CN106784903A - For the platinum transition metal alloy nanometer crystal preparation method of fuel-cell catalyst - Google Patents
For the platinum transition metal alloy nanometer crystal preparation method of fuel-cell catalyst Download PDFInfo
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- CN106784903A CN106784903A CN201611239708.8A CN201611239708A CN106784903A CN 106784903 A CN106784903 A CN 106784903A CN 201611239708 A CN201611239708 A CN 201611239708A CN 106784903 A CN106784903 A CN 106784903A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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 provides a kind of preparation method nanocrystalline for the platinum transition metal alloy of fuel-cell catalyst, comprise the following steps：S1, platinum presoma, transition metal forerunner, benzoic acid are dissolved in N N-dimethylformamides form precursor mixed solution；S2, the precursor mixed solution is placed in microwave electromagnetic field, by microwave action in after the uniform heating response of the precursor mixed solution, the platinum transition metal alloy for obtaining shape of octahedron is nanocrystalline.The present invention has duality principle using microwave, can be uniform rapidly and selectively plus thermal property, to reactant continuous heating during the course of the reaction, effectively accelerates the reaction time, shortens reaction time.For relatively conventional synthesis technique, synthesis cycle reduces nearly ten times, very big to improve reaction efficiency.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly to a kind of platinum-transition metal for fuel-cell catalyst is closed
The preparation method of gold nanocrystals, and the method for preparing fuel-cell catalyst.
Background technology
Proton Exchange Membrane Fuel Cells is the device that a kind of chemical energy that will directly be stored in fuel is changed into electric energy, because of it
High-energy-density and the distinguishing feature such as environment-friendly are considered as a kind of effective solution of following clean energy resource, and its core is
Make chemical energy efficient by anode hydroxide reaction and Cathodic oxygen reduction (Oxygen Reduction Reaction, ORR)
Be converted into electric energy.In all of simple metal, platinum (Pt) is catalyst best to ORR catalytic reactions activity at present,
But its expensive expense is fuel cell large-scale production and commercialized key factor.The nineties in last century, research shows
Platinum and transition metal M are formed into alloy catalyst (M=Fe, Co, Ni etc.), due to the electronics that transition metal atoms M is produced
Coordination effect or strain effect, can significantly improve its catalysis activity to ORR reactions.2007, researchers had found monocrystalline platinum
(111) face compared to other crystal faces, with high catalysis activity, therefore, Recent study person be devoted to always synthesis
Platinum alloy with pattern is nanocrystalline.
The synthetic method that current researchers use has two kinds, and a kind of is using oleyl amine/oleic acid as surfactant
Synthesize in system,, by platinum presoma, transition metal precursor is dissolved in shape in the oleyl amine/Oleic Acid System solution for adding reducing agent for they
Into precursor solution, then precursor solution heats in there-necked flask to synthesize platinum alloy nanocrystalline.Closed using this kind of method
Into platinum alloy it is nanocrystalline because oleyl amine oleic acid is attached to its surface and is difficult to clean completely, therefore its catalytic performance compares Pt/C
Improve and only have several times.Another method is synthesized in N-N dimethylformamides (DMF) system, and this method does not use oil
Amine oleic acid as surfactant, using DMF simultaneously as reducing agent and surfactant.The platinum alloy synthesized using this kind of method
Nano-crystalline granule surface does not have the influence of surfactant, and its catalysis activity is greatly enhanced.But the shortcoming of this kind of method
It is to be up to dozens of hour in the cycle that single sintering is tested, combined coefficient is extremely low.
The content of the invention
For defect of the prior art, it is an object of the invention to provide the platinum that a kind of reaction time is short, combined coefficient is high-
The nanocrystalline preparation method of transition metal alloy.
One aspect of the present invention provides a kind of preparation side of platinum-transition metal alloy nanometer crystals for fuel-cell catalyst
Method, comprises the following steps：
S1, platinum presoma, transition metal forerunner, benzoic acid are dissolved in N-N dimethylformamides and form presoma mixing
Solution；
S2, the precursor mixed solution is placed in microwave electromagnetic field, is mixed in the presoma by microwave action
After the uniform heating response of solution, the platinum-transition metal alloy nanometer crystals of shape of octahedron are obtained.
The present invention also provides the platinum-transition metal alloy nanometer crystals prepared using the above method.
Another aspect of the present invention provides a kind of preparation method of fuel-cell catalyst, including：To be prepared such as above-mentioned method
Platinum-transition metal alloy nanometer crystals be carried on carrier, after making its dispersed, with water, isopropanol and perfluorinated sulfonic acid tree
Fat mixes, and prepares compo, and the compo is coated on electrode.
