CN103268947A - Lithium-air battery cathode bifunctional catalyst and application thereof - Google Patents
Lithium-air battery cathode bifunctional catalyst and application thereof Download PDFInfo
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- CN103268947A CN103268947A CN2013101991308A CN201310199130A CN103268947A CN 103268947 A CN103268947 A CN 103268947A CN 2013101991308 A CN2013101991308 A CN 2013101991308A CN 201310199130 A CN201310199130 A CN 201310199130A CN 103268947 A CN103268947 A CN 103268947A
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- lithium
- air battery
- oxygen
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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
Abstract
The invention discloses a lithium-air battery cathode bifunctional catalyst and application thereof. The catalyst is a compound with a perovskite crystal structure and particularly is Ba0.9Co0.7Fe0.2Nb0.1O3, La0.6Sr0.4Co0.2Fe0.8O3, Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3 or Ba0.5Sr0.5Co0.8Fe0.2O3. The lithium-air battery cathode bifunctional catalyst can be used for obviously reducing the charge/discharge polarization of a battery and achieving high charge/discharge capacity, has excellent charge/discharge multiplying power and long cycle life, can be used for obviously reducing the production cost, and has excellent catalytic efficiency. A lithium-air battery containing the catalyst has the advantage of high energy density and is applicable to the fields of various mobile electronic equipment and electric batteries.
Description
Technical field
The present invention relates to a kind of battery material, be specifically related to a kind of lithium-air battery negative electrode bifunctional catalyst, belong to high-performance chemical power supply eelctro-catalyst field.
Background technology
Because the fast-developing and modern people in fields such as space technology, mobile communication, guided missile, Aero-Space are to the care of energy crisis, environmental protection, the research of high energy-storage battery, exploitation have caused people's extensive concern.Because lithium is that quality minimum in all metallic elements, electrode potential are minimum, so the battery of being made up of lithium has characteristics such as open circuit voltage height, specific discharge capacity are big, having substituted NI-G, Ni-MH battery recent years rapidly becomes most popular high-energy battery.
Lithium-air battery be a kind of be positive electrode active materials with oxygen, be the battery of negative active core-shell material with the lithium metal, also claim by " lithium metal fuel cell ".Because oxygen does not need to be stored in inside battery, its theoretical energy density is up to 5.21 kWh/kg (oxygenous) or 11.14 kWh/kg (oxygen-free gas), far above the theoretical energy density (200-250 Wh/kg) of traditional lithium ion battery, its performance can compare favourably with gasoline (12.22 kWh/kg).Therefore lithium-air battery has broad application prospects in fields such as portable type electronic product and communication apparatus as high-energy-density power supply of new generation, especially can satisfy the requirement of the high-energy-density of electric car power supply.
In the lithium-air battery discharge process, the polarization of lithium metal anode is lower usually, as the oxygen electrode of negative electrode the chemical property (as: charge-discharge performance, enclosed pasture efficient, cyclical stability etc.) of battery is often had decisive influence.
The place that oxygen electrode when when being the lithium-air battery discharge oxygen reduction reaction and charging taking place the metal oxide decomposition reaction takes place, there is typical gas-liquid-solid phase reaction boundary zone, not only the diffusion impedance of oxygen and activation polarization are bigger in the course of reaction, and metal oxide can be in oxygen electrode surface deposition and enrichment, hinders even stops oxonium ion to make the electrode reaction termination with contacting of metal ion.At present, the subject matter that in use exists of the lithium-air battery of organic electrolyte system is: the Li that generates in the discharge process
2O
2Or Li
2The O oxide can deposit and be attached to catalyst surface and oxygen can not directly be contacted with catalyst again, causes slowing down even stopping of oxygen reduction reaction; Li
2O
2Or Li
2The O oxide conducting is poor, and electrode polarization is big; The dynamic performance of oxygen evolution reaction was poor when oxygen reduction reaction was with charging during discharge, and battery efficiency is low; Cycle performance difference etc.For addressing these problems, but improve the electro-catalysis efficient of oxygen and the reverse efficiency of battery is key method, present research work mainly concentrates on the bifunctional catalyst aspect that exploitation can promote that hydrogen reduction and oxygen are separated out.
