CN110661006A - Preparation method of ultralow-palladium-loaded Co-Ag @ Pd/C oxygen reduction catalyst - Google Patents
Preparation method of ultralow-palladium-loaded Co-Ag @ Pd/C oxygen reduction catalyst Download PDFInfo
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- CN110661006A CN110661006A CN201910869435.2A CN201910869435A CN110661006A CN 110661006 A CN110661006 A CN 110661006A CN 201910869435 A CN201910869435 A CN 201910869435A CN 110661006 A CN110661006 A CN 110661006A
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a preparation method of an ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst, which relates to the field of fuel cell catalysts, and is characterized in that firstly, a dispersant and an ethylene glycol solution are added into a flask, and after the mixture is uniformly stirred, oleylamine is added until the mixture is uniformly dispersed; then adding a cobalt chloride and silver nitrate mixed solution which has the same volume and takes ethylene glycol and oleylamine as solvents; then adding activated carbon powder to mix into homogeneous solution and preserving heat for a certain time to obtain a Co-Ag/C precursor; heating the precursor, keeping the temperature for a certain time, centrifuging, washing, freezing and drying to obtain a Co-Ag/C solid material; finally, redispersing the solid material to K2PtCl4And (3) heating and preserving heat for a certain time in the solution, washing and freeze-drying the obtained suspension to obtain the Co-Ag @ Pd/C oxygen reduction catalyst. The invention adopts an organic solvent method to ensureThe obtained catalyst has good crystallinity, fine particles, no serious agglomeration phenomenon and regular appearance. The catalyst has high quality activity, oxygen reduction initial potential close to that of a commercial platinum-carbon catalyst and high stability, and meanwhile, the content of noble metal Pd in the catalyst is low, so that the catalyst has low cost.
Description
Technical Field
The invention relates to the field of fuel cell catalysts, in particular to a preparation method of a low-palladium-supported Co-Ag @ Pd/C oxygen reduction catalyst.
Background
The fuel cell without the Carnot cycle process of the heat engine can efficiently convert chemical energy of organic and inorganic fuels and corresponding oxidants into electric energy, and the energy conversion rate is far higher than that of the traditional heat engine, so the fuel cell is considered as a first-choice clean and efficient power generation technology in the 21 st century, is a fourth type of power generation technology following hydraulic power generation, thermal power generation and nuclear power generation, and has important significance for solving two problems of energy shortage and environmental pollution in the world at present.
The technology is mature at present and the hydrogen fuel cell is popularized to the largest extent, so that the hydrogen fuel cell becomes various research hotspots for solving energy and environmental problems, the actual capacity conversion rate reaches 40% -60%, the research of the fuel cell is advanced in the front of the world in the international day, the international country and the international korea, the research of the fuel cell is mostly focused on the proton exchange membrane type fuel cell, and one of the key reasons for limiting the large-scale popularization of the fuel cell is the high cost of the noble metal catalyst. The PEMFC using hydrogen as fuel and air as oxidant is one of the most rapidly developed fuel cell systems with the highest technical maturity at present, generates current through electrode reaction, and has the advantages of high energy density, long service time, safety and environmental protection.
Nowadays, fuel cells have been successfully used in civil fields such as automobiles, power stations, portable power sources and the like, but low cost and long service life are still the problems facing commercialization, and the core problem is the catalyst. The catalyst for fuel cell needs noble metal platinum, so the cost is high, and in addition, the phenomenon of catalyst poisoning also occurs in the oxidation process, so the preparation of the fuel cell catalyst with high efficiency, cleanness and strong resistance to poisoning becomes the key point of people research. Advances in PEMFC performance or the process of PEMFC commercialization have also been held back in the creation of new high efficiency electrocatalysts. The Pd catalyst has the advantages of abundant element reserves, high catalytic performance, difficult poisoning, etc., and the price of pure metal thereof is far lower than that of Pt, so the Pd catalyst is considered as the most promising anode material of fuel cells and becomes a hot spot of research in recent years. However, in practice, pure Pd catalysts are prone to deactivation, and it is necessary to modify Pd appropriately to improve catalytic performance and stability.
Those skilled in the art have therefore endeavored to develop a more cost effective route to Co-Ag @ Pd/C oxygen reduction catalyst materials with performance meeting the practical requirements.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the present invention is how to provide a method for preparing a Co-Ag @ Pd/C oxygen reduction catalyst material with excellent electrochemical performance, simple preparation process and low cost.
