CN103165905A - Air electrode of lithium-air battery and preparation method thereof - Google Patents
Air electrode of lithium-air battery and preparation method thereof Download PDFInfo
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- CN103165905A CN103165905A CN2013100643478A CN201310064347A CN103165905A CN 103165905 A CN103165905 A CN 103165905A CN 2013100643478 A CN2013100643478 A CN 2013100643478A CN 201310064347 A CN201310064347 A CN 201310064347A CN 103165905 A CN103165905 A CN 103165905A
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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
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses an air electrode of a lithium-air battery and a preparation method of the air electrode of the lithium-air battery. The air electrode comprises a porous tantalum nitrogen (TaN) nanotube and catalytic activity components which are loaded on the TaN nanotube. The catalytic activity components are deposited or loaded on the porous TaN nanotube to form the air electrode through methods of electro-deposition, chemical deposition or high-temperature nitriding. The air electrode of the lithium-air battery and the preparation method of the air electrode of the lithium-air battery reduce content of precious metal in the air electrode and greatly lower cost of the lithium-air battery. In addition, the air electrode is simple in structure, easy to assemble and convenient to use.
Description
Technical field
The invention belongs to the lithium-air battery technical field, be specifically related to a kind of air electrode for lithium air battery and preparation method thereof.
Background technology
LiCoO
2With material with carbon element as the successful commercialization of the positive and negative pole material of lithium ion, but in lithium battery, positive electrode has limited to the energy storage capacity of lithium battery, such as the electrochemistry capacitance of lithium metal is 3860mAh/g, but the electrochemistry capacitance of most of positive electrode only has 200mAh/g.Therefore, seek specific energy higher, more cheap positive electrode is the developing direction of lithium battery always.
As a kind of brand-new metal-air cell, lithium-air battery has good chemical property, owing to not needing to be stored in battery as anodal oxygen (air), aerial oxygen can become negative oxygen ion or cross negative oxygen ion and then generate metal oxide or peroxide by electrochemical reaction by catalyst.But the air electrode of positive electrode current is comprised of noble metal catalyst (as Pt) usually, and the cost of the empty battery of lithium is increased, and restricts the development of its industrialization.If can successfully adopt the catalyst of novel cheapness to replace or reduce the use of noble metal, with greatly reducing the cost of lithium-air battery, great progradation be played in the development of lithium-air battery.
Summary of the invention
The object of the present invention is to provide a kind of air electrode for lithium air battery and preparation method thereof, this preparation method can reduce the content of noble metal in air electrode, greatly reduces the cost of lithium-air battery, to overcome the prior art deficiency.
For realizing purpose of the present invention, the present invention takes following technical scheme to solve:
A kind of air electrode for lithium air battery, catalyst comprise active component and porous TaN nanotube; Active component is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; The content of noble metal (platinum, gold) is less than 4% of oxygen electrode gross mass.
A kind of air electrode for lithium air battery, the key step of its preparation method is:
(1) with the Ta sheet at NH
4Carry out the anode electrochemical corrosion in F, wherein Ta is as anode, and the Pt sheet is as negative pole;
(2) product that obtains of step (l) is in NH
3In atmosphere, 850～1100 ℃ of reduction, obtain the TaN nanotube;
(3) deposit in the TaN nanometer by the active component of electrochemical deposition with air electrode.
Active component in above-mentioned steps (3) is Pt nanoparticle, gold nano grain, α-MnO
2Nano particle,, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; Wherein one or both content of platinum, gold are less than 4% of oxygen electrode gross mass.
Air electrode for lithium air battery of the present invention has good conducting matrix grain, not only has good catalytic activity, and has reduced noble metal platinum or golden consumption in the air electrode.In addition, the air electrode of preparation simple in structure be easy to the assembling, easy to use.
Embodiment
EXAMPLE l
The Ta sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ta is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.The TaO that obtains
2Nanotube is at 850 ℃, NH
3High temperature reduction 1h in atmosphere obtains the TaN nanotube.
By electrochemical deposition with the nanoparticle deposition of Pt in the TaN nanotube, electrolyte is 0.25mM H
2PtC1
6Be dissolved in 0.1M HCl, carry out electro-deposition by cyclic voltammetry.Potential region is-0.6～0.1V, and sweep speed is 20mVs
-1, deposit 10 circulations, namely obtain the Pt/TaN air electrode.This air electrode is the square pole piece of lcm * lcm, thickness is 100um, and wherein the TaN nano-tube array thickness of supporting Pt nano particle is 22um, and the internal diameter of sleeve structure is 50～60nm, Pt nano particle layer thickness is 10～15nm, and the pipe thickness of TaN nanotube is 8～10nm.This air electrode can be to O
2Carry out efficient catalysis, and can directly as the oxygen electrode of lithium-air battery, need not additionally to add collector binding agent and conductive agent.Specific capacity based on the lithium-air battery of this air electrode reaches 1860mAh g
-1Open Circuit Potential can reach 3.8V.Potential difference between charge and discharge platform is 0.5V.
