Towards High Energy Density Nasicon Cathodes for Sodium-Ion Batteries: The Interplay between Structure, Na-Ion Dynamics and Redox Centres
Authors: Senguttuvan Premkumar , Ghosh Subham , Barman Nabadyuti 
Published: July 2021

The successful realization of sustainable energy technologies is nested into the incorporation of resilient storage technologies in grid due to their intermittent nature of energy production. Among these technologies, rechargeable batteries are ubiquitous due to their low cost, easy maintenance, high round trip efficiency and durability. Recently, Na-ion batteries have garnered significant interest for their potential grid application due to inexpensive and earth abundant raw materials. However, their successful commercialization faces several hurdles at both material and cell levels. In particular, the development of high voltage and capacity Na-ion cathodes is one of the key challenges for the successful realization of high energy density sodium ion batteries.1 Whilst layered Na-ion transition metal oxides are the frontrunners for practical application, their poor air stability and cycling stability are still required to be addressed.2 On other hand, phosphate cathodes offer high structural stability and insertion voltages as well rich structural diversity.3

Among them, NASICON-Na3V2(PO4)3 cathode is attractive because of its high intercalation voltage (3.45 V vs. Na+/Na0), moderate capacity (~120 mAh g-1) and excellent rate capability.4 The sodium (de)intercalation process in the NVP cathode proceeds via a two-phase mechanism and the corresponding redox activity is ascribed to the operation of V4+/V3+ couple. Further, other cations are substituted in the place of vanadium of the NVP lattice to seek the participation multiple redox centers, thereby enhancing intercalation capacities. Particularly, the NASICON end member Na4VMn(PO4)3 has garnered significant attention due to its reduced cost, improved insertion voltage and the participation of V5+/V4+, V4+/V3+ and Mn3+/Mn2+ redox couples.5,6 Herein, we will present a comprehensive study on the structural and electrochemical properties of Na3+xV2-xMnx(PO4)3 series. We will show how it is important to modulate electronic and crystal structures of the NASICON framework to attain high capacity and high-rate performances.7 Further, we will also discuss about the impact of alio-/iso-valent cationic substitutions into the NVP framework, which enhances their rate performances and cycle life.8

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