CN101229512A - Method of increasing fuel cell catalyst stability - Google Patents
Method of increasing fuel cell catalyst stability Download PDFInfo
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- CN101229512A CN101229512A CNA2007101573759A CN200710157375A CN101229512A CN 101229512 A CN101229512 A CN 101229512A CN A2007101573759 A CNA2007101573759 A CN A2007101573759A CN 200710157375 A CN200710157375 A CN 200710157375A CN 101229512 A CN101229512 A CN 101229512A
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- 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 discloses a technology used for improving the stability of catalysts in the fuel cell industry; in particular to a process for preparing novel catalysts through graphitize treatment of carbon carriers. The preparation process of the invention, under the protection of inert gas with high-purity, carries out high-temperature heat treatment to common commercial carbon carriers to cause carrier materials to be partially graphitized and eliminate partial impurities in the original supporters, thus improving the stable properties of the high carbon carriers. Furthermore, the graphitized materials are carried out acidification treatment and a direct-reduction process or an ethylene glycol reduction process is adopted to prepare the catalysts in order to improve the stability of fuel cell catalysts. The invention is characterized by new structure, simple technique conditions, lower cost, being relatively suitable for scale production, etc. Hence, the invention belongs to a method that integrates economical efficiency and practicability into a whole and improves the stability of the fuel cell catalysts.
Description
Technical field
The present invention relates to a kind of technology that is used to improve catalyst stability in the fuel cell industries, specifically a kind of method of the catalyst carbon carrier being carried out graphitization processing and preparing new catalyst.
Background technology
At present, performance degradation is the key factor in its life-span of restriction behind the not high and long-play of the stability of catalyst about 2000 hours the life-span of electrode in the fuel cell-powered car.The normal catalyst that uses is that carbon carries platinum (Pt/C) material, and wherein the corrosion of carbon carrier is one of key factor that influences catalyst stability.The corrosion of carbon carrier can cause coming off of Pt particle and run off, and reunion and the migration of aggravation Pt, thereby causes the decline that the catalyst electrochemical surface is long-pending, so that causes the loss of battery performance.Therefore, carbon carrier plays a part very important to raising activity of such catalysts and stability.
Studies show that desirable carbon carrier should possess following condition: (1) higher specific surface area, thus help the high degree of dispersion of noble metal active component; (2) high-graphitized, have the good electron conducting power; (3) suitable pore structure is to reduce the transmission migration resistance of reactant, product and intermediate.At present, the most frequently used carbon carrier is the Vulcan XC-72 that Cabot company produces.The specific area of this carbon carrier is higher, and (the BET specific area is about 245m
2/ g), and have abundant central hole structure.Its shortcoming is: during the battery long-time running, and the less stable of this carrier, easily oxidized or partial corrosion etc., and in the oxidizing process of carbon, the platinum particles of carrier surface also may take place to run off or assemble, and the catalytic activity of catalyst is descended significantly.
Carried out a large amount of research at the stability problem of catalyst both at home and abroad in recent years, the method for solution mainly is to adopt the material of improvement in performance as catalyst carrier.The catalysis journal, reported Zhang Shengsheng etc. adopted tungsten carbide as catalyst carrier, studied its antioxygenic property at 2007,28 (2): 109.J.Power Sources, 2006,161 (2): Chhina etc. has also reported and has adopted the exploratory result of indium oxide thallium as catalyst carrier in 893.J.Power Sources, 2006,158, people such as X.Wang has then selected for use the higher carbon nanotube (MWNT) of stability to replace Vulcan XC-72 commonly used to do carrier material among the 154-159.In addition, SWCN, multi-walled carbon nano-tubes, carbon nano-fiber and carbon nanometer micro ball etc. also are used as catalyst carrier, have all improved the stability of catalyst to some extent.But these preparation methods are more complicated all, and cost is quite high, has therefore limited its large-scale production to a certain extent.At existing problem in the above-mentioned prior art, the method for a kind of novel raising fuel cell catalyst stability of research and design, existing problem is very necessary in the prior art thereby overcome.
