CN103972520A - 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
CN103972520A
CN103972520A CN201410157562.7A CN201410157562A CN103972520A CN 103972520 A CN103972520 A CN 103972520A CN 201410157562 A CN201410157562 A CN 201410157562A CN 103972520 A CN103972520 A CN 103972520A
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China
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oxygen reduction
oxygen
carbon foam
reduction catalyst
elastic carbon
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CN201410157562.7A
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CN103972520B (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

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 Elastic Carbon foam oxygen reduction Catalysts and its preparation method
Technical field
The present invention relates to a kind of Elastic Carbon foam oxygen reduction Catalysts and its preparation method.
Background technology
In recent years, because society is for the urgent demand of the new energy technology of high-efficiency cleaning, the research of fuel cell and metal-air cell correlation technique has received increasing concern.For above-mentioned two kinds of batteries, in its negative electrode, all need to use the catalyst with electro catalytic activity to promote oxygen reduction reaction.These catalyst comprise platinum catalyst, transition metal/nitrogen/carbon, conducting polymer, Heteroatom doping C catalyst etc.These catalyst are all to exist with the form of powder, need in use to use binding agent (Nafion or polytetrafluoroethylene) that they are bonding, then form Catalytic Layer.But the use of binding agent can increase the complexity of technique on the one hand, increases cost, can block again on the other hand the micro-pore of Catalytic Layer inside, and reaction mass transfer is obstructed.These due to the caused series of problems of catalyst structure in lithium-air battery negative electrode, show particularly outstanding, be not only oxygen reduction because of its negative electrode and react the place of carrying out, also want more space to remove to hold product lithium peroxide (F. Cheng, and J. Chen simultaneously chem. Soc. Rev., 2012,41,2172 – 2192).At present, the catalyst that research has a fixed structure has started to be valued by the people, as the people such as Sun on carbon black pellet, grow burr shape Pt nano wire (S. Sun, F. Jaouen, and J. Dodelet, adv. Mater., 2008,20,3900 – 3904), the carbon foam catalyst of three-dimensional structure that prepared by the people such as Liu have (Z. Liu, H. Nie, Z. Yang, J. Zhang, Z. Jin, Y. Lu, Z. Xiao and S. Huang, nanoscale, 2013,5,3283 – 3288), and the melamine C catalyst with a large amount of holes prepared of the people such as Lee (J. Lee, G. Park, S. Kim, M. Liu, and J. Cho, angew. Chem. Int. Ed., 2013,52,1026 – 1030) etc.Although these materials have all possessed certain pore structure, because these catalyst do not have mechanical performance (fragility), so they cannot avoid the use of binding agent, also cannot realize the self-supporting of catalyst.Certainly in lithium-air battery, also have self-supporting negative electrode to exist, but they be mainly carrier by catalyst being attached to self-supporting as realized in nickel foam (Y. Cui, Z. Wen and Y. Liu, energy Environ. Sci., 2011,4,4727), catalyst itself is not have self-supporting character.Here, the present invention discloses a kind of Elastic Carbon foam oxygen reduction Catalysts and its preparation method.
Summary of the invention
The object of the present invention is to provide a kind of Elastic Carbon foam oxygen reduction Catalysts and its preparation method.The present invention is achieved in that and containing under micro amount of oxygen condition, and directly high temperature cabonization melamine formaldehyde resin foam is prepared Elastic Carbon foam.The Elastic Carbon foam of preparing by the method has the three-dimensional net structure of self-supporting, good resilience, excellent oxygen reduction catalytic performance.
Described high temperature cabonization, its process is: melamine formaldehyde resin foam is placed in to body of heater, under micro amount of oxygen condition, is heated to 800-1200 ° of C with the speed of 2-20 ° of C/min, wherein optimum carburizing temperature is 900-1000 oC.
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, its execution mode is: (a), with the residual oxygen in inert gas exchange poly cyanamid-formaldehyde resin foam material, control its swap time; Or (b) under inert gas shielding or under vacuum, in reactor, add a certain amount of can oxygenous chemical substance in high temperature cabonization process, comprise that slaine is (as KClO 3, KMnO 4deng), metal oxide is (as MnO 2, Fe 2o 3deng) etc.
