CN103943869A - Preparation method of film electrode material using graphite coated paper to load NiAu - Google Patents

Preparation method of film electrode material using graphite coated paper to load NiAu Download PDF

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Publication number
CN103943869A
CN103943869A CN201410105310.XA CN201410105310A CN103943869A CN 103943869 A CN103943869 A CN 103943869A CN 201410105310 A CN201410105310 A CN 201410105310A CN 103943869 A CN103943869 A CN 103943869A
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China
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graphite
paper
niau
coated
film electrode
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CN201410105310.XA
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CN103943869B (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 invention provides a preparing method of a film electrode material using graphite coated paper to load NiAu. Clay is used as a curing agent, the clay and graphite are mixed evenly, then the surface of ordinary paper is coated with the evenly-mixed clay and graphite; 5-5.5g of NH4Cl and 1-1.5g of NiCl2 are dissolved in 50mL of water for preparing an electro-deposition solution; the paper coated with the graphite is maintained in the electro-deposition solution under 1.0V voltage for 20-30min for activation of the coated graphite, then a paper-graphite-Ni film electrode is obtained by 160-180min of electro-deposition of Ni under-1.0 V voltage; the paper-graphite-Ni film electrode is stood in a 1mmol L<-1> HAuClO4 solution for 2 to 4 minutes to obtain a paper-graphite-NiAu film electrode. According to the method, the graphite coated paper the is used, Ni is electrically deposited on the surface of the conductive graphite coated paper, then part of Ni is replaced with Au to prepare a NiAu-loading pencil coated paper catalyst, and the catalytic performance of the positive pole of a direct hydronoron fuel cell can be improved. The problem of poor activity the positive pole of a sodium borohydride fuel cell can be solved.