The present invention has duality principle using microwave, can uniform rapidly and selectively add thermal property, to reactant
Continuous heating, effectively accelerates the reaction time during the course of the reaction, shortens reaction time.Relatively conventional synthesis technique comes
Say, synthesis cycle reduces nearly ten times, it is very big to improve reaction efficiency.
Brief description of the drawings
Fig. 1 is the platinum-transition metal alloy nanometer crystals transmission electron microscope photo prepared by one embodiment of the invention.
The volt that platinum-transition metal alloy nanometer crystals of the Fig. 2 prepared by embodiment in Fig. 1 are measured in rotating disk electrode (r.d.e)
Peace curve map, electrode is placed in oxygen-saturated 0.1mol/L high chloro acid solutions, sweeps speed for 100mV/s.
Main element symbol description
Nothing
Following specific embodiment will further illustrate the present invention with reference to above-mentioned accompanying drawing.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
A kind of preparation method of platinum-transition metal alloy nanometer crystals for fuel-cell catalyst, comprises the following steps：
S1, platinum presoma, transition metal forerunner, benzoic acid are dissolved in N-N dimethylformamides and form presoma mixing
Solution；
S2, the precursor mixed solution is placed in microwave electromagnetic field, is mixed in the presoma by microwave action
After the uniform heating response of solution, the platinum-transition metal alloy nanometer crystals of shape of octahedron are obtained.
Microwave is a kind of electric wave of frequency in 300MHz to 300GHz, with duality principle, it can rapidly, it is uniform and select
The heating object of selecting property.Because the polar molecule under microwave action, its polarity orientation is with the change of external electric field
Change, causes the spin motion effect of polar molecule, and now the field energy of microwave field is converted into the heat energy of medium, makes temperature of charge liter
It is high.Meanwhile, because the volume heating that heating using microwave is material to be caused in electromagnetic field by dielectric loss itself, is capable of achieving molecule
Stirring in level, homogeneous heating, thermograde is small, and the nano-crystalline granule of generation is uniform, figure and features rule.And because material is inhaled
The ability for receiving microwave energy depends on the dielectric property of itself, therefore carries out selective heating to each reactant in reaction, so that
The selectivity of reaction is improved, the activity of product obtained from is higher.
Embodiments in accordance with the present invention, platinum presoma described in the step S1 includes chloride, bromide, the iodate of platinum
Thing, hydroxide, nitrate, nitrite, carbonate, phosphate, phosphite, sulfate, sulphite, acetate, grass
At least one of hydrochlorate and acetylacetonate.
Embodiments in accordance with the present invention, the platinum presoma is acetylacetone,2,4-pentanedione platinum.
Embodiments in accordance with the present invention, transition metal precursor described in the step S1 includes the chlorination of transition metal
Thing, bromide, iodide, hydroxide, nitrate, nitrite, carbonate, phosphate, phosphite, sulfate, sulfurous
At least one of hydrochlorate, acetate, oxalates and acetylacetonate.
Embodiments in accordance with the present invention, transition metal includes described in transition metal precursor described in the step S1
At least one of iron, cobalt, nickel, copper, silver, manganese, chromium, vanadium, titanium, molybdenum and tungsten.
Embodiments in accordance with the present invention, the transition metal precursor is nickel acetylacetonate.
Embodiments in accordance with the present invention, the platinum-transition metal alloy nanometer crystals are that platinum-nickel alloy is nanocrystalline, its particle chi
Very little is 5nm-20nm, and pattern is octahedron.Found according to many experiments, the platinum-nickel alloy is nanocrystalline, with regular octahedron shape
Looks, can effectively increase platinum surface area, i.e. material-saving can improve electrode efficiency again.And the platinum nickel on the regular octahedron surface is former
Son possesses the arrangement mode of uniqueness, can significantly improve the chemical reaction speed of hydrogen and oxygen reaction generation water in fuel cell
Degree, moreover it is possible to increase reactivity, increase the service life.
The present invention adds benzoic acid as particle dispersants.The nano-crystalline granule pattern of generation can be effectively set more to advise
Then, more uniformly, agglomeration will not occur, reaction yield also can be higher.