Described Elastic Carbon foam oxygen reduction catalyst, its raw material is melamine formaldehyde resin foamed material, and has following architectural feature: perforate, density range is 4-12 kg/m 3, porosity is greater than 95%, and its pattern is as accompanying drawing 5.
Described Elastic Carbon foam oxygen reduction catalyst, its oxygen reduction catalytic performance and elasticity can be by regulating micro amount of oxygen concentration to regulate and control.
Technique effect of the present invention is: this Elastic Carbon foam oxygen reduction catalyst has following characteristics:
(a) the three-dimensional porous network configuration of self-supporting, as shown in Figure 1, porosity exceedes 99%;
(b) excellent elasticity, as shown in Figure 2, can resilience after catalyst is compressed;
(c) excellent oxygen reduction reacting catalytic performance, as the cyclic voltammogram of accompanying drawing 3, the Elastic Carbon foam oxygen reduction catalyst of preparing under optimum condition, its catalysis spike potential is-0.19V, with 20wt.% Pt/C-0.16V is suitable; As accompanying drawing 4 No. 1 its linear voltammogram of sample, its catalytic reaction take-off potential is 0V, very approaching with the 0.02V of 20wt.% Pt/C.
The carbon foam that (is less than the high vacuum of 10Pa) prepares under the condition that approaches anaerobic is fragility, without any elasticity, and oxygen reduction catalytic performance is also very low.As accompanying drawing 6D, cyclic voltammogram demonstration, its oxygen reduction reaction potential is-0.33V, far below 20wt.% Pt/C catalyst.
The main component of Elastic Carbon foam oxygen reduction catalyst prepared by the present invention is the material with carbon element of nitrogen oxygen codope, and its photoelectricity energy spectrogram (XPS) is as accompanying drawing 8.This catalyst preparation is simple, cost is low, will can be used for the negative electrode of fuel cell and metal-air battery.
Brief description of the drawings
Fig. 1 is the ESEM picture of the three-dimensional porous network configuration of Elastic Carbon foam oxygen reduction catalyst.
Fig. 2 is the compression rebound photo of Elastic Carbon foam oxygen reduction catalyst.
Fig. 3 is the cyclic voltammetry comparison diagram (oxygen reduction catalytic performance comparison diagram) of Elastic Carbon foam oxygen reduction catalyst and 20wt.% Pt/C catalyst.
Linear volt-ampere comparison diagram (1) the nitrogen exchange 0h(CF-0h of the oxygen reduction catalyst that Fig. 4 is different), (2) nitrogen exchange 0.5h(CF-0.5h), nitrogen exchange 10h(CF-10h) and, be less than vacuum condition (CF-vac) and (5) Pt/C of 10Pa.
The scanning electron microscope diagram sheet of Fig. 5 melamine formaldehyde resin foam.
Cyclic voltammetry figure (A) the nitrogen exchange 0h of the carbon foam catalyst of preparing under Fig. 6 different condition, (B) nitrogen exchange 0.5h, (C) nitrogen exchange 10h, (D) high vacuum of <10Pa.
Fig. 7 adds different amount KMnO 4the cyclic voltammetry comparison diagram of the carbon foam catalyst of preparing under condition.
The carbon foam oxygen reduction catalyst photoelectricity power spectrum comparison diagram of preparing under Fig. 8 different condition, (A) full spectrogram, (B) the meticulous general figure of N1s, (C) the meticulous spectrogram of O1s.
embodiment
1 controls inert gas prepares carbon oxygen reduction catalyst swap time
1 melamine resin foam that is of a size of 9 cm × 3, cm × 5 cm sizes is put into 1 diameter 80mm, in the quartz ampoule of long 1000mm, load onto interface.First at normal temperatures with 100 ml min -1speed nitrogen exchange 0 h, oxygen concentration is about 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 naturally drop under room temperature and take out.
The same, change nitrogen swap time, as 0.5,2,5,10 h, the oxygen content of regulation and control reaction system is prepared carbon foam, regulates its elasticity and oxygen reduction catalytic performance.
