CN103972520B - Elastic carbon foam oxygen reduction catalyst and preparation method thereof - Google Patents

Elastic carbon foam oxygen reduction catalyst and preparation method thereof Download PDF

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Publication number
CN103972520B
CN103972520B CN201410157562.7A CN201410157562A CN103972520B CN 103972520 B CN103972520 B CN 103972520B CN 201410157562 A CN201410157562 A CN 201410157562A CN 103972520 B CN103972520 B CN 103972520B
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Prior art keywords
oxygen
reduction catalyst
oxygen reduction
carbon foam
catalyst
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CN201410157562.7A
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CN103972520A (en
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陈水亮
侯豪情
周龑
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Jiangxi Normal University
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Jiangxi Normal University
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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention discloses an elastic carbon foam oxygen reduction catalyst and a preparation method thereof. The elastic carbon foam oxygen reduction catalyst is prepared from high-temperature carbonization of melamine foam materials under a trace oxygen contained condition; the elastic carbon foam oxygen reduction catalyst is provided with self-supporting three dimensional net structure and excellent elasticity; the elastic carbon foam oxygen reduction catalyst is provided with oxygen reduction catalyst performance equivalent to that of the 20wt. % Pt/C. The elastic carbon foam oxygen reduction catalyst can be used for the cathodes of fuel and metal-air batteries.

