CN103151539B - Carbon surface modifies the preparation method of hydrogen bearing alloy and the method for improving the anode-catalyzed performance of direct borohydride fuel cell - Google Patents
Carbon surface modifies the preparation method of hydrogen bearing alloy and the method for improving the anode-catalyzed performance of direct borohydride fuel cell Download PDFInfo
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- CN103151539B CN103151539B CN201310046843.0A CN201310046843A CN103151539B CN 103151539 B CN103151539 B CN 103151539B CN 201310046843 A CN201310046843 A CN 201310046843A CN 103151539 B CN103151539 B CN 103151539B
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- hydrogen
- bearing alloy
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- hydrogen bearing
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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
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Abstract
The present invention is to provide carbon surface and modify the preparation method of hydrogen bearing alloy and the method for improving the anode-catalyzed performance of direct borohydride fuel cell.Hydrogen storing alloy powder and carbon are mixed and puts into ball grinder; after within 1 ~ 2 hour, taking out with 3000 ~ 5000 revs/min of ball millings under nitrogen protection; add 60wt.% polytetrafluoroethylsolution solution and 1.5wt.% sodium carboxymethylcellulose colloid that mass ratio is 1:1 gradually; make the quality of hydrogen storing alloy powder and carbon: the quality=9 ~ 10:1 of polytetrafluoroethylsolution solution and sodium carboxymethylcellulose; and the slurry made containing hydrogen bearing alloy and carbon that stirs; be coated in nickel foam by described slurry, at 70 DEG C, dry 2.5h obtains carbon surface and modifies hydrogen bearing alloy.Carbon surface modifies hydrogen bearing alloy for improving the anode-catalyzed performance of direct borohydride fuel cell.
Description
Technical field
That the present invention relates to is a kind of preparation method of hydrogen bearing alloy, the present invention also relates to a kind ofly to modify hydrogen bearing alloy with carbon surface and be used for improving the method for the anode-catalyzed performance of direct borohydride fuel cell.
Background technology
Direct borohydride fuel cell (DBFC) take boron hydride as the fuel cell of anode, NaBH
4the hydrogen storage material of hydrogen content very high (11wt.%), NaBH in theory
4electrocatalytic Oxidation can be 8e
-reaction, see (1) formula:
BH
4 -+8OH-→BO
2 -+4H
2O+8e
-(1)
DBFC has very high energy density (specific energy is 9300Wh/kg), specific capacity (5668Ah/kg) and cell voltage, and (negative electrode is O
2time 1.64V); NaBH
4nonflammable, toxicity is low (unless eaten, otherwise harmless), do not produce CO
2, NaBH in theory
4non-platinum catalyst can be used; 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 resemble hydrogen and need to soak.These characteristics are highly profitable for the design of fuel cell and assembling.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)
Another kind of for for hydrogen bearing alloy, people's comparative studies such as Choudhury AB
5type and AB
2type hydrogen storage alloy is to NaBH
4catalytic performance, hydrogen bearing alloy can adsorb NaBH
4decompose the hydrogen produced, see (3) formula:
BH
4 -+2H
2O+M→MH
x,ads+BO
2 -+(4-0.5x)H
2(3)
There is oxidation reaction further, ejected electron, see (4) formula in the Hydrogen Energy of hydrogen bearing alloy absorption:
MH
x,ads+x OH
-→M+x H
2O+x e
-(4)
But the catalytic activity of hydrogen bearing alloy is little, is starkly lower than noble metal; Again due to (3) formula energy releasing hydrogen gas, reduce NaBH
4utilance.Wang Guiling can be consulted, Lan Jian, Cao Dianxue etc., direct NaBH
4-H
2o
2the progress of fuel cell, Journal of Chemical Industry and Engineering, 2008,159 (4): 805-813, and Choudhury N A, Raman R K, Sampath S, waits people, An alkalinedirect borohydride fuel cell with hydrogen peroxide as oxidant.Journal of PowerSources, 2005,143:1 – 8.