The Yang Shao-Horn seminar of MIT does a lot of work in this respect, has developed PtAu alloy bifunctional catalysis system, studies show that Au is, and oxygen reduction reaction shows advantages of high catalytic activity, and Pt then has higher sensitivity to oxygen evolution reaction; Although noble metal such as Pt, Au has shown excellent catalytic effect, because its expensive price and rare resource make its very difficult large-scale application at commercial field.
Thereby lithium-air battery negative electrode bifunctional catalyst to be to improve the performance of lithium-air battery efficiently, cheaply to need research and development.
Summary of the invention
Goal of the invention of the present invention provides a kind of lithium-air battery negative electrode bifunctional catalyst, to reduce the discharging and recharging polarization, increase charge/discharge capacity of battery, raising cycle efficieny.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of lithium-air battery negative electrode bifunctional catalyst, this catalyst is Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3, La
0.6Sr
0.4Co
0.2Fe
0.8O
3, Pr
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3Perhaps Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3
The invention also discloses the application of above-mentioned catalyst in the lithium-air battery cathode material.
The Preparation of catalysts method is prior art among the present invention, comprises solid-phase synthesis, sol-gel synthetic method, modification coprecipitation and glycine-nitrate firing method.The catalyst for preparing has perovskite crystal structure, can effectively promote the generation of oxygen reduction reaction when battery discharge, simultaneously, can effectively promote the generation of oxygen evolution reaction again when battery charge, is bifunctional catalyst.
Because technique scheme is used, the present invention compared with prior art has following advantage:
1, the invention provides a kind of lithium-air battery cathod catalyst, have difunctional character, can significantly reduce the charge and discharge polarization of battery, and obtain high charge and discharge capacity, excellent charge and discharge multiplying power and long cycle life.
2, to compare cost low for catalyst provided by the invention and noble metal catalysts such as Pt, has more application prospect.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the prepared bifunctional catalyst of embodiment;
Fig. 2 is the prepared Ba of embodiment 1
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst is to the catalytic activity figure of oxygen reduction reaction;
Fig. 3 is the prepared Ba of embodiment 1
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst in the saturated 0.1 M KOH solution of oxygen to the catalytic activity figure of oxygen evolution reaction;
Fig. 4 is the prepared Ba of embodiment 1
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst in the saturated 0.1 M KOH solution of oxygen to the cyclical stability figure of oxygen reduction reaction and oxygen evolution reaction catalytic activity;
Fig. 5 is the Ba that utilizes embodiment 1 prepared
0.9Co
0.7Fe
0.2Nb
0.1O
3The first discharge capacity figure of button lithium-air battery under different current densities that catalyst is made;
Fig. 6 is the Ba that utilizes embodiment 2 prepared
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalyst is to the catalytic activity figure of oxygen reduction reaction;
Fig. 7 is the Ba that utilizes embodiment 2 prepared
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalyst is to the catalytic activity figure of oxygen evolution reaction.
Embodiment
The present invention is further described below in conjunction with accompanying drawing, embodiment:
The characterizing method of the lithium-air battery negative electrode bifunctional catalyst of the present invention's preparation is as follows:
1. the structure of catalyst and pattern characterize
The present invention adopts X-ray diffraction, and (X-Ray Diffraction XRD) carries out thing mutually and structural analysis to the catalyst for preparing, and concrete test is carried out at Philips Model PW1830 X-ray diffractometer, and condition of work is: radiation Cu
K αTarget, pipe is pressed 40kV, tube current 40mA, scope 20-80
°
The present invention adopts scanning electron microscopy (Scan Electron Microscope, SEM) and transmission electron microscope (Transmission Electron Microscope, TEM) microscopic appearance of preparation catalyst is observed, concrete test is carried out at the TecnaiG220 TEM of the S-4700 of HIT SEM and U.S. FEI Co..
2. the chemical property of catalyst characterizes
The present invention characterizes the chemical property of catalyst by the polarization curve that utilizes Pine rotating disk electrode (r.d.e) test oxygen reduction reaction and oxygen evolution reaction.Electrode test adopts three-electrode system, is electrolyte with the KOH solution of 0.1mol/l, and the Ag/AgCl electrode is reference electrode, and the Pt silk is to electrode, and catalyst and material with carbon element compound system are as work electrode.The effective area of work electrode is 0.196cm
2, effective loading of catalyst is 0.30mg/cm
2
Embodiment 1: solid-phase synthesis prepares Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3(BCFN)
Take by weighing 0.1800mol BaCO according to stoichiometric proportion
3, 0.0467mol Co
3O
4, 0.0200mol Fe
2O
3With 0.0100mol Nb
2O
5Be placed in the agate spheroidal graphite jar, through planetary ball mill ball milling 24h, again through the tablet press machine compressing tablet, be placed on 1000 ℃ of roasting 24h in the box type furnace then, make Ba through pulverizing
0.9Co
0.7Fe
0.2Nb
0.1O
3
Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Powder needed through planetary ball mill ball milling 48h before making electrode slurry, and crossed 100 mesh sieve.
