La0.6Ca0.4CoO3, La0.1Ca0.9MnO3 and LaNiO3 as bifunctional oxygen electrodes

Bursell, Martin; Pirjamali, M.; Kiros, Yohannes

doi:10.1016/s0013-4686(02)00002-6

Cited by 116 publications

(62 citation statements)

References 28 publications

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“…This is a clear indication for deterioration of rhombohedral LaNiO 3 structure as reported elsewhere. 16,17 Moreover, dramatic increase of redox peak intensity (+75% after 100 cycles, dark cyan bars in Fig. 3b inlet) with increasing cycle number correlates with significant ORR activity loss (0.03 mA cm −2 per cycle) in Fig.…”

Section: Xrd Sem and Tem-mentioning

confidence: 86%

On Activity and Stability of Rhombohedral LaNiO3 Catalyst towards ORR and OER in Alkaline Electrolyte

Mariappan

Bhandari

Drillet

2015

ECS Electrochemistry Letters

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LaNiO 3 catalyst was synthesized by RHP method and sprayed onto a GDL. Electrochemical activity for oxygen reactions of asprepared GDE was evaluated under half-cell condition in oxygen-saturated 7 M KOH electrolyte. Best performance in terms of potential difference E between ORR and OER amounted 0.688 V @ 10 mA cm −2 for 20 wt% LaNiO 3 /C HSAG compared to 1 V for 20 wt% Pt/C Vulcan . Moreover, by increasing perovskite:carbon weight ratio up to 3:2, E in oxygen decreased down to 0.57 V that is the lowest value ever reported in the literature. However, phase segregation and loss in ORR activity was observed during cycling. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0081506eel] All rights reserved. Because of high theoretical energy density, low toxicity and attractive price, metal-air batteries and especially zinc/air system is an interesting candidate for portable and stationary energy storage applications. However, large scale commercialization is hindered by inherent drawbacks of the zinc electrode, such as poor reversibility, low energy efficiency, shape change and dendrite formation during the charging process. Moreover, resistance towards carbonate poisoning in alkaline systems and activity/stability of bi-functional catalysts for oxygen reactions have to be improved.1 Suntivich et al. found a volcano-shape correlation between σ * -orbital occupation (e g ) of different La-based perovskites and their activity for both ORR 2 and OER 3 reactions. Among the investigated systems, LaNiO 3 appears to be one of the best candidates in terms of bifunctionality. It is meanwhile wellknown that the reaction rate of these catalysts strongly depends on particle size, intrinsic electronic conductivity, phase stability and preparation method. By co-precipitation of metal nitrate precursors with 1 M NaOH, extremely low Tafel slope value of 43 mV dec −1 (2RT/3F) for OER was measured at a pure Lanthanum Nickel Oxide phase powder without addition of binder materials. 4 This excellent value was attributed to a high carrier density (holes) and dominant presence of Ni 2+ at the surface, and to a large amount of oxygen vacancies. Not only oxidation state of the transition metal but also roughness factor of the powder material is primordial. By using a chlorine-modified precipitation route 5 to further oxidized Ni 2+ to Ni 3+ , Singh et al.,6 measured a seven times larger roughness factor in comparison to that of the product yielded by traditional precipitation method. 4 Bulk perovskite materials are generally synthesized by (i) solid-phase sintering at high temperature, typically by T > 1278 K, ...

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Section: Xrd Sem and Tem-mentioning

confidence: 86%

On Activity and Stability of Rhombohedral LaNiO3 Catalyst towards ORR and OER in Alkaline Electrolyte

Mariappan

Bhandari

Drillet

2015

ECS Electrochemistry Letters

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“…[7][8][9][10] Among various metal oxide-based bi-functional electrocatalysts, La x Ca 1-x MO 3 (M=Co, Ni, Mn) perovskite oxides have attracted consistent attention as potential bi-functional catalysts for metal-air batteries and fuel-cell systems. [11][12][13][14][15][16] Further improvement of activity was achieved by using composite electrodes, e.g. core-corona structural bifunctional catalyst (CCBC) that consists of LiNiO 3 as the core supported on nitrogen-doped carbon nanotube, which can catalyze OER and ORR, respectively, in zinc-air batteries.…”

mentioning

confidence: 99%

Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis

Jung

Risch

Park

et al. 2016

Energy Environ. Sci.