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 method with coated with graphite paper load NiAu catalysis boron hydride electroxidation performance.
Background technology
Direct sodium borohydride fuel cell (DBFC) is the NaBH being dissolved in alkaline electrolyte solution 4the direct fuel cell as 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 4oxidation kinetics than methyl alcohol is fast, and energy density and cell voltage are also better than methyl alcohol.NaBH 4nonflammable, toxicity is low, pollution-free, do not produce CO 2, only there is 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 can be preserved with solution or solid form, can the stable existence several months in alkaline solution.Catalyst and product can recycle, NaBH 4unique accessory substance NaBO of hydrolysis 2to environment nonhazardous effect, and can be used as synthetic NaBH 4raw material, thereby realize recycling of resource.DBFC can work at ambient temperature, battery thereby easily startup.Consider NaBH from engineering science angle 4solution can serve as the coldplate that heat exchange medium carrys out cool batteries and need not be extra; The electric osmose towing of water can be used as cathode reactant, and need not as hydrogen and air, need wetting; These characteristics are useful for the design of fuel cell.
NaBH in theory 4electrocatalytic Oxidation can be 8e -reaction, referring to (1) formula:
BH 4 -+8OH -→BO 2 -+4H 2O+8e - (1)
DBFC is NaBH in theory 4can use non-platinum catalyst, 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 occur NaBH 4hydrolysis, referring to (2) formula:
NaBH 4+2H 2O→4H 2+NaBO 2 (2)
Can consult Kui Cheng; Dianxue Cao; Fan Yang; Dongming Zhang; Peng Yan; Jinling Yin; Guiling wang.Pd doped three-dimensional porous Ni film supported on Ni foam and its high performance towards NaBH 4electrooxidation.Journal of Power Sources, 2013,242:141-147, and Cao Dianxue, Gao Yinyi, Wang Guiling, Miao Rongrong, Liu Yao.A direct NaBH 4– H 2o 2fuel cell using Ni foam supported Au nanoparticles as electrodes.International Journal of Hydrogen Energy, 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, after clay is evenly mixed with graphite, be coated on plain paper surface;
(2) by 5～5.5g NH 4cl and 1～1.5g NiCl 2be dissolved in 50mL water and make electrodeposit liquid;
(3) in electrodeposit liquid, the paper that scribbles graphite is kept to 20～30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160～180min under-1.0V, obtains paper-graphite-Ni membrane electrode;
(4) finally by paper-graphite-Ni membrane electrode at 1mmol L -1hAuClO 4in solution, leave standstill 2～4 minutes, obtain paper-graphite-NiAu membrane electrode, i.e. coated with graphite paper load NiAu catalyst.
The present invention's coated with graphite paper, in the surface of paper of the coating graphite of conduction, then prepares pencil coated paper load NiAu catalyst with Au replacing section Ni by Ni electro-deposition, 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, solved the problem of sodium borohydride fuel cell anode poor activity.
Essence of the present invention is the battery structure that adopts sodium borohydride fuel cell etc., taking coated with graphite paper load NiAu as catalyst, forms the anode of fuel cell.
The invention has the advantages that and utilize the catalyst of coated with graphite paper load NiAu catalyst as sodium borohydride Electrocatalytic Oxidation, solved borohydride fuel anode discharge electric current little and be easy to the problems such as hydrolysis.In this electrode material preparation, do not use binding agent, the more important thing is under electric field action graphite and clay can with the cross-linking compounds of Ni and Au formation paper-graphite-clay-Ni Au, not only good conductivity, and electro catalytic activity is high.The paper load NiAu catalyst not only reserves of graphite, clay, Ni is extremely rich and easy to get, cheap, greatly reduces 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
For the effect of technique of the present invention is described better, be illustrated with instantiation below.
(1) get one of common paper, do after curing agent evenly mixes with graphite and be coated on paper surface with clay, get 1 × 1cm -2as Electrode; (2) by 5g NH 4cl and 1g NiCl 2be dissolved in 50mL water, for potentiostatic method deposit N i.(3) paper that scribbles graphite is kept to 20～30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160～180min under-1.0V, obtains paper-graphite-Ni membrane electrode.(4) finally by paper-graphite-Ni membrane electrode at 1mmol L -1hAuClO 4in solution, leave standstill 2～4 minutes, obtain paper-graphite-NiAu membrane electrode, i.e. coated with graphite paper load NiAu catalyst.
Paper-graphite-NiAu membrane electrode is carried out to following performance test:
1, taking paper-graphite-NiAu film as work electrode, carbon-point is to electrode, taking Ag/AgCl as reference electrode, at the NaOH of 1mol/L and the NaBH of 0.10mol/L 4solution in, under the voltage of-0.4V vs.Ag/AgCl, timing current density reaches 120mA/cm 2.
2, taking paper-graphite-NiAu film as work electrode, carbon-point is to electrode, taking Ag/AgCl as reference electrode, at the NaOH of 2M and the NaBH of 0.50M 4solution in, under the voltage of-0.4V vs.Ag/AgCl, timing current density reaches 350mA/cm 2.
3, utilize paper-graphite-NiAu film catalyzing N aBH 4electroxidation is anode, and the KOH of 3mol/L is anodolyte solution, and the sodium borohydride of 1mol/L is fuel; With the nanometer Pd catalysis H of load in nickel foam 2o 2directly electroreduction is negative electrode, with KOH and the 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 coated with graphite paper load NiAu thin-film electrode material, is characterized in that:
(1) make curing agent with clay, after clay is evenly mixed with graphite, be coated on plain paper surface;
(2) by 5～5.5g NH 4cl and 1～1.5g NiCl 2be dissolved in 50mL water and make electrodeposit liquid;
(3) in electrodeposit liquid, the paper that scribbles graphite is kept to 20～30min under 1.0V voltage, to activate the graphite of coating, then deposit N i160～180min under-1.0V, obtains paper-graphite-Ni membrane electrode;
(4) finally by paper-graphite-Ni membrane electrode at 1mmol L -1hAuClO 4in solution, leave standstill 2～4 minutes, 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109994744A (en) * 2019-01-31 2019-07-09 重庆大学 A kind of nickel cobalt binary catalyst promoting sodium borohydride direct oxidation
CN113036164A (en) * 2019-12-24 2021-06-25 大连大学 Preparation method and application of composite electrode based on mesoporous carbon foam
CN113054206A (en) * 2019-12-27 2021-06-29 大连大学 Method for constructing fructose fuel cell by applying NiNPs/AuNPs/GN/AgNWs/paper plastic electrode

Citations (2)

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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110135966A1 (en) * 2009-12-05 2011-06-09 Vishnu Jayaprakash Novel cow-dung based microbial fuel cell
CN102088089A (en) * 2010-12-27 2011-06-08 浙江大学 Preparation method of combined electrode of fuel cell and test device thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BIN YAO ET AL: ""Paper-basedsolid-statesupercapacitors"", 《NANO ENERGY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109994744A (en) * 2019-01-31 2019-07-09 重庆大学 A kind of nickel cobalt binary catalyst promoting sodium borohydride direct oxidation
CN109994744B (en) * 2019-01-31 2021-09-07 重庆大学 Nickel-cobalt binary catalyst for promoting direct oxidation of sodium borohydride
CN113036164A (en) * 2019-12-24 2021-06-25 大连大学 Preparation method and application of composite electrode based on mesoporous carbon foam
CN113054206A (en) * 2019-12-27 2021-06-29 大连大学 Method for constructing fructose fuel cell by applying NiNPs/AuNPs/GN/AgNWs/paper plastic electrode
CN113054206B (en) * 2019-12-27 2022-06-07 大连大学 Preparation method and application of NiNPs/AuNPs/GN/AgNWs/paper plastic electrode

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