Summary of the invention
The object of the invention is to put forward in technique the preparation method that the carbon surface that can improve the anode-catalyzed performance of direct borohydride fuel cell modifies hydrogen bearing alloy.The present invention also aims to provide a kind of carbon surface to modify hydrogen bearing alloy for improving the method for the anode-catalyzed performance of direct borohydride fuel cell.
The object of the present invention is achieved like this:
The preparation method that carbon surface of the present invention modifies hydrogen bearing alloy is:
Hydrogen storing alloy powder and carbon are mixed and puts into ball grinder; after within 1 ~ 2 hour, taking out with 3000 ~ 5000 revs/min of ball millings under nitrogen protection; add 60wt.% polytetrafluoroethylsolution solution and 1.5wt.% sodium carboxymethylcellulose colloid that mass ratio is 1:1 gradually; make the quality of hydrogen storing alloy powder and carbon: the quality=9 ~ 10:1 of polytetrafluoroethylsolution solution and sodium carboxymethylcellulose; and the slurry made containing hydrogen bearing alloy and carbon that stirs; be coated in nickel foam by described slurry, at 70 DEG C, dry 2.5h obtains carbon surface and modifies hydrogen bearing alloy.
Described hydrogen storing alloy powder is AB
5type hydrogen storage alloy, AB
2type hydrogen storage alloy and their mixture.
Described carbon is carbon nano-tube, active carbon or carbon black.
Carbon surface of the present invention modifies hydrogen bearing alloy for improving the anode-catalyzed performance of direct borohydride fuel cell,
The finishing of charcoal is the absorption of hydrogen and dissociates and provide new activity site:
BH
4 -+2H
2O+C→C-H
x,ads+BO
2 -+(4-0.5x)H
2；
After carbon surface modifies hydrogen bearing alloy, the content of hydrogen bearing alloy Surface Hydrogen improves, C-H
x, adsin part hydrogen enter hydrogen bearing alloy:
C-H
x,ads+M→MH
x-a+C-H
a,ads；
C-H
x, ads+ M → MH
x-a+ C-H
a, adsthe hydrogen storage content MH of middle increase
x-acan by BH
4 -+ 2H
2o+C → C-H
x, ads+ BO
2 -+ (4-0.5x) H
2formula is discharged, and in charcoal, remaining hydrogen storage content also can by C-H
a, ads+ a OH
-→ C+a H
2o+a e
-formula is discharged;
Carbon surface is modified after hydrogen bearing alloy, make hydrogen bearing alloy with can not with BH
4 -direct contact, suppresses NaBH
4+ 2H
2o → 4H
2+ NaBO
2naBH in formula
4the generation of hydrolysis, the charcoal adsorbable NaBH again of finishing simultaneously
4+ 2H
2o → 4H
2+ NaBO
2formula NaBH
4the hydrogen that hydrolysis produces.
Modify with carbon surface the method that hydrogen bearing alloy improves the anode-catalyzed performance of direct borohydride fuel cell, carbon surface modifies hydrogen bearing alloy, not only increases the electrocatalysis characteristic of hydrogen bearing alloy to boron hydride, additionally reduces the effusion of hydrogen, improve NaBH
4utilance.Essence of the present invention is on the basis of direct borohydride fuel cell hydrogen storage alloy anode catalyst, by hydrogen bearing alloy finishing charcoal, increase the electrochemistry oxidation performance of hydrogen bearing alloy to boron hydride, improve the discharge performance of boron hydride anode, inhibit the effusion of hydrogen.The mass ratio of charcoal and hydrogen bearing alloy is 0.5 ~ 3.0:99.5 ~ 97.0, and charcoal comprises active carbon, carbon black, carbon nanotube and other material etc. based on carbon, and their mixture.