It is polar aprotic organic solvent that the present invention adds N-N- dimethylformamides.Because microwave is situated between for polarity electricity
Metallic substance assimilation effect more preferably, therefore in synthetic reaction, selects suitable solvent to be key.Polar solvent absorbs the energy of microwave
Power is stronger, can be heated quickly in microwave field.And oleyl amine oleic acid is used in conventional method as surface adhesion agent, carbon monoxide
Or 14 wrist alcohol etc. as reducing agent, the particle surface of synthesis is not clean, and oleyl amine oleic acid is difficult to clean completely, influence activity.This
Method uses N-N- dimethylformamides as reducing agent and surface adhesion agent, due to there was only a kind of organic solvent of benzoic acid, and
It is readily cleaned, so the particle surface that synthesis is obtained is cleaned very much, activity is higher.
Embodiments in accordance with the present invention, the platinum presoma of 0.05~0.1 mass fraction added in the step S1,0.1
The transition metal precursor of~0.3 mass fraction, and 0.5~1 mass fraction particle dispersants.
Embodiments in accordance with the present invention, the platinum presoma of 0.08 mass fraction added in the step S1,0.2 mass parts
Several transition metal precursors, and 1 mass fraction particle dispersants.
Embodiments in accordance with the present invention, the microwave electromagnetic field is obtained by microwave synthesizer.The microwave synthesizer refers to
Using microwave as the reaction kit of main mode of heating, such as serial microwave synthesizer of Anton Paar companies production, the U.S.
Serial microwave synthesizer of CEM companies production etc..Microwave synthesizer can provide uniform, highdensity microwave field, and power
Stability, can effectively meet the demands such as the controllability and repeatability of microwave electromagnetic field.
Embodiments in accordance with the present invention, the temperature of microwave electromagnetic field heating between 120~180 DEG C, the reaction time
It is 4~12h.Inventor is found through experiments that, the heat time for being synthesized by microwave with this understanding is compared to utilizing water heating kettle
Or be greatly reduced the time required to there-necked flask heating, the material mass of preparation is more excellent.
Embodiments in accordance with the present invention, the preparation method also includes, carrier is added in reaction system, makes to prepare
The platinum-transition metal alloy nanometer crystals be carried on the carrier.
Embodiments in accordance with the present invention, the carrier includes at least one of carbon black, Graphene, doping stannic oxide.Institute
Carrier is stated for high-specific surface area material, with high specific surface area, nanocrystalline load can be made thereon without reuniting.
Embodiments in accordance with the present invention, the mass fraction of the carrier is the 6~7 of the mass fraction of the platinum presoma
Times.
Embodiments in accordance with the present invention, the step S2 also includes, platinum-transition metal alloy is obtained after the completion of reaction
Nanocrystal solution, by the platinum-transition metal alloy nanometer crystals solution centrifugal, cleaning.
Embodiments in accordance with the present invention, the method for the centrifugation can be selected according to the method for this area conventional centrifugal,
Preferably, can be centrifuged using centrifuge.The frequency of centrifugation and time can be carried out according to the parts by weight of the reactant for adding
Corresponding adjustment.Preferred use is centrifuged 5~10min under 8000~10000rpm.
Embodiments in accordance with the present invention, the number of times of the cleaning can be carried out accordingly according to the parts by weight of the reactant for adding
Adjustment.Preferably, clean 3 times.
Another aspect of the present invention also provides the platinum-transition metal alloy nanometer crystals prepared using the above method.
Another aspect of the present invention also provides a kind of preparation method of fuel-cell catalyst, including：
Platinum-transition metal alloy nanometer crystals prepared by such as above-mentioned method are carried on carrier, after making its dispersed, with
The mixing of water, isopropanol and perfluorinated sulfonic resin, prepares compo, and the compo is coated on electrode.
Embodiments in accordance with the present invention, the carrier includes at least one of carbon black, Graphene, doping stannic oxide.
Embodiments in accordance with the present invention, platinum-transition metal alloy nanometer crystals and isopropanol, the perfluorinated sulfonic acid tree of the addition
Fat proportioning is that platinum-transition metal alloy nanometer crystals number is 1.6,1 part of isopropanol, 4 parts of water, 0.4 part of perfluorinated sulfonic resin.
Embodiment 1
Configuration precursor solution：By the benzene first of the acetylacetone,2,4-pentanedione platinum, the nickel acetylacetonate of 51.38mg and 122mg of 31.46mg
Acid is dissolved in the N-N- dimethylformamides (DMF) of 20mL at room temperature, is sufficiently stirred for forming the solution of homogeneous transparent.Before treating
After driving body whole dissolving, 83.7mg carbon blacks (XC 72) is added, be sufficiently stirred for forming suspension at room temperature.
