Boosting Manganese Selenide Anode for Superior Sodium-Ion Storage via Triggering α → β Phase Transition

ACS Nano. 2024 Jan 30;18(4):3801-3813. doi: 10.1021/acsnano.3c12215. Epub 2024 Jan 18.

Abstract

Sodium-ion batteries (SIBs) have been extensively studied owing to the abundance and low-price of Na resources. However, the infeasibility of graphite and silicon electrodes in sodium-ion storage makes it urgent to develop high-performance anode materials. Herein, α-MnSe nanorods derived from δ-MnO2 (δ-α-MnSe) are constructed as anodes for SIBs. It is verified that α-MnSe will be transferred into β-MnSe after the initial Na-ion insertion/extraction, and δ-α-MnSe undergoes typical conversion mechanism using a Mn-ion for charge compensation in the subsequent charge-discharge process. First-principles calculations support that Na-ion migration in defect-free α-MnSe can drive the lattice distortion to phase transition (alpha → beta) in thermodynamics and dynamics. The formed β-MnSe with robust lattice structure and small Na-ion diffusion barrier boosts great structure stability and electrochemical kinetics. Hence, the δ-α-MnSe electrode contributes excellent rate capability and superior cyclic stability with long lifespan over 1000 cycles and low decay rate of 0.0267% per cycle. Na-ion full batteries with a high energy density of 281.2 Wh·kg-1 and outstanding cyclability demonstrate the applicability of δ-α-MnSe anode.

Keywords: anode material; electrochemical mechanism; manganese selenide; phase transition; sodium-ion batteries.