CN108075140A - A kind of preparation method and application of platinum base alloy elctro-catalyst - Google Patents
A kind of preparation method and application of platinum base alloy elctro-catalyst Download PDFInfo
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- CN108075140A CN108075140A CN201611014866.3A CN201611014866A CN108075140A CN 108075140 A CN108075140 A CN 108075140A CN 201611014866 A CN201611014866 A CN 201611014866A CN 108075140 A CN108075140 A CN 108075140A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
The invention belongs to noble metal electrocatalyst fields, are related to a kind of preparation method and application of platinum base alloy elctro-catalyst.The platinum carbon catalyst, alkaline matter and X salting liquids of platinum containing amount 30wt%~70wt% are uniformly mixed preparation suspension, the X is transition metal；More than the condensing reflux 0.5h at 100 200 DEG C, staticly settles, and removes supernatant, washs to neutrality, vacuum drying；Under the reducing atmosphere containing hydrogen, 0.5 3h is heat-treated at 600 800 DEG C；Platinum X-alloy carbon compound described in pickling is to obtain the platinum base alloy elctro-catalyst.The present invention is simple to operate and friendly to environment, suitable for large-scale production；There are higher oxygen reduction activity and stability, can be applied in fuel cell.
Description
Technical field
The invention belongs to noble metal electrocatalyst fields, are related to a kind of preparation method of platinum base alloy elctro-catalyst and answer
With.
Background technology
Fuel cell is the power generator that the chemical energy with fuel is directly translated into electric energy, since it is followed from Kano
The limitation of ring makes it have the advantages of energy conversion efficiency is high, and fuel cell also has environmental-friendly, sustainable power generation, combustion
The advantages that material is diversified and higher than energy, therefore it is subject to the extensive concern in the world.Elctro-catalyst is one of fuel cell important
Component, at present, the catalyst that Proton Exchange Membrane Fuel Cells uses is mainly platinum and its alloy catalyst, but the valency of platinum
Lattice are expensive and reserves in China are relatively low, limit its application in a fuel cell.Therefore, how platinum utilization is improved,
The platinum-based electrocatalyst for preparing high activity is the main problem that we study.
In order to reduce the cost of catalyst and improve catalytic efficiency, a most efficient method is exactly using inexpensive transition
Metal (Co, Ni, Fe and Cr etc.) forms hud typed catalyst with platinum Pt, and this catalyst can not only change the geometry distribution of Pt
(reducing Pt-Pt bond lengths), and relevant electronic structure (such as d electronics vacancy of Pt) can be changed, so as to greatly weaken
The combination power of o-o bond and metal-oxygen key advantageously forms and absorbs the intermediate of oxygen to enhance the redox of the catalyst
(ORR) it is active.
The patent application document of Publication No. US7053021B1 disclosed a kind of organic synthesis on May 30th, 2006
The method of PtVFe alloys.Pt nucleocapsids prepared by this method not only reduce the content of Pt, and substantially increase ORR catalysis and live
Property.The purer Pt/C of its catalytic activity improves 2-4 times.However the method largely uses organic solvent, and it is larger using toxicity
1,2- dihydroxy hexadecanes make reducing agent.Based on the considerations of safety and environmental protection aspect, it is raw that the method is not suitable for high-volume industry
Production.Furthermore since introduced inexpensive metal will gradually dissolve in acid solution or fuel cell, cause the stabilization of catalyst
Property be deteriorated and interfere its application in Proton Exchange Membrane Fuel Cells.
(STAMENKOVIC V R, MUN B S, ARENZ M, the et al.Trends in such as Stamenkovic
Electrocatalysis on Extended and Nanoscale Pt-Bimetallic Alloy
Surfaces.Nature Materials,2007,6(3):241-247.) respectively to sputter and anneal under UHV condition
Method two kinds of body phase atomic ratios have been made as 3:1 Pt3M (M=Ni, Co, Fe, Ti, V) polycrystalline.Wherein, sputtering method obtains
Alloy most surface Pt atomic ratios are 75%, and the alloy most surface Pt atoms that annealing method obtains are then 100%, and test finds two
The activity of person is above polycrystalline Pt.But the process employs electrochemical method synthesis, it is necessary to which special device, is not suitable for big rule
Mould produces.
The patent application document of Publication No. US20090098420A1 discloses a kind of fuel electricity on April 16th, 2009
The preparation method of pond catalyst, first with freeze-drying the conditions such as (freeze-dry) and hydrogeneous gaseous mixture 600 DEG C,
800 DEG C or 900 DEG C of high-temperatures reduce to form alloy, then by chemistry and electrochemistry the method for alloy are gone successfully to obtain respectively
The Pt of 18wt%Pt and 22wt%Pt seriesxCuy/ C catalyst.The result shows that the elution of Cu can cause carrying for 4 times of electro catalytic activities
High and 10 times of high specific activities.But this method of freeze-drying is not suitable for large-scale industrial production.