Accompanying drawing 2 is above-mentioned Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst is to the catalytic activity figure of oxygen reduction reaction, Ba as seen from the figure
0.9Co
0.7Fe
0.2Nb
0.1O
3The 2500 limiting diffusion current density to oxygen reduction reaction when changeing can reach 5.80 mA cm in the saturated 0.1 M KOH solution of oxygen
-2
Accompanying drawing 3 is above-mentioned Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst to the catalytic activity figure of oxygen evolution reaction, just begins the aerobic air elutriation at 0.55V as seen from the figure and goes out in the saturated 0.1 M KOH solution of oxygen, and with the increase of current potential, the oxygen evolution reaction sharply increases.
Accompanying drawing 4 is above-mentioned Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Catalyst in the saturated 0.1 M KOH solution of oxygen to the cyclical stability figure of oxygen reduction reaction and oxygen evolution reaction catalytic activity, as seen from the figure after 100 circles circulate, Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Oxygen evolution reaction catalytic activity there is slight fading, and the catalytic activity of oxygen reduction reaction there is not decay basically.
Accompanying drawing 5 is for utilizing above-mentioned Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3Bifunctional catalyst is made the first discharge capacity of button lithium-air battery under different current densities, and as seen from the figure at the current discharge with 50 mA/g, discharge capacity can reach 1250mAh/g first.
Embodiment 2: sol-gel process prepares Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3(BSCF)
Take by weighing 0.05mol Ba (NO according to stoichiometric proportion
3)
2, 0.05 mol Sr (NO
3)
2, 0.08 mol Co (NO
3)
26H
2O and 0.02mol Fe (NO
3)
39H
2O is dissolved in the deionized water, adds the EDTA-NH of 1 mol/L
3Cushioning liquid, the room temperature lower magnetic force stirs 2h and makes EDTA and the abundant coordination of metal ion, adds the citric acid of 1.5 times of metal ion total mole numbers then as gelling agent, and powerful the stirring uses ammoniacal liquor regulator solution pH value about 6.0.Above-mentioned solution is evaporated until forming colloidal sol 80 ℃ of water-baths, and 200 ℃ of colloidal sol 24h that drying obtains obtain the dark brown xerogel.This xerogel at 800 ℃ of roasting 4h, is obtained black Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3Powder.
Accompanying drawing 6 is for utilizing above-mentioned Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalyst is to the catalytic activity figure of oxygen reduction reaction, by accompanying drawing 6 as can be seen during 2500rpm in the saturated 0.1 M KOH solution of oxygen Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalytic activity to the oxygen reduction reaction can compare favourably with commercial 20wt.% Pt/C catalyst performance.
Accompanying drawing 7 is for utilizing above-mentioned Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalyst is to the catalytic activity figure of oxygen evolution reaction, by accompanying drawing 7 Ba as can be seen
0.5Sr
0.5Co
0.8Fe
0.2O
3Catalyst has shown the catalytic activity stronger than pure carbon.
Embodiment 3: glycine nitrate firing method prepares La
0.6Sr
0.4Co
0.2Fe
0.8O
3
Take by weighing 0.06mol La (NO according to stoichiometric proportion
3)
39H
2O, 0.04mol Sr (NO
3)
2, 0.02mol Co (NO
3)
36H
2O and 0.08mol Fe (NO
3)
39H
2O is dissolved in the 500ml deionized water, adds the 0.24mol glycine again, treat that glycine and metal ion fully form complex after, Fast Heating concentrates mixed liquor, until violent burning, gets Powdered precursor.After this precursor fully ground, obtain La at 800 ℃ of roasting 4h
0.6Sr
0.4Co
0.2Fe
0.8O
3
Embodiment 4: the solid-phase synthesis legal system is equipped with Pr
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3
Take by weighing 0.04mol Pr (NO according to stoichiometric proportion
3)
36H
2O, 0.06mol SrCO
3, 0.02 mol Co (NO
3)
26H
2O, 0.035mol Fe
2O
3With 0.005mol Nb
2O
5Be placed in the agate spheroidal graphite jar, through planetary ball mill ball milling 24h, again through the tablet press machine compressing tablet, be placed on 1000 ℃ of roasting 24h in the box type furnace then, make black Pr through pulverizing
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3
Pr
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3Powder needed through planetary ball mill ball milling 48h before making electrode slurry, and crossed 100 mesh sieve.
