CN109616671A - A kind of method and application for preventing intermetallic compound from reuniting in high temperature and growing up - Google Patents
A kind of method and application for preventing intermetallic compound from reuniting in high temperature and growing up Download PDFInfo
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- CN109616671A CN109616671A CN201811450344.7A CN201811450344A CN109616671A CN 109616671 A CN109616671 A CN 109616671A CN 201811450344 A CN201811450344 A CN 201811450344A CN 109616671 A CN109616671 A CN 109616671A
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- high temperature
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- base metal
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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 discloses a kind of methods and application for preventing intermetallic compound from reuniting in high temperature and growing up, and belong to new energy materials field.Method includes the following steps: (1) is uniform by chloroplatinic acid, base metal salt, carbon material solution and polyvinyl alcohol stirring ultrasonic mixing, then it is freeze-dried；(2) by step (1) products therefrom in H2600-800 DEG C of high temperature quenching, obtains fuel-cell catalyst PtM/C in/Ar environment.The method that the present invention prevents particle agglomeration and grows up is simple, and easy to control, yield is big, is easy to industrialize.The PtM/C catalyst of preparation is used for the oxygen reduction reaction of fuel cell, shows good reactivity worth.
Description
Technical field
The invention belongs to new energy materials fields, and in particular to one kind prevents intermetallic compound from reuniting in high temperature and growing
Big method and application.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) has the important advantages such as energy conversion efficiency height, no pollution, be known as be
21 century mostly important new energy technology.The fuel cell car of domestic and international demonstrating running is in vehicle performance, reliability at present
Reach with environmental suitability etc. and level that orthodox car compares favourably, but due to cost and endurance issues, combustion
The commercialization of material battery still suffers from huge challenge.
Influence the principal element of fuel battery performance and cost first is that the catalyst of cathode, ordered intermetallic compound are urged
Agent is an important directions of current fuel battery cathod catalyst developmental research.Ordered intermetallic compound is in forming process
In be different from common alloy (solid solution), intermetallic compound is usually obtained by high-temperature heat treatment, enthalpy of mixing with higher, because
This is with higher chemistry and structural stability.Nano material partial size is smaller, and surface can be higher, the trend with spontaneous reunion.
Especially in the high temperature environment, the intermetallic compound nano-particle of formation is easy to happen reunion and grows up.Ordered intermetallic chemical combination
It the reunion of composition granule and grows up and has seriously affected the activity of nano material, therefore in the high temperature mistake for forming ordered intermetallic compound
Cheng Zhong finds simple, the efficient method of one kind to inhibit nanoparticle agglomerates and grow up to be particularly important.It is scientific based on this
Very good try is done in boundary.(Sun S, et al., the J. Am. Chem. Soc. 2010,132,4996- such as Sun
4997) prevent high temperature from forming the reunion of orderly PtFe nano particle and growing up using the method for MgO cladding PtFe.Huang etc.
(Huang W, etal., J. Am. Chem. Soc. 2017,139,4762-4768) etc. uses SiO2Coat PtZn's
Method inhibits particle agglomeration in pyroprocess, and orderly PtZn granular size is (3.2 ± 0.4 nm), has good electro-catalysis
Activity.Taeghwan Hyeon, Hyuck Mo Lee etc. utilizes organic matter surface coating technology, inhibits respectively under high temperature
Pt3Fe, PtFe particle agglomeration are grown up.(aeghwan Hyeon, et al., J. Am. Chem. Soc. 2015, 137,
15478−15485； Hyuck Mo, Lee et al., ACS Appl. Mater. Interfaces 2017, 9, 31806
−31815)。
The most complex process of the above method, the method taken for compound between different metal is different, receives to inhibition
Rice material is reunited and no universality of growing up.Then, a kind of simple, efficient general method is found, ordered intermetallic is inhibited
Polymer beads reunite and grow up, and have certain dissemination to the industrial applications of ordered intermetallic compound nano material.