Usual charcoal can be used as the additive improving semi-conducting electrode material conductivity, hydrogen bearing alloy is conductor, and the conductivity of itself is just fine, except continuing to improve except conductivity, the finishing of charcoal can be the absorption of hydrogen on the one hand and dissociates and provide new activity site, see (5) formula:
BH
4 -+2H
2O+C→C-H
x,ads+BO
2 -+(4-0.5x)H
2(5)
After carbon surface modifies hydrogen bearing alloy, the content of hydrogen bearing alloy Surface Hydrogen improves greatly, C-H
x, adsin part hydrogen can enter hydrogen bearing alloy, see (5) formula:
C-H
x,ads+M→MH
x-a+C-H
a,ads(6)
Which enhance the hydrogen storage content of hydrogen bearing alloy, the hydrogen storage content MH that (6) formula increases
x-acan discharge by (4) formula, in charcoal, remaining hydrogen storage content also can discharge by (7) formula:
C-H
a,ads+a OH
-→C+a H
2O+a e
-(7)
Thus improve the catalytic activity of hydrogen bearing alloy, solve the problem that borohydride fuel anode discharge electric current is little.
On the other hand, carbon surface is modified after hydrogen bearing alloy, make hydrogen bearing alloy with can not with BH
4 -direct contact, can suppress (2) formula NaBH
4the generation of hydrolysis, charcoal adsorbable (2) formula NaBH again of finishing simultaneously
4the hydrogen that hydrolysis produces, additionally reduces the effusion of hydrogen, substantially increases NaBH
4utilance.
Embodiment
In order to effect of the present invention is described better, be illustrated with instantiation below.
Embodiment 1
Adopt carbon nano tube modified hydrogen bearing alloy, the ratio of carbon nano-tube and hydrogen bearing alloy is 2:98.Being to electrode with carbon-point, take Ag/AgCl as reference electrode, with carbon nano tube modified hydrogen bearing alloy for work electrode, at the NaBH of NaOH and 0.10M of 2M
4solution in, under the voltage of-0.7V vs.Ag/AgCl, chrono-amperometric density reaches 35mA/cm
2, and NaBH
4be not hydrolyzed.
Embodiment 2
Adopt Activated Carbon Modification hydrogen bearing alloy, the ratio of active carbon and hydrogen bearing alloy is 2:98.Being to electrode with carbon-point, take Ag/AgCl as reference electrode, modifies hydrogen bearing alloy for work electrode, at the NaBH of NaOH and 0.10M of 2M with activated carbon tube
4solution in, under the voltage of-0.7V vs.Ag/AgCl, chrono-amperometric density reaches 32mA/cm
2, and NaBH
4be not hydrolyzed.
Embodiment 3
Adopt carbon black to modify hydrogen bearing alloy, the ratio of carbon black and hydrogen bearing alloy is 2:98.Being to electrode with carbon-point, take Ag/AgCl as reference electrode, with carbon nano tube modified hydrogen bearing alloy for work electrode, at the NaBH of NaOH and 0.10M of 2M
4solution in, under the voltage of-0.7V vs.Ag/AgCl, chrono-amperometric density reaches 30mA/cm
2, and NaBH
4be not hydrolyzed.
Embodiment 4
Adopt carbon nano tube modified hydrogen bearing alloy, the ratio of carbon nano-tube and hydrogen bearing alloy is 2:98.Being to electrode with carbon-point, take Ag/AgCl as reference electrode, with carbon nano tube modified hydrogen bearing alloy for work electrode, at the NaBH of NaOH and 0.30M of 2M
4solution in, under the voltage of-0.7V vs.Ag/AgCl, chrono-amperometric density reaches 130mA/cm
2, and NaBH
4hydrolysis obviously weakens.
Embodiment 5
Adopt carbon nano tube modified hydrogen bearing alloy, the ratio of carbon nano-tube and hydrogen bearing alloy is 2:98.Being to electrode with carbon-point, take Ag/AgCl as reference electrode, with carbon nano tube modified hydrogen bearing alloy for work electrode, at the NaBH of NaOH and 0.80M of 2M
4solution in, under the voltage of-0.7V vs.Ag/AgCl, chrono-amperometric density reaches 240mA/cm
2, and NaBH
4hydrolysis obviously weakens.