Summary of the invention
In view of existing problem in the above-mentioned prior art, the objective of the invention is a kind of method that improves fuel cell catalyst stability of research and design, by improving the degree of graphitization of carbon support material, adopt direct-reduction process to prepare the new fuel cell catalyst then, improved the stability of catalyst.Thereby solve problems such as fuel-cell catalyst preparation method complexity, cost of manufacture height, restriction large-scale production.A kind of method that improves fuel cell catalyst stability of the present invention, it is as follows that it manufactures step:
A, carbon support material are carried out graphitization processing; Carbon support material is placed in the resistant to elevated temperatures graphite crucible, and crucible put into Medium frequency induction high temperature graphitization stove heat treated, be evacuated to about 10Pa earlier during heating, stop to vacuumize when being warming up to 1000 ℃ ~ 2900 ℃, fill highly purified inert gas Ar gas and protect to stove, air pressure is 0.09MPa, and heat treatment time is 0.5 ~ 20 hour, stop heating, the material after the graphitization processing is with the stove cool to room temperature;
B, the material after the graphitization processing is carried out acidification; Material after the graphitization processing is placed in the hydrochloric acid solution, and its concentration of hydrochloric acid solution scope is 0.01-10mol/L, flood after 2-12 hour to filter, and the water flushing is not to there being chlorion, then in 100 ℃ of oven dry of drying oven;
C, employing direct-reduction process prepare catalyst; (10mg/ml) pours in the there-necked flask platinum acid chloride solution; feed nitrogen protection and stirring; add reducing agent formaldehyde; add sodium hydroxide solution (5%) after the stirring again; make whole solution be alkalescent; and then add material after the graphitization processing of being soaked by isopropyl alcohol; then; solution is heated to 80 ℃; constant temperature dropped to room temperature after 1 hour, and logical carbon dioxide is 1 hour in solution. and washing dries to constant weight under 100 ℃ of drying ovens after do not have chlorion after filtration; promptly make the Pt/C eelctro-catalyst, the load amount of precious metals pt is 5% ~ 70% in the catalyst usually.
Direct-reduction process of the present invention prepares catalyst and also can adopt the reduction of ethylene glycol legal system to be equipped with catalyst, adopts the reduction of ethylene glycol method to be meant that it is that reducing agent prepares catalyst that spent glycol replaces formaldehyde.Used highly purified inert gas Ar gas of the present invention also can high pure nitrogen, high-purity argon gas, gas or their mists such as high-pure helium body.Used carbon support material of the present invention can be the VulcanXC-72 that uses always, also can be commercial absorbent charcoal materials such as acetylene black, BP2000, M1300.In the process of carrying out acidification of the present invention, the acid of use can be used watery hydrochloric acid, also can use acidic intermediums such as dilute sulfuric acid, rare nitric acid and acetic acid solution.
The catalyst of preparation of the present invention mainly is the Pt/C catalyst, is called the monometallic carbon carrier catalyst.The bimetallic or the multimetal reforming catalyst that also can prepare the carrier stabilisation, the alloy catalyst that Pt such as bimetallic such as PtRu/C, PtIr/C, PtFe/C, PtCo/C, PtNi/C and transition metal and other noble metals form.Catalyst more than three components that Pt such as multimetal reforming catalyst such as PtRuIr/C, PtCoNi/C and two or more transition metal and noble metal form.The preparation method is identical with preparation Pt/C catalyst, and difference is when the preparation multicomponent catalyst, with the salt solution mix of platinum acid chloride solution and corresponding metal, pours in the there-necked flask.When for example preparing the PtRu/C catalyst, with a certain amount of H
2PtCl
6Solution and RuCl
3Stir under the room temperature after solution mixes, pour in the there-necked flask again, following step is identical with step C.Promptly make bimetallic PtRu/C catalyst.
The present invention mainly by improving the degree of graphitization of carbon support material, adopts direct-reduction process to prepare the new fuel cell catalyst then, has improved the stability of catalyst.The superiority that the present invention is very big is exactly that cost is low, and technology is simple relatively and effect is remarkable, relatively is fit to large-scale production.
Invention novelty and creativeness are illustrated:
1, by improving the degree of graphitization of catalyst carrier, utilizes the high stability of graphite-structure, improve the stability of fuel cell supported catalyst.
2, can carry out acidification to the graphitization carrier, improve the wetability of carrier, adopt direct-reduction process or reduction of ethylene glycol method to make the higher catalyst of stability.
3, whole process easy operating, condition is controlled easily, is suitable for large-scale production.