Present invention employs the methods that heat treatment reduction prepares catalyst, and special preparation facilities, preparation method is not required
Simply, it is easy to mass produce.Simultaneously as having carried out pickling to the catalyst of thermal reduction processing, surface is eliminated in acidity
The transition metal that can be dissolved in environment, makes surface play the role of roughening, improves catalyst towards oxygen reduction reaction
Catalytic activity, there has also been certain raisings for stability.
The content of the invention
It is an object of the invention to propose a kind of preparation method and applications of platinum base alloy elctro-catalyst, this method letter
It is single, it is easily controllable, suitable for large-scale production.
The present invention comprises the steps of：
A kind of preparation method of platinum base alloy elctro-catalyst, by platinum carbon catalyst, the alkali of platinum containing amount 30wt%~70wt%
Property the substance and mixing of X salting liquids, more than ultrasonic disperse 10min, it is made to be uniformly dispersed to obtain suspension, the X is transition metal；
More than the condensing reflux 0.5h at 100-200 DEG C, staticly settles, and removes supernatant, washs to neutrality, vacuum drying；Containing
Under the reducing atmosphere of hydrogen, 0.5-3h is heat-treated at 600-800 DEG C, obtains platinum X-alloy carbon compound；Platinum X described in pickling is closed
Golden carbon compound is to obtain the platinum base alloy elctro-catalyst.
In the platinum carbon catalyst, X salting liquids, the molar ratio of platinum and X are 1:1.
The alkaline matter is potassium hydroxide, sodium hydroxide, lithium hydroxide, beryllium hydroxide, magnesium hydroxide, hydroxide
One or both of strontium, calcium hydroxide, barium hydroxide, ammonium hydroxide, urea are mixed above, adjust the pH=9 of suspension.
The X salt is XF2、XCl2、XBr2、XI2、X(NO3)2Or XSO4, X is cobalt, nickel, iron or chromium.
The acid pickling step includes：Platinum X-alloy carbon compound is put into 0.5-1M sulfuric acid solution pickling, 60 DEG C~80
DEG C stirring 14h-40h.
The platinum content of the platinum base alloy elctro-catalyst is 40%~70%.
The platinum base alloy elctro-catalyst that the preparation method obtains is applied to fuel cell.
The advantageous effect of technical solution of the present invention includes at least：
The method for the heating condensing reflux that the present invention uses, has not only speeded up the sedimentation of sediment, and has made the hydroxide of X
Object is more uniformly distributed what platinum carbon catalyst surface disperseed.
Technical solution of the present invention has finally obtained platinum using the X metals of the chemical method removal platinum alloy superficial layer of pickling
Based alloy elctro-catalyst.Acid pickling step is specifically in 60 DEG C~80 DEG C of acid solution, is flowed back using inert gas shielding, is made
Standby catalyst has higher performance.
Specific embodiment
Test method in embodiment includes：
Cyclic voltammetry：
Electrolyte：N at room temperature2The 0.1M HClO of gas saturation4Aqueous solution, sweep speed 50mV/s, voltage scan range
0.03~1.2V (compared with reversible hydrogen electrode) is taken off using hydrogen and pays areal calculation ECA, and test equipment is collocation rotating disk electrode (r.d.e)
System (Pine Instruments, U.S.) CHI730D types electrochemical analyser (CHI Instruments Inc.,
U.S.).Hydrogen reduction is tested：
Electrolyte：O at room temperature2The 0.1M HClO of saturation4Aqueous solution, rotating circular disk rotating speed 1600rpm, forward scan
10mV/s, voltage scan range are 0.2~1V (compared with reversible hydrogen electrode), and test equipment is collocation rotating disk electrode (r.d.e) system
The CHI730D types electrochemical analyser (CHI Instruments Inc., U.S.) of (Pine Instruments, U.S.).
Stability test：
Electrolyte：N2The 0.1M HClO of gas saturation4Aqueous solution, sweep speed 50mV/s, voltage scan range 0.6~
1.2V (compared with reversible hydrogen electrode), 500 circle of room temperature scanning, test equipment are collocation rotating disk electrode (r.d.e) system (Pine
Instruments, U.S.) CHI730D types electrochemical analyser (CHI Instruments Inc., U.S.).
