Cobalt and Nickel Phosphates as Multifunctional Air-Cathodes for Rechargeable Hybrid Sodium-Air Battery Applications

Baskar Senthilkumar; Ahamed Irshad; Prabeer Barpanda

doi:10.1021/acsami.9b09090

Cobalt and Nickel Phosphates as Multifunctional Air-Cathodes for Rechargeable Hybrid Sodium-Air Battery Applications

ACS Appl Mater Interfaces. 2019 Sep 18;11(37):33811-33818. doi: 10.1021/acsami.9b09090. Epub 2019 Sep 3.

Authors

Baskar Senthilkumar¹, Ahamed Irshad², Prabeer Barpanda³

Affiliations

¹ Laboratoire de Réactivité et Chimie des Solides (LRCS), CNRS UMR 7314 , Université de Picardie Jules Verne , 33 Rue Saint Leu , 80039 Amiens Cedex , France.
² Loker Hydrocarbon Research Institute, Department of Chemistry , University of Southern California , Los Angeles , California 90089 , United States.
³ Faraday Materials Laboratory, Materials Research Centre , Indian Institute of Science , C.V. Raman Avenue , Bangalore 560012 , India.

PMID: 31429545
DOI: 10.1021/acsami.9b09090

Abstract

Noble-metal-free bifunctional electrocatalysts are indispensable to realize low-cost and energy-efficient rechargeable metal-air batteries. In addition, power density, energy density, and cycle life of these metal-air batteries can be improved further by utilizing the fast faradaic reactions of metal ions in the catalyst layer together with the oxygen evolution/reduction reactions (OER/ORR) for charge storage. In this work, we propose mixed metal phosphates of nickel and cobalt, Ni_xCo_3-x(PO₄)₂ (x = 0,1, 1.5, 2, and 3), as multifunctional air-cathodes exhibiting bifunctional electrocatalytic activity and reversible metal redox reaction (M^3+/2+, M = Ni and Co). Submicron-sized Ni_xCo_3-x(PO₄)₂ particles were synthesized by a solution combustion synthesis technique with urea acting as the fuel. Electrocatalytic activity toward the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in 0.1 M NaOH was systematically tuned by varying the Ni-to-Co ratio. The synthesized Ni_xCo_3-x(PO₄)₂ with x = 1.5 (NCP11) showed superior bifunctional catalytic activity to other samples. Moreover, the catalyst material delivered a specific capacity of ∼110 mAh g^-1 by the redox reactions of its metal sites. The hybrid Na-air battery fabricated using the NCP11 catalyst-loaded air-cathode exhibited low overpotential, stable cycling performance, and round-trip energy efficiency exceeding 78% in a 0.1 M NaOH aqueous electrolyte.

Keywords: NASICON; Na-air battery; aqueous electrolyte; bifunctional electrocatalyst; hybrid battery; nickel-cobalt phosphate; sodium super ionic conductor.