Strontium-doped perovskite oxide La1-xSrxMnO3 (x = 0, 0.2, 0.6) as a highly efficient electrocatalyst for nonaqueous Li-O2 batteries

Zhao, Yajun; Yang, Huibin; Zhang, Yidie; Wang, Zhaodong; Yao, Yunjin; He, Xiaojun; Zhang, Chaofeng; Zhang, Dawei

doi:10.1016/j.electacta.2017.02.155

Cited by 53 publications

(42 citation statements)

References 38 publications

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“…[ 27,28 ] Here, we report that a kinetically stable reconstructed oxide overlayer on Mo 3 P boosts its electrocatalytic performance toward exceptional ORR and OER activities, that is, current densities of 7.21 mA cm −2 at 2.0 V versus Li/Li + (ORR) and 6.85 mA cm −2 at 4.2 V versus Li/Li + (OER) in a non‐aqueous electrolyte, exceeding the performance of existing catalysts reported to date. [ 29–38 ] Using this catalyst, we also have demonstrated a Li–air battery cell with a long cycle life of 1200, low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency (90.2%) at the first cycle.…”

Section: Figurementioning

confidence: 98%

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Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

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OER) or only remain active for one of the reactions (different ORR/OER rates). [1-5] This can result in high overpotentials-excess energy above its thermodynamic value (2.96 V)-required to form and decompose lithium peroxide (Li 2 O 2) at the cathode during discharge (ORR) and charge (OER) processes, respectively. Numerous metal catalysts such as platinum (Pt), gold (Au), and ruthenium (Ru), as well as non-metallic catalysts such as transition-metal oxides, transition-metal dichalcogenides, and carbon-based catalysts, have been employed to resolve this issue, however, no major breakthrough has been reported to date. [4,6-11] Therefore, designing a highly active catalyst that can minimize the energy barriers-excess input energy-to form and decompose Li 2 O 2 nanoparticles at the cathode is a key challenge for the development of this technology. Electrocatalytic properties of transition metal phosphides have received great attention and been subject of theoretical and experimental studies. [12-16] Wang et al. demonstrated a convenient and straightforward approach to the synthesis of a 3D selfsupported Ni 5 P 4-Ni 2 P nanosheet cathode, very stable in acidic medium with an outstanding hydrogen evolution reaction (HER) activity. [17] Some other studies include development of The main drawbacks of today's state-of-the-art lithium-air (Li-air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo 3 P) nanoparticles with an exceptional activity-ORR and OER current densities of 7.21 and 6.85 mA cm −2 at 2.0 and 4.2 V versus Li/Li + , respectively-in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance-Tafel slopes of 35 and 38 mV dec −1 for ORR and OER, respectively-resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li-air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo 3 P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials. The advancement of lithium-air (Li-air) batteries, proposed as a potential alternative for existing energy storage systems, is mainly hampered by low energy efficiency and limited cycle life. One of the major drawbacks for today's Li-air batteries is that developed catalysts exhibit sluggish activity for both oxygen reduction and evolution reactions (ORR and

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Section: Figurementioning

confidence: 98%

“…Moreover, Mo 3 P nanoparticles exhibit higher activities for ORR/OER comparing with the state‐of‐the‐art catalysts yet reported as shown in Figure S5 (Section S3.2., Supporting Information). [ 29–38 ]…”

Section: Figurementioning

confidence: 99%

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

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“…This could be explained considering the perovskite design (ABO 3 ), that consists of BO 6 octahedral structure with A‐site cations at the corner of the unit cell. This structure is flexible and can accommodate versatile doping agents (e. g., Sr, Fe, Mn, Co) on A‐site and/or B‐site lattices . These substitutions can modify the electrical, optical and magnetic properties of the perovskite providing also oxygen vacancies that enhance the mobility of O 2 .…”

