12329.).But since the interaction of carbon black and graphene under the preparation condition is weaker, cause carbon black on graphene film
It is unevenly distributed, the part for causing graphene film stacks, so that electrochemical surface area reduces, catalyst activity is not high.Cause
This, there is an urgent need to explore a kind of simple process, low-cost method prepare carbon-based/graphene composite carrier for improving fuel
The activity and stability of cell catalyst.
Summary of the invention
The present invention is to solve the above problems, devise a kind of simple cheap functionalization carbon black/graphene preparation method.
Carrying out functional modification to carbon black using cationic polymer keeps its positively charged, then exists with negatively charged graphene oxide
It is self-assembly of stable functionalization carbon black/graphene oxide three dimensional composite structure under the action of electrostatic force, effectively prevents stone
The irreversible reunion of black alkene lamella, improves the specific surface area of catalyst, exposes more reaction sites, and has manufactured more
Pore structure provides the transmission channel of reactant, promotes mass transfer, to achieve the purpose that improve catalytic activity.
The technical solution that the present invention takes comprises the following steps:
A kind of preparation method of fuel cell electro-catalyst carrier, the method comprises the following steps:
1) cationic polymer in deionized water by carbon black ultrasonic disperse, is added, ultrasonic agitation obtains mixture A；
2) suction filtration is washed with deionized in mixture A, positively charged functionalization carbon black is obtained after vacuum drying
(FCB)；
3) above-mentioned functionalization carbon black is re-dispersed into deionized water, the aqueous dispersions of graphene oxide (GO) is added,
Sonic oscillation is uniformly mixed it, and continues to stir 5-20h at room temperature, obtains functionalization carbon black/graphene oxide mixture
(FCB-GO)；
4) mixture in step 3) is restored, is freeze-dried after centrifuge washing, it is multiple to obtain functionalization carbon black/graphene
Condensation material (FCB-rGO).
In step 1), the mass ratio of carbon black and cationic polymer is 1:5-1:20；The ultrasonic agitation time is 3-12h.
In step 1), cationic polymer includes ammonium salt class N+, sulfosalt class S+, microcosmic salt class P+ cationic polymer, specifically
For diallyl dimethyl ammoniumchloride (PDDA), polyvinylamine (PVAM), polyacrylamide (PAM) etc..
In step 2), vacuum drying temperature is 60-120 DEG C, time 6-24h.
In step 3), the mass ratio of functionalization carbon black and graphene oxide is 1:5-5:1；Graphene oxide aqueous dispersions
Concentration is 0.1-2mg ml-1, preferably 0.5mg ml-1。
In step 4), restoring method mainly have chemical reduction method, solvothermal method, electrochemical reducing, thermal reduction,
Microwave stripping method or joint multistep reduction etc..
In step 4), when restoring method being used to restore for chemical reduction method to mixture, reaction condition are as follows: reaction temperature
25-95 DEG C of degree, in reaction time 3-24 hour, is stirred simultaneously.
In step 4), in chemical reduction method reducing agent include hydration hydrazine and its derivative, it is sodium borohydride, ascorbic acid, strong
Alkali, HI, citric acid or urea etc.；The mass ratio of reducing agent and graphene oxide is 0.7-20.
In step 4), when restoring method is that solvothermal method restores mixture, reaction condition are as follows: reaction temperature
140-200 DEG C, reaction time 8-24h.
In step 4), when restoring method is that thermal reduction restores mixture, reaction condition are as follows: inertia or reproducibility
Atmosphere protection, heating rate 5 DEG C/min, 550-1100 DEG C of reaction temperature, reaction time 0.5-2h.
The present invention is based on simple cheap solution self-assembly methods to be successfully prepared functionalization carbon black/graphene composite material,
Being used as fuel-cell catalyst carrier can effectively improve electrocatalysis characteristic.In the composite construction, carbon black is in graphene table
EDS maps are more uniform, with graphene interactive connection form three-dimensional open-framework, have high-specific surface area, good electric conductivity,
Excellent ion transport capability is easier to the advantages that capturing with evenly dispersed nano metal particles.With the functionalization carbon black/graphene
Composite material is that the elctro-catalyst of carrier preparation has the catalytic performance significantly improved and stability.This preparation method is simply easy
Row, has broad application prospects in fuel cell and electro-catalysis field.
