CN109935848A - A kind of composite catalyst and preparation method thereof - Google Patents
A kind of composite catalyst and preparation method thereof Download PDFInfo
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- CN109935848A CN109935848A CN201711352485.0A CN201711352485A CN109935848A CN 109935848 A CN109935848 A CN 109935848A CN 201711352485 A CN201711352485 A CN 201711352485A CN 109935848 A CN109935848 A CN 109935848A
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- composite catalyst
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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
By introducing high polymer binder in catalyst synthesis processes, elctro-catalyst-binder composite is made, can be achieved catalyst granules with bond agent molecule it is micro-/receive being uniformly distributed on scale, being uniformly distributed for the two can not only greatly improve three-phase reaction interface region in membrane electrode, elctro-catalyst and being uniformly distributed for binder component also contribute to lyophily in Catalytic Layer and hate the formation of fluid apertures and be uniformly distributed simultaneously, optimize liquid electrolyte in fuel cell electrode reaction process, the distribution of sour reaction gas and product in Catalytic Layer, transport behavior, it avoids because electrode component reunion causes parent in Catalytic Layer, liquid zone is hated to be unevenly distributed, occur " liquid floods ", strengthen air mass transfer, to improve the discharge performance and operation stability of fuel cell.
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells fields, are related to a kind of preparation method of fuel cell electro-catalyst.
Background technique
Due to the high, specific power with energy conversion efficiency and specific energy density height, advantages of environment protection, fuel-cell vehicle
One of Main Topics and the direction of numerous Automobile Enterprises and research institution are had become with electrical source of power.Wherein with perfluorinated sulfonic acid
The research of type proton exchange membrane (such as Nafion membrane) hydrogen-oxygen fuel cell is the most extensive, the first " hydrogen developed such as General Corporation
Dynamic No. 1 " the Miriam hydrogen-oxygen fuel cell vehicle etc. released for 2016 of fuel-cell car and Toyota Company.Proton exchange membrane
The peculiar advantage of fuel cell makes it have wide application in distributing power station and Co-generation equipment and vehicle power mains
The research of the types of fuel cells has been carried out in prospect, many countries and area in succession.
The same with other Proton Exchange Membrane Fuel Cells, membrane electrode (MEA) is high temperature proton membrane fuel battery " heart "
Position, composition and structure have important influence to the discharge performance of fuel cell, service life and system reliability.Platinum base
Elctro-catalyst plays irreplaceable role in fuel cell field, but the reserves of platinum are limited, expensive, and it is big to limit it
Sizable application.Platinum is supported on to the dosage that platinum can be effectively reduced on various carrier materials, and improves Pt catalytic activity, is to improve
One of method of utilization efficiency of platinum.The reduction of Pt dosage and it is active improve will result directly in the cost of fuel cell substantially under
Drop, significantly the commercialization process of propellant battery.
Elctro-catalyst is one of critical material of fuel cell membrane electrode, and structure, composition directly affect electrochemical reaction
Speed and stability.The preparation method of conventional catalyst mostly uses liquid phase reduction, based on metal precursor salt and reducing agent
Solution obtains metal nano colloidal solution, is washed out drying and obtains powdered elctro-catalyst.It can also be in catalyst preparation mistake
Carbon carrier is introduced in journey obtains loaded elctro-catalyst powder.Although small based on the available catalyst granules of liquid phase reduction,
The colloidal attitude nanometer electrical catalyst of narrow size distribution, however in elctro-catalyst colloid subsequent wash, during drying, nanometer ruler
Very little electrocatalyst particles are since surface can be high, even if it is existing to be dried the agglomeration for being also easy to that particle occurs at normal temperature
As.Coalescence between catalyst nano-particles, which is grown up, will lead to the reduction of elctro-catalyst chemical activity area, reduce Pt catalyst benefit
With efficiency, cell output is poor.