2 controls add KMnO 4amount prepare carbon oxygen reduction catalyst
1 melamine resin foam that is of a size of 9 cm × 3, cm × 5 cm sizes and one are filled to 0.38 g KMnO 4porcelain boat put and together put into 1 diameter 80mm, in the quartz ampoule of long 1000 mm.At normal temperatures with 100 ml min -1speed nitrogen exchange 10h, then with 10 ° of C min -1heating rate be raised to 1000 ° of C, stop 1h in this temperature, in reaction system, oxygen concentration is about 0.1 ml/L; Then allowing it naturally drop under room temperature takes out.
The same, change KMnO 4addition, as 0.76 g, 1.52 g etc., the oxygen content of regulation and control in reaction system prepared carbon foam, regulates its elasticity and oxygen reduction catalytic performance.
The oxygen reduction catalytic performance test of 3 catalyst
Use three-electrode system (to electrode-platinum filament, reference electrode-Yin/silver chlorate (saturated KCl)) in the saturated 0.1M KOH electrolyte of oxygen, the catalytic performance of detecting catalyst.By the carbon foam pulverizing or Pt/C catalyst with identical mass loading to the glass-carbon electrode of fresh polishing, as work electrode, carry out cyclic voltammetry scan test.By the carbon foam pulverizing or Pt/C catalyst on the rotation glass-carbon electrode using identical mass loading to fresh polishing as work electrode, under the condition of 1600 revs/min, carry out the sweep test of linearity volt-ampere.
Different nitrogen swap times and add the cyclic voltammetric comparison diagram of the C catalyst of preparing under different K MnO4 amount condition, see respectively accompanying drawing 6 and accompanying drawing 7.

Claims (7)

1. an Elastic Carbon foam oxygen reduction catalyst, is characterized in that described catalyst has following characteristics:
A) self-supporting three-dimensional carbon network configuration, porosity exceedes 99%;
B) excellent resilience;
C) the oxygen reduction reacting catalytic performance suitable with 20wt.% Pt/C.
2. the preparation method of the Elastic Carbon foam oxygen reduction catalyst described in claim 1, is characterized in that: taking melamine formaldehyde resin foamed material as raw material, and under micro amount of oxygen condition, high temperature cabonization preparation.
3. the high temperature cabonization described in claim 2, is characterized in that temperature range is 800 ~ 1200 oc, Optimal Temperature is 900-1000 oC.
4. the micro amount of oxygen described in claim 2, is characterized in that oxygen concentration scope is 0.01 ml/L ~ 5 ml/L, and optimum oxygen concentration scope is 0.1 ~ 1 ml/L.
5. the micro amount of oxygen condition described in claim 2 and 4, is characterized in that control mode comprises:
(a) with the residual oxygen in inert gas exchange poly cyanamid-formaldehyde resin foam material, control its swap time; Or (b) under inert gas shielding or under vacuum, can oxygenous chemical substance under being added in high temperature cabonization process in reactor, comprise slaine, as KClO 3or KMnO 4deng, metal oxide, as MnO 2or Fe 2o 3deng.
6. the Elastic Carbon foam oxygen reduction catalyst described in claim 1 and 2, is characterized in that raw material is melamine formaldehyde resin foamed material; The architectural feature of raw material be perforate, density range is 4-12 kg/m 3, porosity is greater than 95%.
7. the Elastic Carbon foam oxygen reduction catalyst described in claim 1 and 2, its oxygen reduction catalytic performance and elasticity can regulate the concentration of micro-oxygen to regulate and control by the method described in right 5.
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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108172793A (en) * 2017-12-27 2018-06-15 辽宁工程技术大学 Centrifuge the method for preparing three-dimensional carbon foam/graphene oxide based composites
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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CN102732037A (en) * 2011-04-08 2012-10-17 中国科学院金属研究所 Graphene foam/polymer high-conductivity composite material preparation method and application thereof
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108172793A (en) * 2017-12-27 2018-06-15 辽宁工程技术大学 Centrifuge the method for preparing three-dimensional carbon foam/graphene oxide based composites
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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