CN103943869B - A kind of preparation method of coated with graphite paper load NiAu thin-film electrode material - Google Patents

A kind of preparation method of coated with graphite paper load NiAu thin-film electrode material Download PDF

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Publication number
CN103943869B
CN103943869B CN201410105310.XA CN201410105310A CN103943869B CN 103943869 B CN103943869 B CN 103943869B CN 201410105310 A CN201410105310 A CN 201410105310A CN 103943869 B CN103943869 B CN 103943869B
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graphite
paper
niau
coated
membrane electrode
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CN103943869A (en
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王贵领
张栋铭
潘越
曹殿学
徐阳
闫鹏
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Heilongjiang hachang carbon material technology Co.,Ltd.
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Harbin Engineering 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
    • 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)
  • Inert Electrodes (AREA)

Abstract

The present invention is to provide a kind of preparation method of coated with graphite paper load NiAu thin-film electrode material.Make curing agent with clay, be coated on plain paper surface by after clay and graphite Homogeneous phase mixing; By 5 ~ 5.5g? NH 4cl and 1 ~ 1.5g? NiCl 2be dissolved in 50mL water and make electrodeposit liquid; In electrodeposit liquid, the paper scribbling graphite is kept 20 ~ 30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160 ~ 180min at-1.0v, obtains paper-graphite-Ni membrane electrode; By paper-graphite-Ni membrane electrode at 1mmolL -1hAuClO 4leave standstill 2 ~ 4 minutes in solution, obtain paper-graphite-NiAu membrane electrode.The present invention's coated with graphite paper, by the surface of Ni electro-deposition in the paper of the coating graphite of conduction, then prepares pencil coated paper load NiAu catalyst with Au replacing section Ni, improves the method for the anode-catalyzed performance of direct borohydride fuel cell.Solve the problem of sodium borohydride fuel cell anode poor activity.

Description

A kind of preparation method of coated with graphite paper load NiAu thin-film electrode material
Technical field
That the present invention relates to is a kind of preparation method of thin-film electrode material, specifically a kind of with the method for coated with graphite paper load NiAu catalysis boron hydride electroxidation performance.
Background technology
Direct sodium borohydride fuel cell (DBFC) is the NaBH be dissolved in alkaline electrolyte solution 4directly as the fuel cell of fuel.Sodium borohydride is the hydrogen storage material of hydrogen content very high (solid is 11wt.%, and saturated sodium borohydride solution is 7.4wt.%).Sodium borohydride has the hydrogen storage ability of larger volume than compressed hydrogen and liquefying hydrogen.NaBH 4faster than the oxidation kinetics of methyl alcohol, energy density and cell voltage are also better than methyl alcohol.NaBH 4nonflammable, toxicity is low, pollution-free, do not produce CO 2, only have weak erosive, so device is simple, volume is little, accumulating is convenient, can exempt the danger of blast, security performance is comparatively superior.Sodium borohydride Solution or solid form are preserved, and in alkaline solution, Absorbable organic halogens exists the several months.Catalyst and product can recycle, NaBH 4unique accessory substance NaBO of hydrolysis 2to environment nonhazardous effect, and can as synthesis NaBH 4raw material, thus realize recycling of resource.DBFC can work at ambient temperature, and thus battery easily starts.Consider from ergonomic point, NaBH 4solution can serve as heat exchange medium carry out cool batteries and need not be extra coldplate; The electric osmose towing of water can be used as cathode reactant, and need not need to soak as hydrogen and air; These characteristics are useful for the design of fuel cell.
NaBH in theory 4electrocatalytic Oxidation can be 8e -reaction, see (1) formula:
BH 4 -+8OH -→BO 2 -+4H 2O+8e -(1)
DBFC is NaBH in theory 4non-platinum catalyst can be used, NaBH 4electro-oxidizing-catalyzing agent is mainly divided into two large classes, and a class is the noble metals such as Pt, Pd, Au, Ir, and wherein the electro catalytic activity of Pt is the highest, but is also easy to NaBH occurs 4hydrolysis, see (2) formula:
NaBH 4+2H 2O→4H 2+NaBO 2(2)
KuiCheng can be consulted; DianxueCao; FanYang; DongmingZhang; PengYan; JinlingYin; Guilingwang.Pddopedthree-dimensionalporousNifilmsupporte donNifoamanditshighperformancetowardsNaBH 4electrooxidation.JournalofPowerSources, 2013,242:141-147, and CaoDianxue, GaoYinyi, WangGuiling, MiaoRongrong, LiuYao.AdirectNaBH 4– H 2o 2fuelcellusingNifoamsupportedAunanoparticlesaselectrodes. InternationalJournalofHydrogenEnergy, 2010,35:807 – 813..
Summary of the invention
The object of the present invention is to provide one can improve the anode-catalyzed performance of direct borohydride fuel cell, solve the preparation method of the coated with graphite paper load NiAu thin-film electrode material of the problem of sodium borohydride fuel cell anode poor activity.
The object of the present invention is achieved like this:
The object of the present invention is achieved like this:
(1) make curing agent with clay, be coated on plain paper surface by after clay and graphite Homogeneous phase mixing;
(2) by 5 ~ 5.5gNH 4cl and 1 ~ 1.5gNiCl 2be dissolved in 50mL water and make electrodeposit liquid;
(3) in electrodeposit liquid, the paper scribbling graphite is kept 20 ~ 30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160 ~ 180min at-1.0v, obtains paper-graphite-Ni membrane electrode;
(4) finally by paper-graphite-Ni membrane electrode at 1mmolL -1hAuClO 4leave standstill 2 ~ 4 minutes in solution, obtain paper-graphite-NiAu membrane electrode, i.e. coated with graphite paper load NiAu catalyst.
The present invention's coated with graphite paper, by the surface of Ni electro-deposition in the paper of the coating graphite of conduction, then prepares pencil coated paper load NiAu catalyst with Au replacing section Ni, improves the method for the anode-catalyzed performance of direct borohydride fuel cell.Overcome collector price high, and the shortcoming such as sodium borohydride decomposition, solve the problem of sodium borohydride fuel cell anode poor activity.
Essence of the present invention is the battery structure adopting sodium borohydride fuel cell etc., with coated with graphite paper load NiAu for catalyst, forms the anode of fuel cell.
The invention has the advantages that the catalyst utilizing coated with graphite paper load NiAu catalyst as sodium borohydride Electrocatalytic Oxidation, solve borohydride fuel anode discharge electric current little and be easy to the problems such as hydrolysis.Do not use binding agent in the preparation of this electrode material, the more important thing is that under electric field action graphite and clay can form the cross-linking compounds of paper-graphite-clay-Ni Au, not only good conductivity with Ni and Au, and electro catalytic activity is high.The reserves of paper load NiAu catalyst not only graphite, clay, Ni are extremely rich and easy to get, cheap, greatly reduce electrode preparation cost, and its catalytic activity is high, stable performance, preparation process is easy, be applicable to suitability for industrialized production, there is prospects for commercial application and market value.
Embodiment
In order to the effect of present invention process is described better, be illustrated with instantiation below.
(1) get common paper one, be coated on paper surface after doing curing agent and graphite Homogeneous phase mixing with clay, get 1 × 1cm -2as Electrode; (2) by 5gNH 4cl and 1gNiCl 2be dissolved in 50mL water, for potentiostatic method deposit N i.(3) paper scribbling graphite is kept 20 ~ 30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160 ~ 180min at-1.0v, obtains paper-graphite-Ni membrane electrode.(4) finally by paper-graphite-Ni membrane electrode at 1mmolL -1hAuClO 4leave standstill 2 ~ 4 minutes in solution, obtain paper-graphite-NiAu membrane electrode, i.e. coated with graphite paper load NiAu catalyst.
Following performance test is carried out to paper-graphite-NiAu membrane electrode:
1, with paper-graphite-NiAu film for work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaBH of NaOH and 0.10mol/L of 1mol/L 4solution in, under the voltage of-0.4Vvs.Ag/AgCl, chrono-amperometric density reaches 120mA/cm 2.
2, with paper-graphite-NiAu film for work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaBH of NaOH and 0.50M of 2M 4solution in, under the voltage of-0.4Vvs.Ag/AgCl, chrono-amperometric density reaches 350mA/cm 2.
3, paper-graphite-NiAu film catalyst NaBH is utilized 4electroxidation is anode, and the KOH of 3mol/L is Anolyte solution, and the sodium borohydride of 1mol/L is fuel; With the nano Pd particle catalysis H of load in nickel foam 2o 2direct electroreduction is negative electrode, with KOH and 0.6mol/L of 3mol/L -1h 2o 2as catholyte; Nafin-115 proton exchange is touched as barrier film; The maximum power density of battery is 245mW/cm -2.