Summary of the invention
For overcome the deficiencies in the prior art and disadvantage, the purpose of the present invention is to provide one kind to prevent intermetallic compound
The method and application reunited and grown up in high temperature.This method prepares the raw material of the electrode active material from commercial reagents, side
Easy, it is cheap.
The purpose of the present invention is achieved through the following technical solutions.
A method of prevent intermetallic compound from reuniting and growing up in high temperature, comprising the following steps:
(1) chloroplatinic acid, base metal salt, carbon material solution and polyvinyl alcohol (PVA) stirring ultrasonic mixing is uniform, then freeze
It is dry；
(2) by step (1) products therefrom in H2600-800 DEG C of high temperature quenching, obtains fuel-cell catalyst in/Ar environment
Pt3M/C, wherein M is base metal.
Preferably, the base metal salt is Fe salt, Co salt, Cr salt or Mn salt.
Preferably, the base metal salt is iron chloride, ferric sulfate, cobalt chloride, cobalt acetate or manganese chloride.
Preferably, the carbon material is graphene oxide (GO) or carbon dust (XC-72).
Preferably, the molar concentration of the carbon material solution is 8 mg/mL.
Preferably, the molar ratio of the chloroplatinic acid and base metal salt is 3:1.
Preferably, the freeze-drying is then first pre-freeze is dried in vacuo, and freeze-drying method is able to maintain Pt4+With your non-gold
Belong to ion presoma to be uniformly dispersed in carbon material.
Preferably, the temperature of the pre-freeze is -30 ~ -50 DEG C, and the time is 3 ~ 6 h.Further preferably -40 DEG C of pre-freezes
6h。
Preferably, the vacuum drying temperature is room temperature.
Preferably, the vacuum drying time is 12-24h
Preferably, the H2H in/Ar environment2Account for the 5-10 % of Ar volume.
Preferably, the time of the high temperature quenching treatment is 6-12h, is quenched time and temperature etc. by control high temperature
Little particle is obtained, is uniformly dispersed and PtM intermetallic compound that structure height is orderly.
Application of the PtM/C made from the process described above in electrode catalyst of fuel cell.
The present invention uses simple freeze-drying method, and base metal salt is impregnated on carbon material carrier, will after dipping
Aqueous carbon material supported presoma (platinum salt and base metal salt), is chilled to below freezing, and water is made to be changed into ice, then compared with
Ice is changed into steam under high vacuum.Due to being not required to heating stirring, it can be adsorbed in carrier in situ, reach and be dispersed in carrier
Effect.Subsequent heat treatment forms the intermetallic compound that partial size is small, structure height is orderly.The method is evaporated without heating, is formed
The presoma of high degree of dispersion, it is suppressed that particle is easy to reunite and grow up after high-temperature calcination reduction.Obtained material may be used as fuel
Cell catalyst, metal-air battery material.
Compared with the existing technology, the present invention has the advantage that and effect:
The present invention provides a kind of inhibition ordered intermetallic compound particle agglomerations and the preparation method and applications grown up, and have
Method is simple, low in cost, is easy to the advantages that industrializing.The electrode active material of preparation shows in hydrogen reduction performance test
Good catalytic performance out.
Detailed description of the invention
Fig. 1 is orderly Pt prepared by embodiment 63The XRD diagram of Mn/C.
Fig. 2 is orderly Pt prepared by embodiment 63The TEM of Mn/C schemes.
Fig. 3 is orderly Pt prepared by embodiment 63The hydrogen reduction performance chart of Mn/C.
Fig. 4 is Pt prepared by embodiment 43Fe/C transmission electron microscope picture.
Fig. 5 is Pt prepared by embodiment 53Co/C transmission electron microscope picture.