302

210

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The world-wide interest in reducing the dependency on fossil fuels demands the development of energy storage systems with high power density from abundant materials, which would enable wide-spread industrial deployment of grid-scale renewable energy systems, as well as the progressive advancement of high-powered electric vehicles (EVs). Perovskite oxide ceramics attracted significant attention as a strong candidate for bi-functional electrocatalyst for metal-air batteries. There has been consistent investigation on the viability of bi-functional electrocatalysts, because energy storage systems cannot operate rechargeably without the proper bi-functional electrocatalyst. Among various electrocatalysts for both oxygen evolution and reduction, making nanoparticles from these materials for practical applications is a great challenge. The newly introduced pervovskite electrocatalyst of ~50 nm size preferentially reduced oxygen to water (< 5 % peroxide yield), exhibited more than 20 times higher gravimetric activity (A/g) than IrO2 in an OER half-cell test, and surpassed the charge/discharge performance of Pt/C (20 wt%) in a zinc-air full cell test. This study describes substantially the systematic engineering of perovskite ceramics into such a bifunctional nanosized electrocatalyst with high stability and activity, which was also explained in detail from the aspect of defect chemistry. Highly efficient bifunctional oxygen electrocatalysts are indispensable to the development of highly efficient regenerative fuel cells and rechargeable metal-air batteries, which could power future electric vehicles. Although perovskite oxides are known to have high intrinsic activity, large particle sizes rendered from traditional synthesis routes limit their practical use due to low mass activity. We report the synthesis of nano-sized perovskite particles with a nominal composition of L ax(Ba0.5Sr0.5)1-xCo0.8Fe0.2O3-d (BSCF), where lanthanum concentration and calcination temperature were controlled to influence oxide defect chemistry and particle growth. This approach produced a bifunctional perovskite electrocatalyst of ~50 nm size with supreme activity and stability for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The electrocatalyst preferentially reduced oxygen to water (<5 % peroxide yield), exhibited more than 20 times higher gravimetric activity (A/g) than IrO2 in an OER half-cell test (0.1 M KOH), and surpassed the charge/discharge performance of Pt/C (20 wt%) in a zinc-air full cell test (6 M KOH).Our work provides a general strategy for designing perovskite oxides as inexpensive, stable and highly active bifunctional electrocatalysts for future electrochemical energy storage and conversion devices.The world-wide interest in reducing the dependency on fossil fuels demands the development of energy storage systems with high power density from abundant materials, which would enable widespread industrial deployment of grid-scale renewable energy systems, as well as the progressive advancement of...

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“…Lanthanum Cobaltite, LaCoO 3, has been studied for its potential use in solid oxide fuel cells, oxygen separation membranes, reduction catalysts, and oxygen sensors [1][2][3][4][5][6][7][8] . At higher temperatures it exhibits ionic-electronic conductivity 9 .…”

Section: Introductionmentioning

confidence: 99%

Study of ferroelastic behavior and microstructure in polycrystalline LaCoO3 using Transmission Electron Microscopy

Kell¹,

Tanase²,

Klie³

2009

J Undergrad Research UIC

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LaCoO 3 is a ferroelastic perovskite-type oxide. It has been shown to undergo creep at room temperature. LaCoO 3 responds to stress by changing its domain structure, resulting in formation of spontaneous strain. The microstructure of a sample of polycrystalline LaCoO 3 with history of stress was investigated using Transmission Electron Microscopy (TEM). It was compared to an unstrained sample to determine what changes are produced. TEM analysis has shown an increase in defect density as well as the appearance of atomic scale ordering. The causes of the observed ordering and their relation to ferroelastic behavior are explored. IntroductionLanthanum Cobaltite, LaCoO 3, has been studied for its potential use in solid oxide fuel cells, oxygen separation membranes, reduction catalysts, and oxygen sensors [1][2][3][4][5][6][7][8] . At higher temperatures it exhibits ionic-electronic conductivity 9 . Additionally, changes in its magnetic susceptibility around 80K and 500K suggest corresponding spin state transitions, the nature of which has been investigated in numerous studies [10][11][12][13][14][15][16][17][18] . More recently, and to a lesser extent, the mechanical properties of LaCoO 3 have been studied 19,20 . Understanding of its mechanical properties will be essential for the development of practical applications for the material. For example, when LaCoO 3 based ceramics are to be used as solid electrolytes and membranes, cracking caused by thermal instabilities could seriously compromise the membranes 20 . LaCoO 3 is a perovskite type oxide, which has general form ABO 3 . The ideal perovskite structure is cubic. However, due to differences in the ionic radius of La and Co a slight distortion results making LaCoO 3 rhombohedral. Its nearly cubic structure, however, allows it to be thought of and indexed as a pseudo-cubic. Fig. 1 shows a pseudo-cubic reprentation of a unit cell. The pseudo-cubic lattice backbone is made of Lanthanum. The Co centered in each cell as well as the O centered on the each face of the cube make up the CoO 6 octahedra.Of particular interest, it has been reported that LaCoO 3 undergoes room temperature creep 21 . Typically, ceramics undergo creep-the continuous deformation of a solid under stress with time-only at temperatures at least as high as about half their melting point 22 (the melting point of LaCoO 3 is about 1800° C). The ability of LaCoO 3 to undergo room temperature creep is indicative of its ferroelastic behavior. The application of stress in LaCoO 3 as with other ferroelastic materials results in a hysteresis loop in the stress-strain behavior. By comparison, so-called "paraelastic" materials exhibit a linear stress-strain behavior. Furthermore in ferroelastic materials application of strain can result in spontaneous strain, which remains in the material after all external stress is removed. This is the result of the reorientation of ferroelastic domains induced by stress. A recent study modeled the creep behavior of LaCoO 3 during the loading and unloading of stress, inco...

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La0.6Ca0.4CoO3, La0.1Ca0.9MnO3 and LaNiO3 as bifunctional oxygen electrodes

Cited by 116 publications

References 28 publications

On Activity and Stability of Rhombohedral LaNiO3 Catalyst towards ORR and OER in Alkaline Electrolyte

On Activity and Stability of Rhombohedral LaNiO3 Catalyst towards ORR and OER in Alkaline Electrolyte

Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis

Study of ferroelastic behavior and microstructure in polycrystalline LaCoO3 using Transmission Electron Microscopy

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