Description

A kind of elasticity carbon foam oxygen reduction catalyst agent and preparation method thereof
Technical field
The present invention relates to a kind of elasticity carbon foam oxygen reduction catalyst agent and preparation method thereof.
Background technology
In recent years, because society is for the urgent demand of the new energy technology of high-efficiency cleaning, fuel cell and metal-air The research of battery correlation technique is of increased attention.For above two battery, it is required in its negative electrode using tool The catalyst having electro catalytic activity is to promote redox reactions.These catalyst include platinum catalyst, transition metal/nitrogen/carbon, Conducting polymer, Heteroatom doping C catalyst etc..These catalyst are all to exist in the form of a powder, need when using to make With binding agent (nafion or politef), they are bonded, then form Catalytic Layer.But the use of binding agent is on the one hand The complexity of technique can be increased, increase cost, on the other hand can block the micro-pore within Catalytic Layer so that reaction passes again Matter is obstructed.These due to the series of problems caused by catalyst structure show in lithium-air battery cathode especially prominent, Because its negative electrode is not only the place that redox reactions are carried out, also to go to accommodate product lithium peroxide in more spaces simultaneously (f. cheng, and j. chen,chem. soc. rev., 2012,41,2172 2192).At present, research has one The catalyst of fixed structure has begun to be valued by the people, and such as sun et al. grows the pt nano wire of burr shape on carbon black pellet (s. sun, f. jaouen, and j. dodelet,adv. mater., 2008,20,3,900 3904), liu et al. Preparation have three dimensional structure carbon foam catalyst (z. liu, h. nie, z. yang, j. zhang, z. jin, y. lu, z. xiao and s. huang,nanoscale, 2013,5,3,283 3288), and lee et al. preparation Have a large amount of holes tripolycyanamide C catalyst (j. lee, g. park, s. kim, m. liu, and j. cho,angew. chem. int. ed., 2013,52,1026 1030) etc..Although these materials all possess certain hole Structure, but because these catalyst do not have mechanical performance (fragility), so they cannot avoid the use of binding agent, also cannot be real The self-supporting of existing catalyst.Certainly also with the presence of self-supporting negative electrode in lithium-air battery, but they mainly pass through to urge Agent be attached to and realize on the carrier of self-supporting such as nickel foam (y. cui, z. wen and y. liu,energy environ. sci., 2011,4,4727), catalyst is to there is not self-supporting property in itself.Here, the present invention is open A kind of elasticity carbon foam oxygen reduction catalyst agent and preparation method thereof.
Content of the invention
It is an object of the invention to provide a kind of elasticity carbon foam oxygen reduction catalyst agent and preparation method thereof.The present invention is It is achieved in that, under the conditions of containing micro amount of oxygen, direct high temperature cabonization melamine formaldehyde resin foam preparation Elastic Carbon bubble Foam.The three-dimensional net structure of self-supporting, good resilience are had by elastic carbon foam prepared by the method, excellent oxygen Reduction catalystses performance.
Described high temperature cabonization, its process is: melamine formaldehyde resin foam is placed in body of heater, in micro amount of oxygen bar Under part, 800-1200 ° of c is heated to the speed of 2-20 ° of c/min, wherein optimum carburizing temperature is 900-1000oc.
Described micro amount of oxygen condition, the concentration of its oxygen is 0.01 ml/l ~ 5 ml/l；Wherein optimum concentration is 0.1 ~ 1 ml/l.
Described micro amount of oxygen condition, embodiments thereof is: (a) exchanges poly cyanamid-formaldehyde resin foam material with noble gases Residual oxygen in material, controls its swap time；Or (b) is under inert gas shielding or under vacuum, add one in the reactor The quantitative chemical substance that can produce oxygen during high temperature cabonization, including slaine (as kclo3, kmno4Deng), metal oxygen Compound is (as mno2, fe2o3Deng) etc..
Described elastic carbon foam oxygen reduction catalyst agent, its raw material is melamine formaldehyde resin foamed materialss, and has Have a following architectural feature: perforate, density range be 4-12 kg/m3, porosity be more than 95%, its pattern such as accompanying drawing 5.
Described elastic carbon foam oxygen reduction catalyst agent, its oxygen reduction catalyst performance and elasticity can be micro- by adjusting Measure oxygen concentration to regulate and control.
The solution have the advantages that: this elastic carbon foam oxygen reduction catalyst agent has the feature that
A the three-dimensional porous network structure of () self-supporting, as shown in Figure 1, porosity is more than 99%；
B () excellent elasticity, as shown in Figure 2, catalyst can be with resilience after being compressed；
(c) excellent redox reactions catalytic performance, the such as cyclic voltammogram of accompanying drawing 3, the bullet of preparation under optimum condition Property carbon foam oxygen reduction catalyst agent, its catalysis spike potential be -0.19v, suitable with the -0.16v of 20wt.% pt/c；As accompanying drawing 4 its linear voltammogram of No. 1 sample, its catalytic reaction take-off potential is 0v, with the 0.02v of 20wt.% pt/c closely.
The carbon foam prepared under conditions of anaerobic (less than the fine vacuum of 10pa) is fragility, does not have any bullet Property, and oxygen reduction catalyst performance is also very low.As accompanying drawing 6d, cyclic voltammogram shows, its redox reactions current potential is- 0.33v, far below 20wt.% pt/c catalyst.
The main component of the elastic carbon foam oxygen reduction catalyst agent of present invention preparation is the material with carbon element of nitrogen oxygen codope, its Photoelectricity energy spectrum diagram (xps) such as accompanying drawing 8.This catalyst preparation is simple, low cost, will can be used for fuel cell and metal-air electricity The negative electrode in pond.
Brief description
Fig. 1 is the scanning electron microscopic picture of the three-dimensional porous network structure of elastic carbon foam oxygen reduction catalyst agent.
Fig. 2 is the compression rebound photo of elastic carbon foam oxygen reduction catalyst agent.
Fig. 3 is the cyclic voltammetry comparison diagram of elastic carbon foam oxygen reduction catalyst agent and 20wt.% pt/c catalyst (oxygen reduction catalyst performance comparison figure).
Linear volt-ampere comparison diagram (1) nitrogen of the different oxygen reduction catalyst agent of Fig. 4 exchanges 0h(cf-0h), (2) nitrogen Exchange 0.5h(cf-0.5h), nitrogen exchanges 10h(cf-10h), the vacuum condition (cf-vac) less than 10pa and (5) pt/c.
The scanning electron microscope diagram piece of Fig. 5 melamine formaldehyde resin foam.
Under Fig. 6 different condition, cyclic voltammetry figure (a) nitrogen of the carbon foam catalyst of preparation exchanges 0h, (b) nitrogen Exchange 0.5h, (c) nitrogen exchanges 10h, (d) < fine vacuum of 10pa.
Fig. 7 adds not commensurability kmno4Under the conditions of preparation carbon foam catalyst cyclic voltammetry comparison diagram.
The carbon foam oxygen reduction catalyst agent light electric spectrum comparison diagram of preparation under Fig. 8 different condition, (a) full spectrogram, (b) The finely general figure of n1s, the fine spectrogram of (c) o1s.
Embodiment
1 control noble gases prepare carbon oxygen reduction catalyst agent swap time
The melamine resin foam that 1 block size is 9 cm × 5 cm × 3 cm sizes puts into 1 diameter 80mm, long In the quartz ampoule of 1000mm, load onto interface.First at normal temperatures with 100 ml min-1Speed nitrogen exchange 0 h, oxygen concentration is about For 1 ml/l；Then with 10 ° of c min-1Heating rate be raised to 1000 ° of c, stop 1h in this temperature, then allow it natural Drop to and take out under room temperature.
Ibid, change nitrogen swap time, such as 0.5,2,5,10 h, the oxygen content preparation carbon foam of regulation and control reaction system, Adjust its elasticity and oxygen reduction catalyst performance.
2 control addition kmno4Amount preparing carbon oxygen reduction catalyst agent
1 block size is the melamine resin foam of 9 cm × 5 cm × 3 cm sizes and one fill 0.38 g kmno4Porcelain boat put and together put into 1 diameter 80mm, in the quartz ampoule of long 1000 mm.At normal temperatures with 100 ml min-1's Speed nitrogen exchanges 10h, then with 10 ° of c min-1Heating rate be raised to 1000 ° of c, this temperature stop 1h, reactant In system, oxygen concentration is about 0.1 ml/l；Then it is allowed to naturally ring to take out under room temperature.
Ibid, change kmno4Addition, such as 0.76 g, 1.52 g etc., the oxygen content in regulation and control reaction system prepares carbon Foam, adjusts its elasticity and oxygen reduction catalyst performance.
The oxygen reduction catalyst performance test of 3 catalyst
Using three-electrode system (to electrode-platinum filament, reference electrode-silver/silver chloride (saturation kcl)) in oxygen saturation In 0.1m koh electrolyte, the catalytic performance of test catalyst.By the carbon foam pulverized or pt/c catalyst with identical quality Load on the glass-carbon electrode of fresh polishing, as working electrode, be circulated voltammetric scan test.By the carbon foam pulverized or Pt/c catalyst using identical mass loading to the rotation glass-carbon electrode of fresh polishing on as working electrode, at 1600 revs/min Carry out linear voltammetric scan test under conditions of clock.
Different nitrogen contrast with the cyclic voltammetric of the C catalyst adding different kmno4 to prepare under the conditions of measuring swap time Figure, is shown in accompanying drawing 6 and accompanying drawing 7 respectively.