Fig. 6 is Pt prepared by embodiment 73Cr/C transmission electron microscope picture.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
GO plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, FeCl3And PVA, make
H2PtCl6Concentration be 12 mmol/L, FeCl3Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, first -40oThen pre-freeze 6h under C is dried in vacuo 24 h.Products therefrom is in 8% H2It is high in/Ar environment
Temperature quenching treatment, calcination temperature 600oC, time 6h.It is living that product is filtered, washed then drying to obtain fuel cell electrode
Property material Pt3Fe/C。
Embodiment 2
GO plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, CoCl2And PVA, make
H2PtCl6Concentration be 12 mmol/L, CoCl2Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 6h under C is dried in vacuo 24 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 700oC, time 6h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Co/C。
Embodiment 3
XC-72 plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, MnCl2And PVA, make
H2PtCl6Concentration be 12 mmol/L, MnCl2Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 6h under C is dried in vacuo 24 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 700oC, time 6h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Mn/C。
Embodiment 4
GO plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, FeCl3And PVA, make
H2PtCl6Concentration be 12 mmol/L, FeCl3Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 3h under C is dried in vacuo 12 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 700oC, time 12h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Fe/C。
Embodiment 5
XC-72 plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, CoCl2And PVA, make
H2PtCl6Concentration be 12 mmol/L, CoCl2Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 3h under C is dried in vacuo 12 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 700oC, time 12h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Co/C。
Embodiment 6
GO plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, MnCl2And PVA, make
H2PtCl6Concentration be 12 mmol/L, MnCl2Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 3h under C is dried in vacuo 12 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 700oC, time 12h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Mn/C。
Embodiment 7
XC-72 plus deionized water are configured to the solution of 10 mg/ml, are sequentially added into H2PtCl6, CrCl3And PVA, make
H2PtCl6Concentration be 12 mmol/L, CrCl3Concentration be 4 mmol/L and PVA concentration be 20 mg/mL, ultrasonic mixing is equal
It is even, it is then freeze-dried, -40oPre-freeze 6h under C is dried in vacuo 12 h.Products therefrom is in 8% H2The quenching of/Ar environment high temperature
Processing, calcination temperature 800oC, time 12h.Product is filtered, washed then drying to obtain fuel cell electrode active material
Pt3Cr/C。
Embodiment 8
The active material for weighing 5 mg embodiment 1-7 preparation respectively, is distributed to 50 μ L Nafion (5%) solution and 950 μ L second
In mixed alkoxide solution, 5 μ L drops are pipetted after glassy carbon electrode surface, drying in electrochemical workstation with liquid-transfering gun after being uniformly dispersed
Test acid system hydrogen reduction performance --- polarization curve performance.Pt prepared by embodiment 63The XRD diagram of Mn/C as shown in Figure 1,
For TEM figure as shown in Fig. 2, hydrogen reduction performance is as shown in figure 3, wherein initial reduction current potential is 0.95 v under 1600 revolving speeds, the limit is electric
Current density is 6.0mA cm-2, it is shown that more excellent hydrogen reduction performance.The hydrogen reduction of the active material of other embodiments preparation
Performance chart is similar with Fig. 3, shows more excellent hydrogen reduction performance.
Pt prepared by embodiment 4,5,73Fe/C, Pt3Co/C, Pt3The TEM figure of Cr/C such as Fig. 4, shown in 5,6.From Fig. 4,5,
6 it is found that Pt3Fe/C, Pt prepared by embodiment 4,5,73Co/C, Pt3Cr/C particle is uniformly dispersed, and agglomeration does not occur.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method for preventing intermetallic compound from reuniting in high temperature and growing up, which comprises the following steps:
(1) chloroplatinic acid, base metal salt, carbon material solution and polyvinyl alcohol stirring ultrasonic mixing is uniform, then it is freeze-dried；
(2) by step (1) products therefrom in H2600-800 DEG C of high temperature quenching, obtains fuel-cell catalyst PtM/ in/Ar environment
C。
2. the method according to claim 1, wherein the base metal salt is Fe salt, Co salt or Mn salt.