The present invention has that novel structure, process conditions are simple, cost is lower, relatively be fit to advantage such as large-scale production, and it puts goods on the market in enormous quantities and will produce positive social benefit and remarkable economic efficiency.
Description of drawings
The present invention has six accompanying drawings, wherein
The XRD diffraction spectrogram of carbon dust VX-1800 and VX among accompanying drawing 1, the embodiment 1
Accompanying drawing 2, embodiment 1 prepared catalyst Pt/VX-1800 and Pt/VX cyclic voltammetric comparison diagram.
The XRD diffraction spectrogram of carbon dust VX-2100 and VX among accompanying drawing 3, the embodiment 2
Cyclic voltammetric comparison diagram before and after accompanying drawing 4, the oxidation of Pt/VX electrode 1.75V constant voltage
Cyclic voltammetric comparison diagram before and after accompanying drawing 5, the oxidation of Pt/VX-2100 electrode 1.75V constant voltage
The thermogravimetric analysis figure of accompanying drawing 6, Pt/VX and Pt/VX-2100
The specific embodiment
Specific embodiments of the invention are as follows:
Embodiment 1
Commercial carbon powder material Vulcan XC-72 about 200g is placed in the resistant to elevated temperatures graphite crucible, and graphite crucible is put into Medium frequency induction high temperature graphitization stove carry out graphitization processing.Its temperature is chosen as 1800 ℃.Treatment process is as follows: be evacuated to earlier about 10Pa, feeding temperature-raising adopts manually and heats up then, stops when being warming up to holding temperature vacuumizing, and filling highly purified Ar gas to stove internal gas pressure is 0.09MPa.And in outlet temperature after constant 0.5 hour, sample is with the stove cool to room temperature.With this material with carbon element is carrier, uses direct method of reducing to prepare the Pt/C catalyst.Fig. 1 is the XRD comparison diagram of this routine graphitized carbon carrier and original carbon dust, and Fig. 2 is the cyclic voltammogram of the catalyst of preparation.
Embodiment 2:
Commercial carbon powder material Vulcan XC-72 about 200g is placed in the resistant to elevated temperatures graphite crucible, and graphite crucible is put into Medium frequency induction high temperature graphitization stove carry out graphitization processing.Its temperature is chosen as 2100 ℃.Treatment process is as follows: when holding temperature equals or is higher than 2000 ℃, be evacuated to earlier about 10Pa, then feeding temperature-raising, adopt manually and heat up, be warming up to 2000 ℃ of insulations earlier 0.5 hour, stop to vacuumize, filling Ar gas to stove internal gas pressure is 0.09MPa, continues to be warming up to 2100 ℃ of holding temperatures.And in outlet temperature after constant 0.5 hour, sample is with the stove cool to room temperature.The gained material soaked 12 hours in 5.0% dilute sulfuric acid after, filter, oven dry.With the material with carbon element after the oven dry is carrier, uses the reduction of ethylene glycol legal system to be equipped with the Pt/C catalyst.Fig. 3 is the XRD comparison diagram of this routine graphitized carbon carrier and original carbon dust, and Fig. 4 is the cyclic voltammetric comparison diagram of the catalyst 1.75V constant potential oxidation front and back of preparation.
Embodiment 3:
Commercial carbon powder material Vulcan XC-72 about 200g is placed in the resistant to elevated temperatures graphite crucible, and graphite crucible is put into Medium frequency induction high temperature graphitization stove carry out graphitization processing.Its temperature is chosen as 2100 ℃.Treatment process is as follows: when holding temperature equals or is higher than 2000 ℃, be evacuated to earlier about 10Pa, then feeding temperature-raising, adopt manually and heat up, be warming up to 2000 ℃ of insulations earlier 0.5 hour, stop to vacuumize, inflated with nitrogen to stove internal gas pressure is 0.09MPa, continues to be warming up to 2100 ℃ of holding temperatures.And in outlet temperature after constant 3 hours, sample is with the stove cool to room temperature.The gained material soaked 12 hours in 5.0% watery hydrochloric acid after, filter, oven dry.With the material with carbon element after the oven dry is carrier, uses direct method of reducing to prepare the Pt/C catalyst.
Fig. 5 is catalyst thermogravimetric analysis figure.