In order to realize the aim, the invention provides a preparation method of an ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst, which is characterized by comprising the following steps:
step 1, adding a dispersant and a glycol solution into a 100ml round-bottom flask, stirring and mixing uniformly, and adding oleylamine to obtain a uniform solution;
step 2, preparing a mixed solution of cobalt chloride and silver nitrate by using ethylene glycol and oleylamine as a mixed solvent;
step 3, adding the mixed solution in the step 2 into the flask in the step 1 in the same volume;
step 4, adding activated carbon powder into the flask obtained in the step 1, mixing the activated carbon powder and the activated carbon powder into a homogeneous solution, and keeping the temperature of the homogeneous solution for a certain time to obtain a Co-Ag/C precursor;
step 5, heating the precursor in the step 4, keeping the temperature for a certain time, and then centrifugally washing, freezing and drying to obtain a Co-Ag/C solid material;
step 6, re-dispersing the Co-Ag/C solid powder obtained in the step 5 to K2PtCl4And (3) heating and preserving heat for a certain time in the solution, washing and freeze-drying the obtained suspension to obtain the Co-Ag @ Pd/C oxygen reduction catalyst.
Further, the volume ratio of the ethylene glycol to the oleylamine in the step 1 is 1:3.5, the concentration of the dispersing agent in the homogeneous solution is 6mg/ml, and the stirring time is 30 min.
Further, the dispersant in the step 1 is one of PVP, sodium citrate or cetyl trimethyl ammonium bromide.
Further, in the step 2, the volume ratio of the ethylene glycol to the oleylamine is 1:1, the concentration of the silver nitrate is 10mM-0.5M, the cobalt chloride is cobalt chloride hexahydrate, and the concentration ratio of the cobalt chloride hexahydrate to the silver nitrate is 1:3.
Further, the activated carbon powder in the step 4 is obtained by activating VulcanXC-72 activated carbon powder with 40% concentrated nitric acid, the mixing is ultrasonic and magnetic stirring for 2-3h, the heat preservation temperature is 80 ℃, and the heat preservation time is 1-2 h.
Further, the process of activating the VulcanXC-72 activated carbon powder by the concentrated nitric acid in the step 4 is HNO of 5mol/L3And (3) strongly stirring and refluxing for 12h, controlling the temperature at 90 ℃, washing with deionized water for three times and ethanol for one time after heat treatment and hydroxylation, then carrying out vacuum drying at 100 ℃, grinding and sieving with a 200-mesh sieve to obtain the activated carbon powder in the step (4).
Further, in the step 5, the heating mode is a condensation oil bath, the temperature is set to be one of 160 ℃, 180 ℃ or 200 ℃, the heat preservation time is 12 hours, and the centrifugal washing is 10000-turn centrifugation after ultrasonic cleaning is carried out for 20min by adopting a mixed solution of normal hexane and ethanol with a volume ratio of 1:5, and the operation is repeated for three times.
Further, the freeze drying in the step 5 is to freeze with liquid nitrogen and then carry out vacuum freeze drying at-55 ℃.
Further, K in step 62PtCl4The solvent of the solution is ethylene glycol and water with the volume ratio of 1:1, the concentration is 0.04mM, the volume is 20ml, and the Co-Ag/C solid powder is prepared by mixing the Co-Ag in the step 5and/C, grinding the solid material to obtain powder.
Further, in the step 6, the heating mode is oil bath at 60 ℃, and the heat preservation time is 5 hours.