3. the method according to claim 1, wherein the base metal salt is iron chloride, ferric sulfate, chlorination
Cobalt, cobalt acetate or manganese chloride；The carbon material is graphene oxide or carbon dust.
4. the method according to claim 1, wherein the molar ratio of the chloroplatinic acid and base metal salt is 3:
1。
5. the method according to claim 1, wherein the freeze-drying is then first pre-freeze is dried in vacuo.
6. according to the method described in claim 5, the time is 3 ~ 6 it is characterized in that, the temperature of the pre-freeze is -30 ~ -50 DEG C
h。
7. according to the method described in claim 5, it is characterized in that, the vacuum drying time is 12-24h.
8. the method according to claim 1, wherein the H2H in/Ar environment2Account for the 5-10% of Ar volume.
9. the method according to claim 1, wherein the time of high temperature quenching treatment is 6-12h.
10. application of the PtM/C in electrode catalyst of fuel cell made from the described in any item methods of claim 1-9.
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Cited By (7)
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| CN110975877A (en) * | 2019-11-25 | 2020-04-10 | 华南理工大学 | Quenching modification method for improving electrocatalytic performance of metal oxide, prepared metal oxide electrocatalyst and application |
| CN111048793A (en) * | 2019-12-27 | 2020-04-21 | 苏州擎动动力科技有限公司 | Preparation method of platinum-based octahedral catalyst |
| CN112928284A (en) * | 2021-02-26 | 2021-06-08 | 华南理工大学 | Controllable intermetallic compound preparation method based on seed crystal induction |
| CN114400338A (en) * | 2022-03-25 | 2022-04-26 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
| CN114583189A (en) * | 2022-03-08 | 2022-06-03 | 中南大学 | Preparation method of efficient precious metal-rare earth alloy methanol poisoning resistant oxygen reduction catalyst |
| CN114784296A (en) * | 2022-03-08 | 2022-07-22 | 中南大学 | Preparation method of platinum-ruthenium-doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing methanol and ethanol oxidation |
| CN114864972A (en) * | 2022-04-21 | 2022-08-05 | 华南理工大学 | High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110975877A (en) * | 2019-11-25 | 2020-04-10 | 华南理工大学 | Quenching modification method for improving electrocatalytic performance of metal oxide, prepared metal oxide electrocatalyst and application |
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| CN111048793A (en) * | 2019-12-27 | 2020-04-21 | 苏州擎动动力科技有限公司 | Preparation method of platinum-based octahedral catalyst |
| CN112928284A (en) * | 2021-02-26 | 2021-06-08 | 华南理工大学 | Controllable intermetallic compound preparation method based on seed crystal induction |
| CN114583189A (en) * | 2022-03-08 | 2022-06-03 | 中南大学 | Preparation method of efficient precious metal-rare earth alloy methanol poisoning resistant oxygen reduction catalyst |
| CN114784296A (en) * | 2022-03-08 | 2022-07-22 | 中南大学 | Preparation method of platinum-ruthenium-doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing methanol and ethanol oxidation |
| CN114784296B (en) * | 2022-03-08 | 2024-02-02 | 中南大学 | Preparation method of platinum-ruthenium doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing oxidation of methanol and ethanol |
| CN114583189B (en) * | 2022-03-08 | 2024-02-06 | 中南大学 | Preparation method of efficient noble metal-rare earth alloy methanol poisoning resistant oxygen reduction catalyst |
| CN114400338A (en) * | 2022-03-25 | 2022-04-26 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
| CN114400338B (en) * | 2022-03-25 | 2022-06-28 | 中国科学院过程工程研究所 | Mn-PtM/C type platinum-based oxygen reduction catalyst and preparation method and application thereof |
| CN114864972A (en) * | 2022-04-21 | 2022-08-05 | 华南理工大学 | High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof |
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