Detailed description of the invention
Fig. 1 is functionalization carbon black/graphene composite material stereoscan photograph；
Fig. 2 is graphene and functionalization carbon black/graphene composite material raman spectrum；
Fig. 3 is graphene and functionalization carbon black/graphene composite material nitrogen adsorption desorption isothermal curve；
Fig. 4 is the transmission electron microscope photo of PtCo/FCB-rGO；
Fig. 5 a is cyclic voltammetric (CV) curve of PtCo/rGO and PtCo/FCB-rGO, and testing electrolyte used is N2Saturation
0.1mol/L HClO4Aqueous solution, sweeping speed is 50mV/s；
Fig. 5 b is hydrogen reduction (ORR) polarization curve of PtCo/rGO and PtCo/FCB-rGO, and testing electrolyte used is O2
The 0.1mol/L HClO of saturation4Aqueous solution, sweeping speed is 10mV/s, and RDE revolving speed is 1600rpm；
Fig. 6 is the polarization curves of oxygen reduction that PtCo/FCB-rGO accelerates decaying front and back, and accelerating attenuation test is with N2Saturation
0.1mol/L HClO4Solution is electrolyte, and scanning voltage range 0.6-1.2V sweeps fast 50mV s-1, 1500 circle of scanning；
Fig. 7 is the transmission electron microscope photo of PtRu/FCB-rGO；
Fig. 8 is the transmission electron microscope photo of PdNiAu/FCB-rGO.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, but is not so limited,
It is all that modifying or equivalently replacing the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention,
It should all cover within the protection scope of the present invention.
Embodiment 1
In deionized water by carbon black ultrasonic disperse, cationic polymer PDDA is added, so that the quality of carbon black and PDDA
Than for 1:10.Ultrasonic agitation is washed with deionized suction filtration, positively charged functionalization charcoal is obtained after vacuum drying after 3 hours
Black (FCB).FCB is re-dispersed into deionized water, the aqueous dispersions of the graphene oxide of concentration 1mg/ml are added, so that function
The mass ratio that carbon black and graphene oxide can be changed is 2:1, and sonic oscillation is uniformly mixed it, and continues to stir 7h at room temperature,
Obtain functionalization carbon black/graphene oxide mixture (FCB-GO).Ascorbic acid is added into this mixture dispersion liquid, so that
The mass ratio of ascorbic acid and graphene oxide is 20, and after 12 hours are stirred to react at 95 DEG C, centrifuge washing obtains function
Change carbon black/graphene composite material (FCB-rGO).The composite material in the above way prepared is carrier, using polynary alcohol reflux
Method, and after pickling, obtain PtCo catalyst.As a comparison, being separately prepared for simple graphene according to the above method is carrier
PtCo catalyst.Performance test results are as shown in figures 1 to 6.As shown in Figure 1, functionalization carbon black pellet is relatively evenly distributed in stone
Black alkene on piece, forms three dimensional pore structures therewith.The structure is conducive to improve the specific surface area of catalyst, the more activity of exposure
Site, more can be into the transmission of ion, thus improves electrocatalytic reaction rate.As shown in Figure 2, from graphene to functionalization carbon black/
Graphene composite material, IG/IDValue increases to 0.97 by 0.72, illustrates that the fault of construction of graphene is repaired, this is also
An important factor for improving hydrogen reduction electro catalytic activity.From the figure 3, it may be seen that compared to graphene, functionalization carbon black/graphene composite wood
The BET specific surface area of material is greatly improved.As shown in Figure 4, PtCo nano particle and complex carrier have stronger mutual
Effect, can be evenly distributed in complex carrier surface, and partial size is smaller, soilless sticking phenomenon.By Fig. 5 a, Fig. 5 b and Fig. 6 it is found that
Functionalization carbon black/graphene composite carrier shows superior performance, and the PtCo catalyst activity carried is much higher than common PtCo/
Graphen catalyst.As shown in Figure 7, PtCo/FCB-rGO catalyst also shows that excellent stability.