Embodiment 2
The Ta sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ta is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.The TaO that obtains
2Nano-tube array is at 1100 ℃, NH
3High temperature reduction 1h in atmosphere obtains the TaN nanotube.
By electrochemical deposition with the nanoparticle deposition of gold in the TaN nanotube, electrolyte is 0.25mM H
2AuC1
6Be dissolved in 0.1M HCl, carry out electro-deposition by cyclic voltammetry.Potential region is-0.6～0.1V, and sweep speed is 20mVs
-1, deposit 10 circulations, namely obtain the coaxial sleeve structure of Au/TaN.This combination electrode is the square pole piece of lcm * lcm, thickness is 100um, and wherein the TaN nano-tube array thickness of load gold nano grain is 23um, and the internal diameter of sleeve structure is 60～70nm, the gold nano grain layer thickness is 10～15nm, and the pipe thickness of TaN nanotube is 9～10nm.Specific capacity based on the lithium-air battery of this air electrode reaches 2100mAh g
-1Open Circuit Potential can reach 3.7V.Potential difference between charge and discharge platform is 0.6V.
Embodiment 3
The Ta sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ta is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.With the TaO that obtains
2Nano-tube array is placed in the ammonium molybdate solution 1h of 1mM, afterwards the pole piece that takes out carefully rinsed with clear water, and 280 ℃ of oven dry 3h, will obtain load has MoO
3TaO
2Nano-tube array is placed in tube furnace, at NH
31000 ℃ of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 ℃ of min
-1Can obtain the MoN/TaN air electrode.Specific capacity based on the lithium-air battery of this air electrode reaches 1970mAh g
-1Open Circuit Potential can reach 3.7V.Potential difference between charge and discharge platform is 0.5V.
Embodiment 4
The Ta sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ta is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.With the TaO that obtains
2Nano-tube array is placed in the manganese sulfate of 1mM and the potassium sulfate mixed solution 1h of 1mM, afterwards the pole piece that takes out carefully rinsed with clear water, and 480 ℃ of oven dry 3h, will obtain load has MnO
2TaO
2Nano-tube array is placed in tube furnace, at NH
3850 ℃ of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 ℃ of min
-1Can obtain the MoN/TaN air electrode.Specific capacity based on the lithium-air battery of this air electrode can reach 2200mAh g
-1Open Circuit Potential reaches 3.8V.Potential difference between charge and discharge platform is 0.6V.
Claims (3)
1. an air electrode for lithium air battery, is characterized in that, air electrode comprises active component and porous TaN nanotube; Active component is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; Wherein one or both content of platinum, gold are less than 4% of oxygen electrode gross mass.
2. a method for preparing the described air electrode for lithium air battery of claim l, is characterized in that, the air electrode preparation process is:
(1) with the Ta sheet at NH
4Carry out the anode electrochemical corrosion in F, wherein Ta is as anode, and the Pt sheet is as negative pole;
(2) product that obtains of step (1) is in NH
3In atmosphere, 850～1100 ℃ of reduction, obtain the TaN nano-tube array;
(3) by electrochemical deposition, active component is deposited in the TaN nanometer.
3. a kind of air electrode for lithium air battery according to claim 2 and preparation method thereof, is characterized in that, active component is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle,, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; Wherein one or both content of platinum, gold are less than 4% of oxygen electrode gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013100643478A CN103165905A (en) | 2013-02-28 | 2013-02-28 | Air electrode of lithium-air battery and preparation method thereof |
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| CN2013100643478A CN103165905A (en) | 2013-02-28 | 2013-02-28 | Air electrode of lithium-air battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022009871A1 (en) * | 2020-07-06 | 2022-01-13 | 国立大学法人京都大学 | Alloy, aggregate of alloy nanoparticles, and catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215917A (en) * | 1997-10-27 | 1999-05-05 | 冲电气工业株式会社 | Fabricating method for semiconductor device |
| US20060249726A1 (en) * | 2005-05-07 | 2006-11-09 | Samsung Electronics Co., Ltd. | Semiconductor devices including nano tubes and methods of operating and fabricating the same |
| CN102034985A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Oxygen electrode of lithium air battery as well as preparation method and application thereof |
-
2013
- 2013-02-28 CN CN2013100643478A patent/CN103165905A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215917A (en) * | 1997-10-27 | 1999-05-05 | 冲电气工业株式会社 | Fabricating method for semiconductor device |
| US20060249726A1 (en) * | 2005-05-07 | 2006-11-09 | Samsung Electronics Co., Ltd. | Semiconductor devices including nano tubes and methods of operating and fabricating the same |
| CN102034985A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Oxygen electrode of lithium air battery as well as preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022009871A1 (en) * | 2020-07-06 | 2022-01-13 | 国立大学法人京都大学 | Alloy, aggregate of alloy nanoparticles, and catalyst |
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Application publication date: 20130619 |