Microporous La 0.8 Sr 0.2 MnO 3 perovskite nanorods as efficient electrocatalysts for lithium–air battery

Abstract Efficient electrocatalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the most critical factor to influence the performance of lithium–air batteries. We present La0.8Sr0.2MnO3 (LSM) perovskite nanorods as high active electrocatalyst fabricated via a soft template method for lithium–air batteries. The as–prepared LSM nanorods are microporous with numerous defects and large surface area (20.6 m2 g−1), beneficial to the ORR and OER in the discharge and charge processes, respectively. Lithium–air batteries based on the microporous LSM nanorods electrocatalysts show enhanced electrochemical performances, including high first discharge specific capacity (6890 mAh g−1(electrode) at 200 mA g−1), low overpotential, good rate capability (up to 400 mA g−1), and cycle stability (only 1.1% voltage loss after 30 circles of specific capacity limit of 1000 mAh g−1 tested at 200 mA g−1). The improved performance might be due to the synergistic effect of the unique microporous and one–dimensional structure and numerous defects of the prepared LSM catalyst.

[1]  Timur I. Abdullin,et al.  Improved Silver Halide Crystals for Photographic Emulsion , 2012 .

[2]  C. Jin,et al.  Preparation and electrochemical properties of urchin-like La0.8Sr0.2MnO3 perovskite oxide as a bifunctional catalyst for oxygen reduction and oxygen evolution reaction , 2013 .

[3]  A. Manthiram,et al.  Crystal chemistry and superconductivity of the copper oxides , 1990 .

[4]  M. Shen,et al.  Hollow spherical La0.8Sr0.2MnO3 perovskite oxide with enhanced catalytic activities for the oxygen reduction reaction , 2014 .

[5]  Fengyun Sun,et al.  Synthesis and characterization of single crystalline MnOOH and MnO2 nanorods by means of the hydrothermal process assisted with CTAB , 2006 .

[6]  Tao Huang,et al.  Nano-sized La0.8Sr0.2MnO3 as oxygen reduction catalyst in nonaqueous Li/O2 batteries , 2012, Journal of Solid State Electrochemistry.

[7]  C. Jin,et al.  Electrochemical study of Ba0.5Sr0.5Co0.8Fe0.2O3 perovskite as bifunctional catalyst in alkaline media , 2013 .

[8]  Hubert A. Gasteiger,et al.  Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries. , 2011, Journal of the American Chemical Society.

[9]  Dan Xu,et al.  Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries , 2013, Nature Communications.

[10]  J. Munch,et al.  Effect of Electric Charges on the Growth Process of Micelles , 1993 .

[11]  W. Bennett,et al.  Hierarchically porous graphene as a lithium-air battery electrode. , 2011, Nano letters.

[12]  Yunlong Zhao,et al.  Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries , 2012, Proceedings of the National Academy of Sciences.

[13]  C. Brinker,et al.  Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites , 2001, Nature.

[14]  J. Goodenough,et al.  A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles , 2011, Science.

[15]  Sanjeev Mukerjee,et al.  Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery , 2010 .

[16]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[17]  Yang Shao-Horn,et al.  The discharge rate capability of rechargeable Li–O2 batteries , 2011 .

[18]  M. Thommes.  Physical Adsorption Characterization of Nanoporous Materials , 2010 .

[19]  Jun Lu,et al.  A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries , 2013, Nature Communications.

[20]  Z. Wen,et al.  A tubular polypyrrole based air electrode with improved O2 diffusivity for Li–O2 batteries , 2012 .

[21]  I. Takeuchi,et al.  La(0.8)Sr(0.2)MnO(3-δ) decorated with Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ): a bifunctional surface for oxygen electrocatalysis with enhanced stability and activity. , 2014, Journal of the American Chemical Society.

[22]  C. Jin,et al.  Facile synthesis of gold-nanoparticle-decorated Gd(0.3)Ce(0.7)O(1.9) nanotubes with enhanced catalytic activity for oxygen reduction reaction. , 2014, ACS applied materials & interfaces.