Heating using microwave：By in above-mentioned suspension addition 30mL quartz ampoules, CEM DISCOVER ring focusing single modes are put into micro-
Ripple synthesis system, regulation parameter to temperature is increased to 120 DEG C, is incubated 12h and is stirred continuously.
Centrifugation, cleaning：The reaction solution that microwave synthesis is obtained is centrifuged 10min under 8000rpm and obtains platinum-nickel alloy nanometer
Crystalline substance, then by these nanocrystalline cleaning three times in the mixed liquor of water and ethanol, obtain being carried on the PtNi on carbon black after drying and close
It is golden octahedra nanocrystalline.
The PtNi alloys that will be prepared are octahedra nanocrystalline by scanning transmission electron microscope observation, and its pattern is as schemed
Shown in 1.As can be seen that particle has fabulous dispersiveness, the shape of octahedron of rule, and even particle size, it is left in 8nm
It is right.The PtNi alloy nanometer crystals being carried on to gained using rotating disk electrode (r.d.e) on carbon black have carried out the catalysis to oxygen reduction reaction
Performance test, gained volt-ampere curve are as shown in Fig. 2 sweep speed is 5mV/s, 1600 revs/min of electrode rotating speed.Can be with from figure
Find out, the mass activity under 0.9V (with respect to reversible hydrogen electrode) reaches 0.42A/mgPt, be three times of business Pt/C, it is to oxygen
Reduction reaction shows good catalysis activity.
Embodiment 2
Put precursor solution：By the benzene first of the acetylacetone,2,4-pentanedione platinum, the nickel acetylacetonate of 25.69mg and 61.06mg of 19.67mg
Acid is dissolved in the N-N- dimethylformamides (DMF) of 17mL at room temperature, is sufficiently stirred for forming the solution of homogeneous transparent.
Heating using microwave：By in above-mentioned solution addition 30mL quartz ampoules, CEM DISCOVER ring focusing single mold microwaves are put into
Synthesis system, regulation parameter is warming up to 180 DEG C, is incubated 4h and is stirred continuously.
Load Graphene：The reaction solution that microwave synthesis is obtained is added in ultrasonic cell disintegration instrument ultrasound 10min
52.33mg Graphenes, then in ultrasonic cell disintegration instrument ultrasound 30min.
Centrifugation, cleaning：Suspension after ultrasonication is centrifuged 5min under 10000rpm and obtains PtNi alloy nanometer crystals,
Again by these nanocrystalline cleaning three times in the mixed liquor of water and ethanol, obtain being carried on the PtNi alloys on Graphene after drying
It is octahedra nanocrystalline.
Prepare fuel-cell catalyst：The PtNi alloys octahedron manocrystalline powders 1.6mg on Graphene will be carried on, with
The perfluorinated sulfonic resin mixing of the water of 4ml, the isopropanol of 1ml and 4 μ l, mixed solution is coated on the electrode of fuel cell.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, embodiment of above is only for explaining claims.Right protection scope of the present invention is not limited to specification.Appoint
How those familiar with the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of platinum-transition metal alloy nanometer crystals for fuel-cell catalyst, comprises the following steps：
S1, platinum presoma, transition metal forerunner, benzoic acid are dissolved in N-N dimethylformamides form precursor mixed solution；
S2, the precursor mixed solution is placed in microwave electromagnetic field, by microwave action in the precursor mixed solution
After uniform heating response, the platinum-transition metal alloy nanometer crystals of shape of octahedron are obtained.
2. preparation method according to claim 1, it is characterised in that platinum presoma described in the step S1 includes platinum
Chloride, bromide, iodide, hydroxide, nitrate, nitrite, carbonate, phosphate, phosphite, sulfate,
At least one of sulphite, acetate, oxalates and acetylacetonate.
3. preparation method according to claim 2, it is characterised in that the platinum presoma is acetylacetone,2,4-pentanedione platinum.
4. preparation method according to claim 1, it is characterised in that transition metal precursor bag described in the step S1
Include chloride, bromide, iodide, hydroxide, nitrate, nitrite, carbonate, phosphate, the phosphorous of transition metal
At least one of hydrochlorate, sulfate, sulphite, acetate, oxalates and acetylacetonate；The transition metal include iron,
At least one of cobalt, nickel, copper, silver, manganese, chromium, vanadium, titanium, molybdenum and tungsten.
5. preparation method according to claim 4, it is characterised in that the transition metal precursor is nickel acetylacetonate.
6. preparation method according to claim 1, it is characterised in that the microwave electromagnetic field is obtained by microwave synthesizer
.