In order to overcome the problems referred above, the present invention forms elctro-catalyst-bonding by introducing binder in catalyst preparation process
The method of agent compound, realize catalyst and binder it is micro-, receive and uniformly mix on scale, it is poly- to can effectively avoid nanocatalyst
Knot is grown up；Catalyst and binder can also be improved secondly based on elctro-catalyst-binder composite in the uniform shape of Catalytic Layer
State, expand three-phase reaction interface region, improves cell output and operation stability.
Summary of the invention
In view of the deficiencies of the prior art and disadvantage, the present invention proposes to be introduced directly into binder in a kind of catalyst synthesis processes
Prepare elctro-catalyst-binder composite method, realize catalyst and binder it is micro-, receive and uniformly mix on scale.
A kind of composite catalyst, the composite catalyst include metal active constituent and binder, the matter of the binder
It measures content and is not less than 5%, and be not higher than 40%；The average grain diameter of the binder is 50-100nm.
The partial size of the metal active constituent is 3-20nm.
The metal active constituent is Pt；The metal active constituent be PtM multicomponent catalyst, wherein M be Co, Pd,
One or more of Ni, Fe, Ru, Au, Sn, Cu.
The binder is polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polystyrene, one or two kinds of in Nafion
Above mixture.
The composite catalyst further includes carbon carrier, and mass content of the carbon carrier in the composite catalyst is
20-80%.
The preparation method of the composite catalyst, includes the following steps,
(1) preparing metal active component precursor salt solution, and it is made to be uniformly dispersed；
(2) dispersion liquid of binder is prepared, and it is molten to be added into addition step (1) described metal active constituent precursor salt
In liquid, the uniform mixed solution of ultrasonic disperse；
(3) reducing agent is added in the mixed solution obtained by step (2), control reaction carries out between 25-90 DEG C；
(4) mixed liquor after reaction obtained by step (3) is filtered, washs to obtain composite catalyst；
The mass ratio of metal and binder is 20:40-65:5 in precursor salt in the step (2).
Carbon carrier, the quality of the carbon carrier and metal are additionally added in step (1) the precursor salt solution preparation process
Than for 80:20~20:80.
Step (1) the metal active constituent precursor salt is Pt precursor salt, Co precursor salt, Pd precursor salt, Ni
One or both of precursor salt, Fe precursor salt, Ru precursor salt, Au precursor salt, Sn precursor salt, Cu precursor salt
More than；
The concentration of the metal active constituent precursor salt solution is 20-100 mMs every liter；Solvent is water, methyl pyrrole
The mixed solvent of one or more of pyrrolidone, ethyl alcohol.
Binder is polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polyphenyl in the dispersion liquid of step (2) described binder
The mixture of any one in ethylene or two kinds or more；Solvent be one or both of water, methyl pyrrolidone, ethyl alcohol with
On mixed solvent；The concentration of dispersion liquid is 0.1%-1%.
Step (3) reducing agent is NaBH4、KBH4, ascorbic acid, hydrogen, sodium formate, one of ethylene glycol or two
Kind or more.
In above-mentioned elctro-catalyst-binder composite preparation process, how effective optimal control synthetic parameters, design optimization
The interfacial structure of catalyst and binder is to realize that the two functions the key point of characteristic in compound.If binder content
Excessively high and absorption is wrapped in nanometer electrical catalyst surface, and the electrocatalysis characteristic and blocking electrode that can largely effect on catalyst reacted
Electronics conduction pathway in journey, is unfavorable for the generation of electrode reaction；Binder content is too low, and it is poly- that microcell occurs for nanometer electrical catalyst
Knot, catalyst activity component particle increase, and exposed effective active area reduces, and reduce electrode reaction rate.By rationally selecting
The binder introduced in catalysis preparation process and the carbon carrier material with conducting function are selected, binder can be weakened and be catalyzed
The adsorption strength on agent surface, while constructing to have both in micro/nano-scale region and hating liquid ventilation (binder), electron channel (carbon load
Body), the three-phase reaction interface area of electrochemical reaction active (nanocatalyst).