Embodiment 2
In deionized water by carbon black ultrasonic disperse, cationic polymer PVAM is added, so that the quality of carbon black and PVAM
Than for 1:15.Ultrasonic agitation is washed with deionized suction filtration, positively charged functionalization charcoal is obtained after vacuum drying after 6 hours
Black (FCB).FCB is re-dispersed into deionized water, the aqueous dispersions of the graphene oxide of concentration 2mg/ml are added, so that function
The mass ratio that carbon black and graphene oxide can be changed is 1:1, and sonic oscillation is uniformly mixed it, and continues to stir 12h at room temperature,
Obtain functionalization carbon black/graphene oxide mixture (FCB-GO).Hydrazine hydrate is added into this mixture dispersion liquid, so that water
The mass ratio for closing hydrazine and graphene oxide is 1:1, and after 6 hours are stirred to react at 95 DEG C, centrifuge washing obtains functionalization charcoal
Black/graphene composite material (FCB-rGO).The composite material in the above way prepared is carrier, using microwave-assisted polyalcohol
Method, is prepared for PtRu catalyst, and transmission electron microscope photo is shown in Fig. 7.
Embodiment 3
In deionized water by carbon black ultrasonic disperse, cationic polymer PAM is added, so that the mass ratio of carbon black and PAM
For 1:20.Ultrasonic agitation is washed with deionized suction filtration, positively charged functionalization carbon black is obtained after vacuum drying after 3 hours
(FCB).FCB is re-dispersed into deionized water, the aqueous dispersions of the graphene oxide of concentration 0.5mg/ml are added, so that function
The mass ratio that carbon black and graphene oxide can be changed is 3:1, and sonic oscillation is uniformly mixed it, and continues to stir 10h at room temperature,
Obtain functionalization carbon black/graphene oxide mixture (FCB-GO).Sodium borohydride is added into this mixture dispersion liquid, so that
The mass ratio of sodium borohydride and graphene oxide is 10, and after 12 hours are stirred to react at 60 DEG C, centrifuge washing obtains functionalization
Carbon black/graphene composite material (FCB-rGO).The composite material in the above way prepared is carrier, using solvent thermal process, system
Fig. 8 is seen for PdNiAu catalyst, transmission electron microscope photo.
Embodiment 4
In deionized water by carbon black ultrasonic disperse, cationic polymer PDDA is added, so that the quality of carbon black and PDDA
Than for 1:10.Ultrasonic agitation is washed with deionized suction filtration, positively charged functionalization charcoal is obtained after vacuum drying after 3 hours
Black (FCB).FCB is re-dispersed into deionized water, the aqueous dispersions of the graphene oxide of concentration 2mg/ml are added, so that function
The mass ratio that carbon black and graphene oxide can be changed is 2:1, and sonic oscillation is uniformly mixed it, and continues to stir 10h at room temperature,
Obtain functionalization carbon black/graphene oxide mixture (FCB-GO).This mixture is transferred in autoclave, in 180
After reacting 12 hours at DEG C, centrifuge washing obtains functionalization carbon black/graphene composite material (FCB-rGO).
Embodiment 5
In deionized water by carbon black ultrasonic disperse, cationic polymer PDDA is added, so that the quality of carbon black and PDDA
Than for 1:10.Ultrasonic agitation is washed with deionized suction filtration, positively charged functionalization charcoal is obtained after vacuum drying after 5 hours
Black (FCB).FCB is re-dispersed into deionized water, the aqueous dispersions of the graphene oxide of concentration 0.5mg/ml are added, so that
The mass ratio of functionalization carbon black and graphene oxide is 4:1, and sonic oscillation is uniformly mixed it, and continues to stir at room temperature
6h obtains functionalization carbon black/graphene oxide mixture (FCB-GO).After the drying of this mixture filtering and washing, it is transferred to
In quartz ampoule, in 5%H2Under/Ar atmosphere, 800 DEG C are warming up to the rate of 5 DEG C/min and is kept for 1 hour, nitrogen purging cooling,
Obtain functionalization carbon black/graphene composite material (FCB-rGO).