[23]  Yarong Wang,et al.  A hierarchical NiCo2O4 spinel nanowire array as an electrocatalyst for rechargeable Li–air batteries , 2014 .

[24]  W. Hou,et al.  Synthesis of rod-like mesoporous silica using mixed surfactants of cetyltrimethylammonium bromide and cetyltrimethylammonium chloride as templates , 2003 .

[25]  Xueliang Sun,et al.  Challenges and opportunities of nanostructured materials for aprotic rechargeable lithium–air batteries , 2013 .

[26]  Myounggu Park,et al.  Lithium‐Air Batteries: Survey on the Current Status and Perspectives Towards Automotive Applications from a Battery Industry Standpoint , 2012 .

[27]  Y. Ein‐Eli,et al.  The impact of nano-scaled materials on advanced metal–air battery systems , 2013 .

[28]  Yarong Wang,et al.  Carbon-coating functionalized La0.6Sr1.4MnO4+δ layered perovskite oxide: enhanced catalytic activity for the oxygen reduction reaction , 2015 .

[29]  Qing-Li Gao,et al.  Ultra-high lithium storage capacity achieved by porous ZnFe2O4/α-Fe2O3 micro-octahedrons , 2014 .

[30]  Z. Çelik-Butler,et al.  Piezoelectric ZnO nanorod carpet as a NEMS vibrational energy harvester , 2014 .

[31]  Chenghao Yang,et al.  La0.6Sr1.4MnO4 layered perovskite anode material for intermediate temperature solid oxide fuel cells , 2012 .

[32]  Xin-bo Zhang,et al.  Synthesis of perovskite-based porous La(0.75)Sr(0.25)MnO3 nanotubes as a highly efficient electrocatalyst for rechargeable lithium-oxygen batteries. , 2013, Angewandte Chemie.

[33]  Si Hyoung Oh,et al.  Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries. , 2012, Nature chemistry.

[34]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[35]  Linda F. Nazar,et al.  Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge , 2013 .

[36]  Jun Chen,et al.  Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. , 2011, Nature chemistry.

[37]  L. Nazar,et al.  The role of vacancies and defects in Na0.44MnO2 nanowire catalysts for lithium–oxygen batteries , 2012 .

[38]  Stefan A Freunberger,et al.  The carbon electrode in nonaqueous Li-O2 cells. , 2013, Journal of the American Chemical Society.

[39]  J. Goodenough,et al.  Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. , 2011, Nature chemistry.

[40]  T. Venkatesan,et al.  Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale , 2013 .

[41]  K. M. Abraham,et al.  A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery , 1996 .

[42]  M. Antonietti,et al.  Nitrogen‐Containing Hydrothermal Carbons with Superior Performance in Supercapacitors , 2010, Advanced materials.

[43]  A. Manthiram,et al.  Decoupled bifunctional air electrodes for high-performance hybrid lithium-air batteries , 2014 .

[44]  B. McCloskey,et al.  Lithium−Air Battery: Promise and Challenges , 2010 .

[45]  Jianglan Shui,et al.  Vertically aligned N-doped coral-like carbon fiber arrays as efficient air electrodes for high-performance nonaqueous Li-O2 batteries. , 2014, ACS nano.

[46]  P. Bruce,et al.  Rechargeable LI2O2 electrode for lithium batteries. , 2006, Journal of the American Chemical Society.

[47]  Jun Chen,et al.  Porous perovskite CaMnO3 as an electrocatalyst for rechargeable Li-O2 batteries. , 2014, Chemical communications.

[48]  Qijun Sun,et al.  Phosphorus-doped porous carbons as efficient electrocatalysts for oxygen reduction , 2013 .

[49]  Guy Riddihough,et al.  Finding the Perfect Recipe , 2011 .

[50]  C. Jin,et al.  Facile synthesis and excellent electrochemical properties of NiCo2O4 spinel nanowire arrays as a bifunctional catalyst for the oxygen reduction and evolution reaction , 2013 .

[51]  Robert W. Black,et al.  Non‐Aqueous and Hybrid Li‐O2 Batteries , 2012 .