The invention has the following technical effects:
the nanometer Co-Ag @ Pd/C oxygen reduction catalyst material is synthesized by an organic solvent method, has good crystallinity, fine particles, no serious agglomeration phenomenon and regular appearance. In a 0.1MKOH solution system, the material shows good electrochemical performance: the oxygen reduction initiation potential remained over 70% of the initial capacity after 100 cycles compared to commercial Pt/C, with a smooth and narrow electric double layer width, compared to the peak current.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a TEM image of a preferred embodiment of the present invention;
FIG. 2 is a Maping diagram of a preferred embodiment of the present invention;
FIG. 3 is a diagram of the quantitative analysis of the metal components in accordance with a preferred embodiment of the present invention;
FIG. 4 is a CV curve of a preferred embodiment of the present invention;
FIG. 5 is an LSV curve of a preferred embodiment of the invention;
FIG. 6 is a CV curve for a preferred embodiment of the present invention cycling to 200 cycles at 0.01V/s sweep speed.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
Adding PVP and ethylene glycol solution into a 100ml round-bottom flask, stirring for 30min, uniformly mixing, adding oleylamine, and adding ethylene glycol and oleylamineThe volume ratio is 1:3.5, and finally, a PVP homogeneous solution of 6mg/ml is prepared. The method comprises the steps of taking ethylene glycol and oleylamine in a volume ratio of 1:1 as a mixed solvent, preparing a mixed solution of cobalt chloride hexahydrate and silver nitrate solution in a concentration ratio of 1:3, and adding the mixed solution with the same volume as the PVP homogeneous solution into a round-bottom flask. Adding VulcanXC-72 activated carbon powder into a round-bottom flask, and passing the activated carbon powder through HNO at 5mol/L3Stirring and refluxing for 12h, controlling the temperature to be 90 ℃, carrying out heat treatment and hydroxylation, washing with deionized water for three times, washing with ethanol for one time, carrying out vacuum drying at 100 ℃, grinding, and sieving with a 200-mesh sieve to obtain the activated carbon powder. And stirring for 3 hours by ultrasonic and magnetic force to obtain a homogeneous solution, and then keeping the temperature of the solution at 80 ℃ for 2 hours to obtain the Co-Ag/C precursor. Placing the precursor in a condensing oil bath at 180 ℃, preserving heat for 12h, ultrasonically cleaning for 20min by using a mixed solution of n-hexane and ethanol with the volume ratio of 1:5, centrifuging at 10000 r, repeating the cleaning and centrifuging process for more than three times, freezing by using liquid nitrogen, and then carrying out vacuum freeze drying at-55 ℃ to obtain the Co-Ag/C solid material. The powder obtained by grinding the Co-Ag/C solid material is dispersed to 20ml K with the concentration of 0.04mM2PdCl4And (3) adding the solution into the solution, carrying out oil bath at 60 ℃ for 5h, and washing and freeze-drying the obtained suspension to obtain the Co-Ag @ Pd/C oxygen reduction catalyst.
As shown in the TEM image of FIG. 1, the Co-Ag @ Pd/C oxygen reduction catalyst particles obtained in this example were uniform spheres and had a particle diameter of about 10 nm. As shown in fig. 2, the catalyst particles contain three metal elements of Co, Ag, and Pd. As shown in FIG. 3, the catalyst only supports the ultralow content of Pd, and the mass percent is only 2.2%.
The prepared Co-Ag @ Pd/C catalyst powder is used as a cathode oxygen reduction active material and used as a cathode catalyst of the magnesium air fuel cell, and electrochemical tests are carried out, wherein the specific process is as follows:
5mg of catalyst is weighed, 200 mul of deionized water, 300ul of ethanol and 100 mul of Nafiom solution (produced by DuPont company, mass fraction is 5%) are added, ultrasonic treatment is carried out for 5 minutes, then a liquid transfer gun is used for dropping the mixed suspension on 3cm by 3cm carbon paper, and then the carbon paper is transferred to a vacuum drying oven for drying for 6 hours. Then the anode and the nickel mesh are combined together to form an air cathode, a plastic plate is used for manufacturing an open device, a square hole of 3cm x 3cm is formed in the middle of the device and is fixed by a rubber band and a screw, and the anode is made of magnesium material (20 x 2mm metal sheets, 320, 800 and 2000 # sandpaper are used for polishing the metal sheets, copper wires are used as leads, and the joints are sealed by rubber) and is soaked in 3.5% sodium chloride solution. Thereby completing a simple magnesium-air battery.