Section: Figurementioning

confidence: 99%

“…This structure is flexible and can accommodate versatile doping agents (e. g., Sr, Fe, Mn, Co) on A-site and/or B-site lattices. [17,18] These substitutions can modify the electrical, optical and magnetic properties of the perovskite providing also oxygen vacancies that enhance the mobility of O 2 . Nevertheless, non-stoichiometric transition metal oxides [19] are more active towards the ORR thanks to the introduction of oxygen vacancies at their surface.…”

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Enhancing Oxygen Reduction Reaction Catalytic Activity Using a Sub‐Stoichiometric CaTiO_3−δ Additive

et al. 2019

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Platinum scarcity and its high cost have led to the requirement of alternative materials catalysing the oxygen reduction reaction (ORR), which is the main rate‐determining step occurring in electrochemical devices, including metal‐air batteries and fuel cells. We report a study on a sub‐stoichiometric calcium titanate (CaTiO3−δ, CTO) compound used as promoter for the ORR in order to reduce the Pt loading and improve its electrocatalytic activity. Composite catalysts based on Pt/C with different amounts of CTO were prepared and their activity was investigated by rotating disk electrode (RDE). The obtained results proved a higher catalytic activity for the composite electrode, with respect to pure Pt/C, in terms of electrochemically active surface area, oxygen reduction current density, onset potential and stability.

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“…When Ca was substituted with Sr, as with a series of systemically varied (001)‐oriented epitaxial films of La 1− x Sr x MnO 3 , it was found that samples incorporating a moderate quantity (i.e., 33–50 %) of Sr yielded better electronic conductivity and evinced enhanced charge transfer, all of which contributed to higher levels of ORR activity measured . In a separate set of experiments to ascertain the effect of varying the amount of Sr dopant within La 1− x Sr x MnO 3 perovskites in an alkaline electrolyte, the observed kinetic currents of the optimized sample (i.e., La 0.4 Sr 0.6 MnO 3 ) were detected to be approximately nine times higher than that of pure LaMnO 3 perovskites alone; it was hypothesized that the combination of a higher amount of surface‐adsorbed oxygen and a larger active specific surface area led to this evident activity enhancement . Additional experiments performed on manganese perovskite catalysts, characterized by either a simple AMnO 3 type or a more complex AMn 7 O 12 chemical composition generated using a solid‐state protocol with variable reaction conditions, re‐affirmed the intrinsic catalytic activity of manganese perovskites.…”

Section: Applications In Direct Methanol Fuel Cellsmentioning

confidence: 97%

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

Tan

Salvatore

et al. 2019

Chemistry A European J

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With the ultimate goal of simultaneously finding cost‐effective, more earth‐abundant, and high‐performance alternatives to commercial Pt/Pd‐based catalysts for electrocatalysis, this review article highlights advances in the use of perovskite metal oxides as both catalysts and catalyst supports towards the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) within a direct methanol fuel cell (DMFC) configuration. Specifically, perovskite metal oxides are promising as versatile functional replacements for conventional platinum‐group metals, in part because of their excellent ionic conductivity, overall resistance to corrosion, good proton‐transport properties, and potential for interesting acidic surface chemistry, all of which contribute to their high activity and reasonable stability, especially within an alkaline electrolytic environment.

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Strontium-doped perovskite oxide La1-xSrxMnO3 (x = 0, 0.2, 0.6) as a highly efficient electrocatalyst for nonaqueous Li-O2 batteries

Cited by 53 publications

References 38 publications

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Enhancing Oxygen Reduction Reaction Catalytic Activity Using a Sub‐Stoichiometric CaTiO_3−δ Additive

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

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Strontium-doped perovskite oxide La1-xSrxMnO3 (x = 0, 0.2, 0.6) as a highly efficient electrocatalyst for nonaqueous Li-O2 batteries

Cited by 53 publications

References 38 publications

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Enhancing Oxygen Reduction Reaction Catalytic Activity Using a Sub‐Stoichiometric CaTiO3−δ Additive

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

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Product

Resources

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Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Enhancing Oxygen Reduction Reaction Catalytic Activity Using a Sub‐Stoichiometric CaTiO_3−δ Additive