Compared with prior art, the invention has the following advantages that
(1) side of elctro-catalyst-binder compound is formed by being introduced directly into binder in catalyst preparation process
Method realizes that catalyst uniformly mixes on micro/nano-scale with binder, realizes the size of nanocatalyst and the control of size distribution
System；
(2) catalyst and binder are improved in the uniform state of Catalytic Layer, and then adjusts Catalytic Layer in-laws, hate fluid apertures
Structure distribution improves gas transport and phosphoric acid distribution, expands three-phase reaction interface region, improves cell output and fortune
Row stability.
Detailed description of the invention
Fig. 1 is catalyst slurry of the embodiment of the present invention 1 based on Pt/C-PTFE compound and PtCo/C-PTFE compound
Catalyst slurry (PtCo/C powder+PTFE) the aerodynamic particle size distribution map prepared with conventional method in comparative example 1；
Fig. 2 is Catalytic Layer scanning electron microscopic picture of the embodiment of the present invention 1 based on Pt/C-PTFE compound slurries.
Specific embodiment
Below with reference to specific embodiment, the present invention is further illustrated, to better understand the present invention.
Comparative example:
Under mechanical agitation, 50 mMs of every liter of boron are gradually added into 20 mMs of every liter of chloroplatinous acid aqueous solutions of potassium
Sodium hydride aqueous solution after being added dropwise, continues to be stirred to react 180 minutes.Then above-mentioned reaction liquid is carried out using centrifugal process
Washing purifying, removes supernatant, solid product is placed in vacuum drying oven 60 DEG C of baking 4h, powder is then ground to, obtains powdered
Pt black appliances catalyst.The TEM of respective sample is as shown in Figure 1.
Embodiment 1
Under mechanical agitation, 50 mMs of every liter of boron are gradually added into 20 mMs of every liter of chloroplatinous acid aqueous solutions of potassium
Sodium hydride aqueous solution after being added dropwise, continues to be stirred to react 60 minutes, the PTFE aqueous solution of 1wt% is then added, by reactant
System is warming up to 60 DEG C, continues to be stirred to react 120 minutes.Then washing purifying is carried out to above-mentioned reaction liquid using centrifugal process, moved
Except supernatant, finally disperse solid product in again spare in aqueous solution.The TEM of respective sample is as shown in Figure 2.
Embodiment 2
Under mechanical agitation, it is gradually added into 50 mMs every liter into 50 mMs of every liter of chloroplatinous acid aqueous solutions of potassium and resists
Bad hematic acid aqueous solution after being added dropwise, continues to be stirred to react 60 minutes, the PTFE aqueous solution of 1wt% is then added, by reactant
System is warming up to 80 DEG C, continues to be stirred to react 120 minutes.Then washing purifying is carried out to above-mentioned reaction liquid using centrifugal process, moved
Except supernatant, finally disperse solid product in again spare in aqueous solution.Gained Pt elctro-catalyst nano particle diameter is about
8nm or so, narrow size distribution.
Embodiment 3
Under mechanical agitation, 50 millis are gradually added into 50 mMs of every liter of potassium chloroplatinites and potassium chloropalladate aqueous solution
Mole every liter of aqueous ascorbic acid after being added dropwise, continues to be stirred to react 60 minutes, the PTFE that 1wt% is then added is water-soluble
Reaction system is warming up to 80 DEG C by liquid, continues to be stirred to react 120 minutes.Then above-mentioned reaction liquid is carried out using centrifugal process
Washing purifying, removes supernatant, finally disperses solid product in again spare in aqueous solution.Gained Pt-Pd double elements electricity is urged
Agent nano particle diameter is about 6nm or so, narrow size distribution.