Embodiment 1：
10mL deionized waters are added in beaker, then by 0.0746g Co (NO3)2·6H2O is added in beaker, stirring
Uniformly, 0.1g 50wt%Pt/C, ultrasonic 30min are added in, adds in by volume 1:4 diluted concentrated ammonia liquors, adjust pH=9,110
DEG C condensing reflux 2h, staticly settles, removes supernatant, then centrifuge sediment, and drying is dried in vacuo at 60 DEG C.Then
In 600 DEG C, 10%H2Thermal reduction processing 3h, cooled to room temperature under/Ar atmosphere.By obtained catalyst and 30mL, 1mol/
The H of L2SO4Solution mixes, then ultrasonic 30min is stirred for 24 hours in 80 DEG C of oil baths.It then centrifuges, washs for several times, 60 DEG C
Lower vacuum drying drying.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 53m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 273mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 27% for the 15%, mass activity of oxygen reduction reaction.
Embodiment 2：
Operating process is, in the present embodiment, the type of X salt is cobalt chloride with embodiment 1 different from 1 part of embodiment
(CoCl2)。
In the present embodiment, CoCl2Addition be 0.0333g.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 47m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 271mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 26% for the 16%, mass activity of oxygen reduction reaction.
Embodiment 3：
Operating process is, in the present embodiment, the type of X salt is nickel chloride with embodiment 1 different from 1 part of embodiment
(NiCl2)。
In the present embodiment, NiCl2Addition is 0.0332g.
After carrying out cyclic voltammetry to the platinum-nickel alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 48m2/g Pt；
After carrying out hydrogen reduction test to the platinum-nickel alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 266mA/mg Pt；
After carrying out stability test to the platinum-nickel alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 25% for the 15%, mass activity of oxygen reduction reaction.
Embodiment 4：
Operating process is that alkaline matter used is in the present embodiment with embodiment 1 different from 1 part of embodiment
The aqueous solution of 0.05M potassium hydroxide.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 40m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 247mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 31% for the 28%, mass activity of oxygen reduction reaction.
Embodiment 5：
Operating process is that the condition of condensing reflux is 120 in the present embodiment with embodiment 1 different from 1 part of embodiment
DEG C condensing reflux 2h.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 48m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 269mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 26% for the 16%, mass activity of oxygen reduction reaction.
Embodiment 6：
Operating process is that the condition of condensing reflux is 160 in the present embodiment with embodiment 1 different from 1 part of embodiment
DEG C condensing reflux 1h.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 40m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 241mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 23% for the 15%, mass activity of oxygen reduction reaction.
Embodiment 7：
Operating process is different from 1 part of embodiment with embodiment 1, the present embodiment when carrying out heat-treatment alloying,
Heat treatment condition is 700 DEG C, 5%H2Thermal reduction processing 2h under/Ar atmosphere.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 46m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 260mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 23% for the 14%, mass activity of oxygen reduction reaction.
Embodiment 8：
Operating process is different from 1 part of embodiment with embodiment 1, the present embodiment when carrying out heat-treatment alloying,
Heat treatment condition is 800 DEG C, 5%H2Thermal reduction processing 1h under/Ar atmosphere.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 43m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 250mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 22% for the 12%, mass activity of oxygen reduction reaction.
Embodiment 9：
Operating process is that the Pt/C used in the present embodiment is 70wt%Pt/ with embodiment 1 different from 1 part of embodiment
C, the Co (NO of addition3)2·6H2The amount of O is 0.104g, other preparation process can refer to embodiment one.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 34m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 184mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 22% for the 8%, mass activity of oxygen reduction reaction.
Comparative example 1：
Operating process is that the condition of condensing reflux is 50 in the present embodiment with embodiment 1 different from 1 part of embodiment
DEG C condensing reflux is for 24 hours.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 38m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 160mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 29% for the 17%, mass activity of oxygen reduction reaction.
Comparative example 2：
Operating process is that the condition of condensing reflux is 80 in the present embodiment with embodiment 1 different from 1 part of embodiment
DEG C condensing reflux 12h.
After carrying out cyclic voltammetry to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst is obtained
Electrochemical surface area be 40m2/g Pt；
After carrying out hydrogen reduction test to the platinum cobalt alloy carbon particle catalyst, the platinum carbon particle catalyst hydrogen reduction is obtained
The mass activity of reaction is 208mA/mg Pt；
After carrying out stability test to the platinum cobalt alloy carbon particle catalyst, the electrification of the platinum carbon particle catalyst is obtained
It learns surface area losses and falls to 26% for the 14%, mass activity of oxygen reduction reaction.
It is understood based on above-described embodiment, the inexpensive transition metal such as cobalt is added in platinum carbon catalyst, go to close by pickling
The platinum cobalt alloy elctro-catalyst that golden step is formed has very high electro catalytic activity, initial redox reaction (ORR) activity
273mA/mg Pt and 53m can be reached respectively with initial electrochemical surface area2/g Pt.According to the application preparation method institute
The platinum alloy C catalyst being prepared possesses higher platinum content.