Embodiment 4:
Commercial carbon powder material acetylene black about 200g is placed in the resistant to elevated temperatures graphite crucible, and graphite crucible is put into Medium frequency induction high temperature graphitization stove carry out graphitization processing.Its temperature is chosen as 1500 ℃.Treatment process is as follows: be evacuated to earlier about 10Pa, feeding temperature-raising adopts manually and heats up then, stops when being warming up to holding temperature vacuumizing, and filling highly purified Ar gas to stove internal gas pressure is 0.09MPa.And in outlet temperature after constant 0.5 hour, sample is with the stove cool to room temperature.The gained material soaked 12 hours in 5.0% watery hydrochloric acid after, filter, oven dry.With the material with carbon element after the oven dry is carrier, uses direct method of reducing to prepare the Pt/C catalyst.
Embodiment 5:
Commercial carbon powder material acetylene black about 200g is placed in the resistant to elevated temperatures graphite crucible, and graphite crucible is put into Medium frequency induction high temperature graphitization stove carry out graphitization processing.Its temperature is chosen as 2500 ℃.Treatment process is as follows: when holding temperature equals or is higher than 2000 ℃, be evacuated to earlier about 10Pa, then feeding temperature-raising, adopt manually and heat up, be warming up to 2000 ℃ of insulations earlier 0.5 hour, stop to vacuumize, filling Ar gas to stove internal gas pressure is 0.09MPa, continues to be warming up to 2500 ℃ of holding temperatures.And in outlet temperature after constant 0.5 hour, sample is with the stove cool to room temperature.The gained material soaked 12 hours in 5.0% watery hydrochloric acid after, filter, oven dry.With the material with carbon element after the oven dry is carrier, uses the reduction of ethylene glycol legal system to be equipped with the Pt/C catalyst.
Adopt above-mentioned graphitization processing process, improved the stability of carbon powder material.And the graphitization processing temperature is high more, and degree of graphitization improves constantly, and carrier is stable more.The stability of the catalyst of respective carrier preparation also improves concrete outcome such as accompanying drawing relatively.
Fig. 1 is the XRD figure of the graphitized carbon powder material of embodiment 1 gained, and the XRD figure that has listed file names with original carbon powder material among the figure compares.As can be seen through after 1800 ℃ of graphitization processing, the gradually sharpening of 002 characteristic peak of this material with carbon element.2 θ angles obviously move to right, and have reflected the raising of its degree of graphitization, and the stable stability of carrier also improves.
Fig. 2 is that the cyclic voltammetric of embodiment 1 prepared catalyst Pt/VX-1800 (Vulcan XC-72 is through 1800 ℃ of graphitization processing) characterizes, and has also listed Pt/VX (Vulcan XC-72 is untreated) cyclic voltammetric sign under the same conditions among the figure simultaneously and has compared.The electrochemical surface of Pt/VX-1800 catalyst is long-pending slightly littler than Pt/VX as can be seen, and this is because through after the high-temperature heat treatment, the specific area of carrier reduces to cause the dispersiveness of noble metal poor slightly.But the amplitude that reduces is very faint, and is smaller to the performance impact of battery.
Fig. 3 is the XRD figure of the carbon powder material that 2100 ℃ of graphitization processing obtain among the embodiment 2, and the XRD figure that has also listed file names with original carbon powder material among the figure compares.Through after 2100 ℃ of graphitization processing, compare 1800 ℃ of material with carbon elements that graphitization processing obtains among the embodiment 1 as can be seen, its graphitization characteristic peak 002 peak is more sharp-pointed, and degree of graphitization is higher.
Fig. 4 is the cyclic voltammetric comparison diagrams of embodiment 2 prepared catalyst Pt/VX before and after the oxidation of 1.75V constant potential.
Fig. 5 is the cyclic voltammetric comparison diagrams of embodiment 2 prepared catalyst Pt/VX-2100 before and after the oxidation of 1.75V constant potential.
Find that through contrast Pt/VX-2100 catalyst electrochemically resistant corrosive power obviously is better than Pt/VX.The high potential oxidation that the Pt/VX-2100 catalyst can stand 2.0V still keeps most catalytic activity.And under the same case, the VX corrosion is very serious, causes coming off in a large number and running off of Pt, makes catalyst failure.Therefore, the stability of carrier has improved the stability of catalyst to the catalyst important influence by the graphitization processing of carrier.The present invention can reach the purpose of drafting.