Accompanying drawing 1 is the X-ray diffraction collection of illustrative plates of above-mentioned catalyst, a:Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3B:Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3C:La
0.6Sr
0.4Co
0.2Fe
0.8O
3D:Pr
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3, catalyst disclosed by the invention is typical perovskite crystalline structure as seen from Figure 1.
Claims (3)
1. lithium-air battery negative electrode bifunctional catalyst, it is characterized in that: described catalyst is Ba
0.9Co
0.7Fe
0.2Nb
0.1O
3, La
0.6Sr
0.4Co
0.2Fe
0.8O
3, Pr
0.4Sr
0.6Co
0.2Fe
0.7Nb
0.1O
3Perhaps Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3
2. lithium-air battery negative electrode bifunctional catalyst according to claim 1, it is characterized in that: described catalyst is perovskite crystal structure.
3. claim 1 or 2 application of described lithium-air battery negative electrode bifunctional catalyst in the lithium-air battery cathode material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140540A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Lithium-air battery based on binder-free air electrode and preparation method of lithium-air battery |
| CN105140541A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Air electrode for adhesive-free lithium-air battery and fabrication method and application of air electrode |
| KR101611407B1 (en) | 2014-09-12 | 2016-04-11 | 울산과학기술원 | Cathod catalyst for ait battery and method of manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130020207A1 (en) * | 2011-07-19 | 2013-01-24 | Yang Shao-Horn | Electrochemical Methods and Systems Using Catalytic Materials |
| US20130045437A1 (en) * | 2011-08-18 | 2013-02-21 | Fanglin Chen | Sulfur-Tolerant Anode Material for Direct Hydrocarbon Solid Oxide Fuel Cells |
-
2013
- 2013-05-24 CN CN2013101991308A patent/CN103268947A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130020207A1 (en) * | 2011-07-19 | 2013-01-24 | Yang Shao-Horn | Electrochemical Methods and Systems Using Catalytic Materials |
| US20130045437A1 (en) * | 2011-08-18 | 2013-02-21 | Fanglin Chen | Sulfur-Tolerant Anode Material for Direct Hydrocarbon Solid Oxide Fuel Cells |
Non-Patent Citations (4)
| Title |
|---|
| EDITH BUCHER ET AL.: "Oxygen nonstoichiometry and exchange kinetics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ，Edith Bucher et al.", 《SOLID STATE IONICS》, vol. 179, 31 December 2008 (2008-12-31), pages 1032 - 1035 * |
| ZHIBIN YANG ET AL.: "Ba0.9Co0.7Fe0.2Nb0.1O3−δ as cathode material for intermediate temperature solid oxide fuel cells", 《ELECTROCHEMISTRY COMMUNICATIONS》, 1 June 2011 (2011-06-01), pages 882 - 885 * |
| 宋世栋: "钙钛矿型双功能氧电极的研究", 《中国优秀博硕士学位论文全文数据库（博士）-工程科技I辑》, 15 November 2006 (2006-11-15), pages 8 - 22 * |
| 罗丹等: "中温固体氧化物燃料电池阴极La0.6Sr0.4Co0.2Fe0.8O3的制备及其结构性能分析", 《动力工程》, vol. 26, no. 6, 31 December 2006 (2006-12-31), pages 899 - 903 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101611407B1 (en) | 2014-09-12 | 2016-04-11 | 울산과학기술원 | Cathod catalyst for ait battery and method of manufacturing the same |
| CN105140540A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Lithium-air battery based on binder-free air electrode and preparation method of lithium-air battery |
| CN105140541A (en) * | 2015-07-30 | 2015-12-09 | 苏州大学 | Air electrode for adhesive-free lithium-air battery and fabrication method and application of air electrode |
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Application publication date: 20130828 |