Claims (1)

1. a preparation method for paper-graphite-NiAu thin-film electrode material, is characterized in that:
(1) make curing agent with clay, the surperficial paper obtaining scribbling graphite of plain paper will be coated on after clay and graphite Homogeneous phase mixing;
(2) by 5 ~ 5.5gNH 4cl and 1 ~ 1.5gNiCl 2be dissolved in 50mL water and make electrodeposit liquid;
(3) in electrodeposit liquid, the paper scribbling graphite that step (1) obtains is kept 20 ~ 30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160 ~ 180min at-1.0v, obtains paper-graphite-Ni membrane electrode;
(4) finally by paper-graphite-Ni membrane electrode at 1mmolL -1hAuClO 4leave standstill 2 ~ 4 minutes in solution, obtain paper-graphite-NiAu membrane electrode.
CN201410105310.XA 2014-03-21 2014-03-21 A kind of preparation method of coated with graphite paper load NiAu thin-film electrode material Active CN103943869B (en)

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CN109994744B (en) * 2019-01-31 2021-09-07 重庆大学 Nickel-cobalt binary catalyst for promoting direct oxidation of sodium borohydride
CN113036164B (en) * 2019-12-24 2022-05-27 大连大学 Preparation method and application of composite electrode based on mesoporous carbon foam
CN113054206B (en) * 2019-12-27 2022-06-07 大连大学 Preparation method and application of NiNPs/AuNPs/GN/AgNWs/paper plastic electrode

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102088089A (en) * 2010-12-27 2011-06-08 浙江大学 Preparation method of combined electrode of fuel cell and test device thereof

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US20110135966A1 (en) * 2009-12-05 2011-06-09 Vishnu Jayaprakash Novel cow-dung based microbial fuel cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102088089A (en) * 2010-12-27 2011-06-08 浙江大学 Preparation method of combined electrode of fuel cell and test device thereof

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"Paper-basedsolid-statesupercapacitors";Bin Yao et al;《Nano Energy》;20130923;第2卷;第1071-1078页 *

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