Fig. 6 is the thermogravimetric analysis comparison diagram of embodiment 2 prepared catalyst Pt/VX-2100 and conventional Pt/VX catalyst.Can see that the oxidizing temperature that the Pt/VX catalyst begins is low to moderate about 150 ℃, and the Pt/VX-2100 catalyst just begins oxidation about 400 ℃.Reacted the Pt/VX-2100 catalyst stability of heat also obviously has been better than Pt/VX.
The effect of invention:
1, graphitization heat treatment of the present invention has improved the stability of fuel cell carbon carrier, for the preparation of catalyst, Improved the resistance to overturning of catalyst.
2, carrier is after Overheating Treatment, and specific area descends to some extent, but shows catalysis by the cyclic voltammetry test The catalytic activity of agent descends little, illustrates that carrier is not through having noble metal after the graphitization processing among the present invention Dispersion cause too big impact.
3, the test of constant potential oxidation shows that catalyst electrochemically resistant that the present invention makes learns the ability of corrosion and carry to some extent Height, and the thermogravimetric analysis experiment shows that the catalyst that the present invention makes has better heat endurance.
4, process conditions of the present invention are simple, and operating condition is easy to control, and cost is lower, and is more suitable Large-scale production.
Claims (6)
1. method that improves fuel cell catalyst stability, it is as follows to it is characterized in that manufacturing step:
A, carbon support material are carried out graphitization processing; Carbon support material is placed in the resistant to elevated temperatures graphite crucible, and crucible put into Medium frequency induction high temperature graphitization stove heat treated, be evacuated to about 10Pa earlier during heating, stop to vacuumize when being warming up to 1000 ℃ ~ 2900 ℃, fill highly purified inert gas Ar gas and protect to stove, air pressure is 0.09MPa, and heat treatment time is 0.5 ~ 20 hour, stop heating, the material after the graphitization processing is with the stove cool to room temperature;
B, the material after the graphitization processing is carried out acidification; Material after the graphitization processing is placed in the hydrochloric acid solution, and its concentration of hydrochloric acid solution scope is 0.01-10mol/L, flood after 2-12 hour to filter, and the water flushing is not to there being chlorion, then in 100 ℃ of oven dry of drying oven;
C, employing direct-reduction process prepare catalyst; (10mg/m1) pours in the there-necked flask platinum acid chloride solution; feed nitrogen protection and stirring; add reducing agent formaldehyde; add sodium hydroxide solution (5%) after the stirring again; make whole solution be alkalescent; and then add material after the graphitization processing of being soaked by isopropyl alcohol; then; solution is heated to 80 ℃, and constant temperature dropped to room temperature after 1 hour, and logical carbon dioxide is 1 hour in solution; washing is not after have chlorion after filtration; dry to constant weight under 100 ℃ of drying ovens, promptly make the Pt/C catalyst, the load amount of precious metals pt is 5% ~ 70% in the catalyst usually.
2. a kind of method that improves fuel cell catalyst stability according to claim 1, it is characterized in that direct-reduction process prepares catalyst and also can adopt the reduction of ethylene glycol legal system to be equipped with catalyst, adopt the reduction of ethylene glycol method to be meant that it is that reducing agent prepares catalyst that spent glycol replaces formaldehyde.
3. a kind of method that improves fuel cell catalyst stability according to claim 1 is characterized in that used highly purified inert gas Ar gas, also can high pure nitrogen, and high-purity argon gas, gas or their mists such as high-pure helium body.
4. a kind of method that improves fuel cell catalyst stability according to claim 1 is characterized in that used carbon support material can be the Vulcan XC-72 that uses always, also can be commercial absorbent charcoal materials such as acetylene black, BP2000, M1300.
5. a kind of method that improves fuel cell catalyst stability according to claim 1 is characterized in that carrying out in the process of acidification, and the acid of use can be used watery hydrochloric acid, also can use acidic intermediums such as dilute sulfuric acid, rare nitric acid and acetic acid solution.