Claims (7)
1. a kind of preparation method of platinum base alloy elctro-catalyst, which is characterized in that by the platinum carbon of platinum containing amount 30wt%~70wt%
Catalyst, alkaline matter and the mixing of X salting liquids, more than ultrasonic disperse 10min make it be uniformly dispersed to obtain suspension, and the X is
Transition metal；More than the condensing reflux 0.5h at 100-200 DEG C, staticly settles, and removes supernatant, washs to neutrality, vacuum is done
It is dry；Under the reducing atmosphere containing hydrogen, 0.5-3h is heat-treated at 600-800 DEG C, obtains platinum X-alloy carbon compound；Pickling
The platinum X-alloy carbon compound is to obtain the platinum base alloy elctro-catalyst.
2. preparation method according to claim 1, which is characterized in that in the platinum carbon catalyst, X salting liquids, platinum and X
Molar ratio be 1:1.
3. preparation method according to claim 1, which is characterized in that the alkaline matter is potassium hydroxide, hydroxide
One kind in sodium, lithium hydroxide, beryllium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, urea or
Two or more mixing adjust the pH=9 of suspension.
4. preparation method according to claim 1, which is characterized in that the X salt is XF2、XCl2、XBr2、XI2、X
(NO3)2Or XSO4, X is cobalt, nickel, iron or chromium.
5. preparation method according to claim 1, which is characterized in that acid pickling step includes：
Platinum X-alloy carbon compound is put into the aqueous solution pickling of 0.5-1M sulfuric acid, 14h-40h is stirred at 60 DEG C~80 DEG C.
6. preparation method according to claim 1, which is characterized in that the platinum content of the platinum base alloy elctro-catalyst is
40%~70%.
7. the platinum base alloy elctro-catalyst that preparation method described in claim 1 obtains is applied to fuel cell.
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Cited By (8)
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| CN109713323A (en) * | 2018-11-27 | 2019-05-03 | 浙江大学 | A kind of preparation method of PtNi/C alloy catalyst |
| CN111589454A (en) * | 2020-05-15 | 2020-08-28 | 无锡威孚高科技集团股份有限公司 | High-temperature preparation method of binary alloy catalyst of proton exchange membrane fuel cell |
| CN111744473A (en) * | 2019-03-27 | 2020-10-09 | 宁波中科科创新能源科技有限公司 | Preparation method of Pt-based multi-component alloy nano electro-catalyst |
| CN112510220A (en) * | 2020-11-19 | 2021-03-16 | 武汉大学 | Core-shell type platinum-based alloy electrocatalyst with high oxygen reduction performance and preparation method thereof |
| CN113161563A (en) * | 2021-04-28 | 2021-07-23 | 郑州中科新兴产业技术研究院 | Platinum-cobalt alloy catalyst for fuel cell and preparation method thereof |
| CN114171745A (en) * | 2021-10-09 | 2022-03-11 | 氢电中科（广州）新能源设备有限公司 | Method for optimizing carbon-supported platinum-based alloy catalyst process |
| CN114182267A (en) * | 2022-02-14 | 2022-03-15 | 北京理工大学 | Electrochemical surface treatment method of electrode catalyst for fuel cell |
| CN114464823A (en) * | 2022-01-21 | 2022-05-10 | 先进能源产业研究院(广州)有限公司 | Oxygen reduction reaction catalyst and preparation method thereof |
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| CN111744473A (en) * | 2019-03-27 | 2020-10-09 | 宁波中科科创新能源科技有限公司 | Preparation method of Pt-based multi-component alloy nano electro-catalyst |
| CN111589454A (en) * | 2020-05-15 | 2020-08-28 | 无锡威孚高科技集团股份有限公司 | High-temperature preparation method of binary alloy catalyst of proton exchange membrane fuel cell |
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| CN113161563A (en) * | 2021-04-28 | 2021-07-23 | 郑州中科新兴产业技术研究院 | Platinum-cobalt alloy catalyst for fuel cell and preparation method thereof |
| CN114171745A (en) * | 2021-10-09 | 2022-03-11 | 氢电中科（广州）新能源设备有限公司 | Method for optimizing carbon-supported platinum-based alloy catalyst process |
| CN114464823A (en) * | 2022-01-21 | 2022-05-10 | 先进能源产业研究院(广州)有限公司 | Oxygen reduction reaction catalyst and preparation method thereof |
| CN114182267A (en) * | 2022-02-14 | 2022-03-15 | 北京理工大学 | Electrochemical surface treatment method of electrode catalyst for fuel cell |
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Application publication date: 20180525 |