The electrochemical performance test adopts a Land battery performance test system and a CHI660A electrochemical workstation for characterization, a polarization curve is characterized by the CHI660A electrochemical workstation, a glassy carbon electrode with phi of 3mm and loaded with 5 mu L of catalyst solution (catalyst: ethanol: Nafion of 5mg:2ml:100ul) is used as a working electrode, a platinum sheet electrode with 2.5mm of 2.5mm is used as a counter electrode, a saturated calomel electrode (Shanghai apparatus electroscience and company Limited) is used as a reference electrode, the scanning range is-1.0V-0.2V, and the scanning speed is 0.01V; a Land CT2001A charge-discharge tester produced by Wuhanjinnuo electrons is adopted to test the discharge performance of the magnesium-air battery, a constant current discharge mode is adopted, the tester is respectively connected with an air cathode and a magnesium material anode, and the current density is set to be 5mA cm-2。
As shown in FIG. 4, we can see that the catalyst has the highest higher oxygen reduction current peak on the cyclic voltammogram from the tenth circle to the sixteenth circle, and the peak intensity reaches 0.0503mA cm-2. As shown in FIG. 5, the initial reduction potential was also less than 0.1v different from that of the Pt/C commercial catalyst (Shanghai Hesen electric Co., Ltd.). As shown in fig. 6, the oxygen reduction peak current density decreased first and then after 200 CV cycles, and remained at 75% of the maximum after the end of the cycle.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method of an ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst is characterized by comprising the following steps:
step 1, adding a dispersant and a glycol solution into a 100ml round-bottom flask, stirring and mixing uniformly, and adding oleylamine to obtain a uniform solution;
step 2, preparing a mixed solution of cobalt chloride and silver nitrate by using ethylene glycol and oleylamine as a mixed solvent;
step 3, adding the mixed solution in the step 2 into the flask in the step 1 in the same volume;
step 4, adding activated carbon powder into the flask obtained in the step 1, mixing the activated carbon powder and the activated carbon powder into a homogeneous solution, and keeping the temperature of the homogeneous solution for a certain time to obtain a Co-Ag/C precursor;
step 5, heating the precursor in the step 4, keeping the temperature for a certain time, and then centrifugally washing, freezing and drying to obtain a Co-Ag/C solid material;
step 6, re-dispersing the Co-Ag/C solid powder obtained in the step 5 to K2PtCl4And (3) heating and preserving heat for a certain time in the solution, washing and freeze-drying the obtained suspension to obtain the Co-Ag @ Pd/C oxygen reduction catalyst.
2. The method of claim 1 wherein the volume ratio of ethylene glycol to oleylamine in step 1 is 1:3.5, the concentration of dispersant in the homogeneous solution is 6mg/ml and the stirring time is 30 min.
3. The method of preparing an ultra-low palladium supported Co-Ag @ Pd/C oxygen reduction catalyst according to claim 1, wherein the dispersant of step 1 is one of PVP, sodium citrate or cetyltrimethylammonium bromide.
4. The method of preparing an ultra-low palladium supported Co-Ag @ Pd/C oxygen reduction catalyst as claimed in claim 1, wherein in step 2 the ethylene glycol to oleylamine volume ratio is 1:1, the silver nitrate concentration is 10mM-0.5M, the cobalt chloride is cobalt chloride hexahydrate, and the ratio of the cobalt chloride hexahydrate to the silver nitrate concentration is 1:3.
5. The preparation method of the ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst as claimed in claim 1, wherein the activated carbon powder in the step 4 is obtained by activating VulcanXC-72 activated carbon powder with 40% concentrated nitric acid, the mixing is ultrasonic and magnetic stirring for 2-3h, the heat preservation temperature is 80 ℃, and the heat preservation time is 1-2 h.
6. The preparation method of the ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst according to claim 5, wherein the step 4 of activating the VulcanXC-72 activated carbon powder by the concentrated nitric acid is to use 5mol/L of HNO3And (3) strongly stirring and refluxing for 12h, controlling the temperature at 90 ℃, washing with deionized water for three times and ethanol for one time after heat treatment and hydroxylation, then carrying out vacuum drying at 100 ℃, grinding and sieving with a 200-mesh sieve to obtain the activated carbon powder in the step (4).
7. The method for preparing the ultralow palladium supported Co-Ag @ Pd/C oxygen reduction catalyst according to claim 1, wherein the heating manner in the step 5 is a condensation oil bath, the temperature is set to be one of 160 ℃, 180 ℃ or 200 ℃, the holding time is 12h, the centrifugal washing is 10000-turn centrifugation after ultrasonic cleaning for 20min by using a mixed solution of n-hexane and ethanol in a volume ratio of 1:5, and the process is repeated three times.
8. The method of claim 1 wherein the freeze-drying step of step 5 is performed by freezing with liquid nitrogen and then vacuum freeze-drying at-55 ℃.
9. The method of preparing an ultra-low palladium supported Co-Ag @ Pd/C oxygen reduction catalyst of claim 1, wherein K is in step 62PtCl4The solvent of the solution is 1:1 by volumeAnd (3) ethylene glycol and water, wherein the concentration is 0.04mM, the volume is 20ml, and the Co-Ag/C solid powder is obtained by grinding the Co-Ag/C solid material obtained in the step (5).
10. The method of preparing an ultra-low palladium supported Co-Ag @ Pd/C oxygen reduction catalyst as claimed in claim 1, wherein the heating manner in step 6 is an oil bath at 60 ℃ and the holding time is 5 h.
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