6. a kind of method that improves fuel cell catalyst stability according to claim 1 is characterized in that the catalyst for preparing mainly is the Pt/C catalyst, is called the monometallic carbon carrier catalyst; The bimetallic or the multimetal reforming catalyst that also can prepare the carrier stabilisation, the alloy catalyst that Pt such as bimetallic such as PtRu/C, PtIr/C, PtFe/C, PtCo/C, PtNi/C and transition metal and other noble metals form; Catalyst more than three components that Pt such as multimetal reforming catalyst such as PtRuIr/C, PtCoNi/C and two or more transition metal and noble metal form; The preparation method is identical with preparation Pt/C catalyst, and difference is when the preparation multicomponent catalyst, with the salt solution mix of platinum acid chloride solution and corresponding metal, pours in the there-necked flask.
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Cited By (9)
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| WO2011095943A1 (en) * | 2010-02-05 | 2011-08-11 | Basf Se | Process for producing a catalyst and catalyst |
| CN103657629A (en) * | 2013-12-30 | 2014-03-26 | 北京化工大学 | Method for preparing high-dispersibility nano Pt-SnO2/C catalyst |
| CN105214685A (en) * | 2015-09-11 | 2016-01-06 | 浙江理工大学 | A kind of platinum cobalt alloy structured catalysis material for brine electrolysis and preparation method thereof |
| CN109216716A (en) * | 2018-08-06 | 2019-01-15 | 浙江高成绿能科技有限公司 | A kind of preparation method of the fuel cell Pt/C catalyst of high Pt carrying capacity |
| CN109244491A (en) * | 2018-08-06 | 2019-01-18 | 浙江高成绿能科技有限公司 | A kind of fuel cell Pt/WO3The preparation method of C catalyst |
| CN111916771A (en) * | 2019-05-10 | 2020-11-10 | 上海捷氢科技有限公司 | High-activity and high-stability PtNi nano-alloy catalyst and preparation method and application thereof |
| CN113782753A (en) * | 2021-09-10 | 2021-12-10 | 无锡威孚高科技集团股份有限公司 | Proton exchange membrane fuel cell catalyst and preparation method thereof |
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| WO2011095943A1 (en) * | 2010-02-05 | 2011-08-11 | Basf Se | Process for producing a catalyst and catalyst |
| CN102762297A (en) * | 2010-02-05 | 2012-10-31 | 巴斯夫欧洲公司 | Process for producing a catalyst and catalyst |
| CN102762297B (en) * | 2010-02-05 | 2015-06-10 | 巴斯夫欧洲公司 | Process for producing a catalyst and catalyst |
| CN103657629A (en) * | 2013-12-30 | 2014-03-26 | 北京化工大学 | Method for preparing high-dispersibility nano Pt-SnO2/C catalyst |
| CN103657629B (en) * | 2013-12-30 | 2016-03-30 | 北京化工大学 | High dispersancy nano Pt-SnO 2the preparation method of/C catalyst |
| CN105214685A (en) * | 2015-09-11 | 2016-01-06 | 浙江理工大学 | A kind of platinum cobalt alloy structured catalysis material for brine electrolysis and preparation method thereof |
| CN109216716A (en) * | 2018-08-06 | 2019-01-15 | 浙江高成绿能科技有限公司 | A kind of preparation method of the fuel cell Pt/C catalyst of high Pt carrying capacity |
| CN109244491A (en) * | 2018-08-06 | 2019-01-18 | 浙江高成绿能科技有限公司 | A kind of fuel cell Pt/WO3The preparation method of C catalyst |
| CN109216716B (en) * | 2018-08-06 | 2023-09-05 | 浙江高成绿能科技有限公司 | Preparation method of Pt/C catalyst for fuel cell with high Pt loading |
| CN111916771A (en) * | 2019-05-10 | 2020-11-10 | 上海捷氢科技有限公司 | High-activity and high-stability PtNi nano-alloy catalyst and preparation method and application thereof |
| CN111916771B (en) * | 2019-05-10 | 2022-02-18 | 上海捷氢科技股份有限公司 | High-activity and high-stability PtNi nano-alloy catalyst and preparation method and application thereof |
| CN113782753A (en) * | 2021-09-10 | 2021-12-10 | 无锡威孚高科技集团股份有限公司 | Proton exchange membrane fuel cell catalyst and preparation method thereof |
| CN114373944A (en) * | 2021-12-15 | 2022-04-19 | 青岛创启新能催化科技有限公司 | Preparation method of anti-reversal alloy catalyst for fuel cell |
| CN114388827A (en) * | 2021-12-16 | 2022-04-22 | 同济大学 | Batch preparation method of catalyst for fuel cell |
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