Claims (5)

1. a kind of elasticity carbon foam oxygen reduction catalyst agent, described method for preparing catalyst is: with melamine formaldehyde resin Foamed materialss are raw material, and under the conditions of micro amount of oxygen, high temperature cabonization prepares, the temperature range of described high temperature cabonization is 800～ 1200℃；The oxygen concentration range of described micro amount of oxygen condition is 0.01ml/l～5ml/l, and prepared catalyst has following spy Levy:
A () self-supporting three-dimensional carbon network structure, porosity is more than 99%；
(b) excellent resilience；
C () excellent oxygen reduction catalyst performance, its catalysis take-off potential is close with 20wt.%pt/c catalyst.
2. a kind of elasticity according to claim 1 carbon foam oxygen reduction catalyst agent, is characterized in that described micro amount of oxygen condition Control mode include:
A () exchanges the residual oxygen in poly cyanamid-formaldehyde resin foam material with noble gases, control its swap time；Or (b) The chemicals of oxygen under inert gas shielding or under vacuum, can be produced during being added in high temperature cabonization in the reactor Matter, including slaine or metal-oxide, wherein slaine is kclo3Or kmno4, metal-oxide is mno2Or fe2o3.
3. a kind of elasticity according to claim 1 carbon foam oxygen reduction catalyst agent, is characterized in that the structure of described raw material Be characterized as perforate, density range be 4-12kg/m3, porosity be more than 95%.
4. a kind of elasticity according to claim 2 carbon foam oxygen reduction catalyst agent, the oxygen reduction of described catalyst is urged Change performance and elasticity to regulate and control by the concentration adjusting micro amount of oxygen with described control method.
5. a kind of elasticity carbon foam oxygen reduction catalyst agent described in claim 1, is characterized in that the temperature of described high temperature cabonization For 900-1000 DEG C；The oxygen concentration range of described micro amount of oxygen condition is 0.1～1ml/l.
CN201410157562.7A 2014-04-18 2014-04-18 Elastic carbon foam oxygen reduction catalyst and preparation method thereof Expired - Fee Related CN103972520B (en)

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CN107317040A (en) * 2017-06-22 2017-11-03 清华大学 The floatation type gas-diffusion electrode reacted for gas consumption and its preparation
CN108172793B (en) * 2017-12-27 2020-08-11 辽宁工程技术大学 Method for preparing three-dimensional carbon foam/graphene oxide-based composite material through centrifugal separation
CN109360992A (en) * 2018-10-23 2019-02-19 青岛科技大学 A kind of metal-nitrogen-carbon nanosheet preparation method and application of three-dimensional continuous carbon skeleton adulteration
CN113480830A (en) * 2021-06-19 2021-10-08 中国大唐集团科学技术研究院有限公司中南电力试验研究院 Method for preparing heat-conducting composite material by utilizing melamine formaldehyde foam

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DE10243240A1 (en) * 2002-09-17 2004-03-25 Basf Ag Foam useful for electrical and electrochemical applications, comprises at least 70 wt.% of carbon with pores in the cell framework material of 0.2-50 nm in size and a volume of 0.01-0.8 cm3/g
CN101941693B (en) * 2010-08-25 2012-07-25 北京理工大学 Graphene aerogel and preparation method thereof
CN102732037B (en) * 2011-04-08 2014-09-10 中国科学院金属研究所 Graphene foam/polymer high-conductivity composite material preparation method and application thereof
CN102874792A (en) * 2012-10-23 2013-01-16 江西师范大学 Novel carbon sponge preparation method

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