Embodiment 4
Under mechanical agitation, 50 millis are gradually added into 50 mMs of every liter of potassium chloroplatinites and ruthenium hydrochloride aqueous solutions of potassium
Mole every liter of potassium borohydride aqueous solution after being added dropwise, continues to be stirred to react 60 minutes, the PTFE that 1wt% is then added is water-soluble
Reaction system is warming up to 80 DEG C by liquid, continues to be stirred to react 120 minutes.Then above-mentioned reaction liquid is carried out using centrifugal process
Washing purifying, removes supernatant, finally disperses solid product in again spare in aqueous solution.Gained Pt-Ru double elements electricity is urged
Agent nano particle diameter is about 6nm or so, narrow size distribution.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of composite catalyst, it is characterised in that: the composite catalyst includes metal active constituent and binder, described viscous
The mass content for tying agent is not less than 5%, and is not higher than 40%；The average grain diameter of binder is 50-100nm.
2. composite catalyst as described in claim 1, it is characterised in that: the partial size of the metal active constituent is 3-20nm.
3. composite catalyst as described in claim 1, it is characterised in that: the metal active constituent is Pt；The metal active
Group is divided into PtM multicomponent catalyst, and wherein M is one or more of Co, Pd, Ni, Fe, Ru, Au, Sn, Cu.
4. composite catalyst as described in claim 1, it is characterised in that: the binder be polytetrafluoroethylene (PTFE), Kynoar,
Polyethylene, polystyrene, mixture one or more kinds of in Nafion.
5. composite catalyst as described in claim 1, it is characterised in that: the composite catalyst further includes carbon carrier, the carbon
Mass content of the carrier in the composite catalyst is 20-80%.
6. a kind of preparation method of any composite catalyst of claim 1-4, it is characterised in that: include the following steps,
(1) preparing metal active component precursor salt solution, and it is made to be uniformly dispersed；
(2) dispersion liquid of binder is prepared, and is added into and step (1) described metal active constituent precursor salt solution is added
In, the uniform mixed solution of ultrasonic disperse；
(3) reducing agent is added in the mixed solution obtained by step (2), control reaction carries out between 25-90 DEG C；
(4) mixed liquor after reaction obtained by step (3) is filtered, washs to obtain composite catalyst；
The mass ratio of metal and binder is 20:40~65:5 in precursor salt in the step (2).
7. the preparation method of composite catalyst as claimed in claim 6, it is characterised in that: step (1) the precursor salt solution
It is additionally added carbon carrier in preparation process, the mass ratio of the carbon carrier and metal is 80:20~20:80.
8. the preparation method of composite catalyst as claimed in claim 6, it is characterised in that:
Step (1) the metal active constituent precursor salt is Pt precursor salt, Co precursor salt, Pd precursor salt, Ni forerunner
One or both of body salt, Fe precursor salt, Ru precursor salt, Au precursor salt, Sn precursor salt, Cu precursor salt with
On；
The concentration of the metal active constituent precursor salt solution is 20-100mM/L；Solvent is water, methyl pyrrolidone, ethyl alcohol
One or more of mixed solvent.
9. the preparation method of composite catalyst as claimed in claim 6, it is characterised in that:
In the dispersion liquid of step (2) described binder binder be polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polystyrene,
The mixture of any one in Nafion or two kinds or more；Solvent is one or both of water, methyl pyrrolidone, ethyl alcohol
Above mixed solvent；The concentration of dispersion liquid is 0.1-1wt%.
10. the preparation method of composite catalyst as claimed in claim 6, it is characterised in that:
Step (3) reducing agent is NaBH4、KBH4, ascorbic acid, hydrogen, sodium formate, one or both of ethylene glycol with
On.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129508A (en) * | 2019-12-17 | 2020-05-08 | 一汽解放汽车有限公司 | Transition metal doped platinum-carbon catalyst and preparation method and application thereof |
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| CN1919459A (en) * | 2006-08-25 | 2007-02-28 | 武汉理工大学 | Preparing process for metal granular catalyst modified by ionic conduction polymer |
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| CN111129508A (en) * | 2019-12-17 | 2020-05-08 | 一汽解放汽车有限公司 | Transition metal doped platinum-carbon catalyst and preparation method and application thereof |
| CN111129508B (en) * | 2019-12-17 | 2021-07-02 | 一汽解放汽车有限公司 | Transition metal doped platinum-carbon catalyst and preparation method and application thereof |
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