7. preparation method according to claim 1, it is characterised in that the temperature of the microwave electromagnetic field heating for 120~
Between 180 DEG C, the reaction time is 4~12h.
8. preparation method according to claim 1, it is characterised in that also including before heating using microwave or after heating to forerunner
Add carrier in body mixed solution, the carrier is high-specific surface area material, including carbon black, Graphene, doping stannic oxide
At least one.
9. the platinum-transition metal alloy nanometer crystals that prepared by the method for claim 1.
10. a kind of preparation method of fuel-cell catalyst, it is characterised in that including：
Platinum-transition metal alloy nanometer crystals prepared by method as claimed in claim 1 are carried on carrier, make its dispersed
Afterwards, mix with water, isopropanol and perfluorinated sulfonic resin, prepare compo, the compo is coated on electrode, institute
At least one of carrier is stated for high-specific surface area material, including carbon black, Graphene, doping stannic oxide.
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Cited By (14)
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|---|---|---|---|---|
| CN107845815A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity |
| CN108417848A (en) * | 2018-02-12 | 2018-08-17 | 华南理工大学 | A kind of platinum-nickel alloy catalyst nano material and the preparation method and application thereof having efficient electric catalytic oxidation-reduction performance |
| CN108470920A (en) * | 2018-04-08 | 2018-08-31 | 北京化工大学 | A kind of graphene-supported platinum cobalt tungsten alloy nano-particle composite catalyst and preparation method thereof for acid medium |
| CN109830702A (en) * | 2019-02-13 | 2019-05-31 | 深圳市雄韬电源科技股份有限公司 | A kind of fuel-cell catalyst and its preparation method and application |
| CN109921046A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | Ingredient and the controllable Pt alloy oxygen reduction catalyst and preparation method thereof of structure and morphology |
| CN110021759A (en) * | 2019-03-27 | 2019-07-16 | 内蒙古科技大学 | Platinum-nickel alloy method for preparing catalyst |
| 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 |
| CN111293322A (en) * | 2020-02-24 | 2020-06-16 | 北京化工大学 | Carbon-supported octahedral platinum-copper-molybdenum ternary alloy catalyst for fuel cell and preparation method thereof |
| CN112077334A (en) * | 2020-09-03 | 2020-12-15 | 南京晓庄学院 | Preparation method and application of transition metal doped ruthenium-rhodium alloy |
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| CN107845815A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity |
| CN109921046A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | Ingredient and the controllable Pt alloy oxygen reduction catalyst and preparation method thereof of structure and morphology |
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| CN108470920A (en) * | 2018-04-08 | 2018-08-31 | 北京化工大学 | A kind of graphene-supported platinum cobalt tungsten alloy nano-particle composite catalyst and preparation method thereof for acid medium |
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| CN110021759A (en) * | 2019-03-27 | 2019-07-16 | 内蒙古科技大学 | Platinum-nickel alloy method for preparing catalyst |
| CN110021759B (en) * | 2019-03-27 | 2023-01-10 | 内蒙古科技大学 | Preparation method of platinum-nickel alloy catalyst |
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| CN112201797A (en) * | 2020-09-01 | 2021-01-08 | 深圳航天科技创新研究院 | Metal catalyst, mass production preparation method thereof and fuel cell |
| CN112077334A (en) * | 2020-09-03 | 2020-12-15 | 南京晓庄学院 | Preparation method and application of transition metal doped ruthenium-rhodium alloy |
| CN113206259A (en) * | 2021-04-22 | 2021-08-03 | 华中科技大学 | Platinum-based intermetallic nanocrystalline with ordered structure, and preparation and application thereof |
| CN114068969A (en) * | 2021-11-20 | 2022-02-18 | 郑州中科新兴产业技术研究院 | N-doped carbon-based platinum-cobalt alloy oxygen reduction catalyst, preparation method and application thereof |
| CN114068969B (en) * | 2021-11-20 | 2024-01-19 | 郑州中科新兴产业技术研究院 | N-doped carbon-based platinum cobalt alloy oxygen reduction catalyst, preparation method and application thereof |
| CN114388737A (en) * | 2021-12-24 | 2022-04-22 | 西安理工大学 | Self-supporting electrode, preparation method thereof and lithium-sulfur battery |
| CN115254140A (en) * | 2022-08-24 | 2022-11-01 | 西安交通大学 | Noble metal-non-noble metal alloy nano material and synthesis method thereof |
| CN115254140B (en) * | 2022-08-24 | 2023-10-10 | 西安交通大学 | Noble metal-non-noble metal alloy nano material and synthesis method thereof |
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