Claims (1)
1. carbon surface modifies hydrogen bearing alloy for improving a method for the anode-catalyzed performance of direct borohydride fuel cell, it is characterized in that: carbon surface is modified hydrogen bearing alloy and be used for improving the anode-catalyzed performance of direct borohydride fuel cell,
The finishing of charcoal is the absorption of hydrogen and dissociates and provide new activity site:
BH
4 -+2H
2O+C→C-H
x,ads+BO
2 -+(4-0.5x)H
2；
After carbon surface modifies hydrogen bearing alloy, the content of hydrogen bearing alloy Surface Hydrogen improves, C-H
x, adsin part hydrogen enter hydrogen bearing alloy:
C-H
x,ads+M→MH
x-a+C-H
a,ads；
C-H
x, ads+ M → MH
x-a+ C-H
a, adsthe hydrogen storage content MH of middle increase
x-aby MH
x-a+ (x-a) OH
-→ M+ (x-a) H
2o+ (x-a) e
-formula is discharged, and in charcoal, remaining hydrogen storage content presses C-H
a, ads+ a OH
-→ C+a H
2o+a e
-formula is discharged;
Carbon surface is modified after hydrogen bearing alloy, make hydrogen bearing alloy with can not with BH
4 -direct contact, suppresses NaBH
4+ 2H
2o → 4H
2+ NaBO
2naBH in formula
4the generation of hydrolysis, the charcoal of finishing simultaneously adsorbs NaBH again
4+ 2H
2o → 4H
2+ NaBO
2formula NaBH
4the hydrogen that hydrolysis produces;
The preparation method that described carbon surface modifies hydrogen bearing alloy is: be that the carbon of 2:98 mixes with hydrogen storing alloy powder and puts into ball grinder by mass ratio, after within 1 ~ 2 hour, taking out with 3000 ~ 5000 revs/min of ball millings under nitrogen protection, add 60wt.% polytetrafluoroethylsolution solution and 1.5wt.% sodium carboxymethylcellulose colloid that mass ratio is 1:1 gradually, make the quality of hydrogen storing alloy powder and carbon: the quality=9 ~ 10:1 of polytetrafluoroethylsolution solution and sodium carboxymethylcellulose, and the slurry made containing hydrogen bearing alloy and carbon that stirs, described slurry is coated in nickel foam, the carbon surface that dry 2.5h obtains at 70 DEG C modifies hydrogen bearing alloy, wherein said hydrogen storing alloy powder is AB
5type hydrogen storage alloy, AB
2type hydrogen storage alloy and their mixture, described carbon is carbon nano-tube, active carbon or carbon black.
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|---|---|---|---|
| CN201310046843.0A CN103151539B (en) | 2013-02-06 | 2013-02-06 | Carbon surface modifies the preparation method of hydrogen bearing alloy and the method for improving the anode-catalyzed performance of direct borohydride fuel cell |
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|---|---|
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| CN103151539B true CN103151539B (en) | 2015-08-12 |
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| CN106934188B (en) * | 2015-12-24 | 2019-06-25 | 北京有色金属研究总院 | A kind of screening technique of hydrogen evolution electrode material alloying component |
| CN109286028A (en) * | 2018-12-11 | 2019-01-29 | 北京颐源新能源科技有限公司 | A kind of direct sodium borohydride fuel cell anode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809937A (en) * | 2002-12-24 | 2006-07-26 | 特克萨科双向电池系统有限责任公司 | Active electrode composition with conductive polymeric binder |
| CN1901261A (en) * | 2006-07-20 | 2007-01-24 | 复旦大学 | Novel high performance alkaline fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809937A (en) * | 2002-12-24 | 2006-07-26 | 特克萨科双向电池系统有限责任公司 | Active electrode composition with conductive polymeric binder |
| CN1901261A (en) * | 2006-07-20 | 2007-01-24 | 复旦大学 | Novel high performance alkaline fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| CNTs含量对LaNi5储氢材料性能的影响;张伟等;《电源技术》;20070630;第131卷(第6期);第488-490页 * |
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