High-Voltage Stabilization of O3-Type Layered Oxide for Sodium-Ion Batteries by Simultaneous Tin Dual Modification

Tengfei Song; Lin Chen; Dominika Gastol; Bo Dong; José F Marco; Frank Berry; Peter Slater; Daniel Reed; Emma Kendrick

doi:10.1021/acs.chemmater.2c00522

High-Voltage Stabilization of O3-Type Layered Oxide for Sodium-Ion Batteries by Simultaneous Tin Dual Modification

Chem Mater. 2022 May 10;34(9):4153-4165. doi: 10.1021/acs.chemmater.2c00522. Epub 2022 Apr 29.

Authors

Tengfei Song¹, Lin Chen¹, Dominika Gastol^{1

2}, Bo Dong^{3

2}, José F Marco⁴, Frank Berry³, Peter Slater^{3

2}, Daniel Reed^{1

2}, Emma Kendrick^{1

2}

Affiliations

¹ School of Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
² The Faraday Institution, Harwell Science and Innovation Campus, Didcot OX11 0RA, U.K.
³ School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
⁴ Instituto de Química Física ″Rocasolano″, CSIC, Serrano 119, Madrid 28006, Spain.

Abstract

O3-type layered oxide materials are considered to be a highly suitable cathode for sodium-ion batteries (NIBs) due to their appreciable specific capacity and energy density. However, rapid capacity fading caused by serious structural changes and interfacial degradation hampers their use. A novel Sn-modified O3-type layered NaNi_1/3Fe_1/3Mn_1/3O₂ cathode is presented, with improved high-voltage stability through simultaneous bulk Sn doping and surface coating in a scalable one-step process. The bulk substitution of Sn⁴⁺ stabilizes the crystal structure by alleviating the irreversible phase transition and lattice structure degradation and increases the observed average voltage. In the meantime, the nanolayer Sn/Na/O composite on the surface effectively inhibits surface parasitic reactions and improves the interfacial stability during cycling. A series of Sn-modified materials are reported. An 8%-Sn-modified NaNi_1/3Fe_1/3Mn_1/3O₂ cathode exhibits a doubling in capacity retention increase after 150 cycles in the wide voltage range of 2.0-4.1 V vs Na/Na⁺ compared to none, and 81% capacity retention is observed after 200 cycles in a full cell vs hard carbon. This work offers a facile process to simultaneously stabilize the bulk structure and interface for the O3-type layered cathodes for sodium-ion batteries and raises the possibility of similar effective strategies to be employed for other energy storage materials.