Claims (10)
1. a kind of preparation method of fuel cell electro-catalyst carrier, it is characterised in that: the method comprises the following steps:
1) cationic polymer in deionized water by carbon black ultrasonic disperse, is added, ultrasonic agitation obtains mixture A；
2) suction filtration is washed with deionized in mixture A, positively charged functionalization carbon black (FCB) is obtained after vacuum drying；
3) above-mentioned functionalization carbon black is re-dispersed into deionized water, the aqueous dispersions of graphene oxide (GO), ultrasound is added
Oscillation is uniformly mixed it, and continues to stir 5-20h at room temperature, obtains functionalization carbon black/graphene oxide mixture (FCB-
GO)；
4) mixture in step 3) is restored, is freeze-dried after centrifuge washing, obtain functionalization carbon black/graphene composite wood
Expect (FCB-rGO).
2. preparation method according to claim 1, it is characterised in that: in step 1), the matter of carbon black and cationic polymer
Amount is than being 1:5-1:20；The ultrasonic agitation time is 3-12h.
3. preparation method according to claims 1 and 2, which is characterized in that in step 1), cationic polymer includes ammonium salt
Class N+, sulfosalt class S+, microcosmic salt class P+ cationic polymer, specially diallyl dimethyl ammoniumchloride (PDDA), polyethylene
Amine (PVAM), polyacrylamide (PAM) etc..
4. preparation method according to claim 1, it is characterised in that: in step 2), vacuum drying temperature is 60-120 DEG C,
Time is 6-24h.
5. preparation method according to claim 1, it is characterised in that: in step 3), functionalization carbon black and graphene oxide
Mass ratio be 1:5-5:1；The concentration of graphene oxide aqueous dispersions is 0.1-2mg ml-1, preferably 0.5mg ml-1。
6. preparation method according to claim 1, it is characterised in that: in step 4), restoring method mainly has electronation
Method, solvothermal method, electrochemical reducing, thermal reduction, microwave stripping method or joint multistep reduction etc..
7. preparation method according to claim 1 or 6, it is characterised in that: in step 4), restoring method is used to go back for chemistry
When former method restores mixture, reaction condition are as follows: 25-95 DEG C of reaction temperature, in reaction time 3-24 hour, stir simultaneously.
8. preparation method according to claim 7, it is characterised in that: in step 4), reducing agent includes in chemical reduction method
It is hydrated hydrazine and its derivative, sodium borohydride, ascorbic acid, highly basic, HI, citric acid or urea etc.；Reducing agent and graphene oxide
Mass ratio be 0.7-20.
9. preparation method according to claim 6, it is characterised in that: in step 4), restoring method is solvothermal method
When being restored to mixture, reaction condition are as follows: 140-200 DEG C of reaction temperature, reaction time 8-24h.
10. preparation method according to claim 6, it is characterised in that: in step 4), restoring method is thermal reduction to mixed
When conjunction object is restored, reaction condition are as follows: inertia or reducing atmosphere protection, heating rate 5 DEG C/min, reaction temperature 550-
1100 DEG C, reaction time 0.5-2h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307225A (en) * | 2021-05-31 | 2021-08-27 | 中国矿业大学 | Method for preparing hydrogen by stably catalyzing methane cracking through carbon black enhanced activated carbon and application |
| CN114538409A (en) * | 2022-01-28 | 2022-05-27 | 湖南邦普循环科技有限公司 | Preparation method and application of nitrogen-doped carbon dot-reduced graphene oxide composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102974341A (en) * | 2012-12-10 | 2013-03-20 | 天津工业大学 | Method for preparing proton exchange membrane fuel cell catalyst with nanocrystalline structure |
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- 2017-12-15 CN CN201711349480.2A patent/CN109935846A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974341A (en) * | 2012-12-10 | 2013-03-20 | 天津工业大学 | Method for preparing proton exchange membrane fuel cell catalyst with nanocrystalline structure |
Non-Patent Citations (6)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307225A (en) * | 2021-05-31 | 2021-08-27 | 中国矿业大学 | Method for preparing hydrogen by stably catalyzing methane cracking through carbon black enhanced activated carbon and application |
| CN113307225B (en) * | 2021-05-31 | 2023-08-22 | 中国矿业大学 | Method for preparing hydrogen by stable catalytic methane pyrolysis by using carbon black enhanced active carbon and application |
| CN114538409A (en) * | 2022-01-28 | 2022-05-27 | 湖南邦普循环科技有限公司 | Preparation method and application of nitrogen-doped carbon dot-reduced graphene oxide composite material |
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Application publication date: 20190625 |