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Recent Advances on Transition Metal Chalcogenide for Sodium-Ion Batteries

College of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
Authors to whom correspondence should be addressed.
These authors contributed equally to this work.
Batteries 2023, 9(9), 467;
Submission received: 23 August 2023 / Revised: 8 September 2023 / Accepted: 13 September 2023 / Published: 16 September 2023


Sodium-ion batteries (SIBs) are expected to replace lithium-ion batteries (LIBs) as a new generation of energy storage devices due to their abundant sodium reserves and low cost. Among the anode materials of SIBs, transition metal chalcogenides (TMXs) have attracted much attention because of their large layer spacing, narrow band gap, and high theoretical capacity. However, in practical applications, TMXs face problems, such as structural instability and poor electrical conductivity. In this review, the research progress and challenges of TMXs in SIBs in recent years are summarized, the application of nanostructure design, defect engineering, cladding engineering, and heterogeneous construction techniques and strategies in improving the electrochemical performance of TMXs anode are emphatically introduced, and the storage mechanism of sodium is briefly summarized. Finally, the application and development prospects of TMX anodes in electrochemical energy storage are discussed and prospected.

Graphical Abstract

1. Introduction

Since LiCoO2 was first commercialized as the LIB anode electrode, the development of LIBs has matured and been widely used in various electronic products, energy storage systems, and other fields in just thirty years due to their high energy density and excellent cycling performance [1]. According to USGS statistics, by 2020, the global lithium reserves are about 21 million tons of metal, but the annual lithium consumption is more than 85,000 tons and continues to rise every year. The low reserves and high consumption of lithium crust, as well as the resulting resource shortage and cost problems, make it difficult to sustain the large-scale application of LIBs [2,3]. The current development of LIB technology is relatively mature, but due to the use of flammable organic electrolytes and the strong activity of lithium metal, it is still prone to fire, thermal runaway, and other safety hazards [4]. In this case, various types of energy storage devices have been developed to meet the needs of development. The development is currently limited due to various reasons, such as the Li-Se battery’s electronic transfer ability being excellent and the theoretical volume capacity being high, but the volume expansion is serious and the utilization rate of active substances is not high, so the capacity attenuation is serious. Water-based zinc-ion batteries have a low cost, small size, light weight, and good safety, but zinc dendrite growth is serious, and energy density is limited. Supercapacitors have excellent power density, long lifecycles, and a friendly raw material environment, but the production cost is high, and the energy density is low [5,6,7,8]. Sodium is a neighboring element in the same group as lithium, and the two have similar physical and chemical properties, closer electrode potentials (only 0.3 V difference with lithium), and analogous ion storage mechanisms. In addition, the sodium reserves in the Earth’s crust are far more abundant than lithium resources, and easy extraction can effectively reduce production costs; they are expected to replace LIBs as the main force of future energy storage utilization [9,10,11,12]. However, because the radius of Na-ion is much larger than Li-ion, the layer spacing of the host material is required to meet the Na+ insertion/extraction, resulting in a large number of anodes that can work for SIBs [13]. Therefore, the development of host materials with large interlayer spacing and excellent electrochemical properties is the key to the large-scale application of SIBs.
Various kinds of electrode materials have been investigated in the development of SIBs. The charge storage mechanism in SIBs can be divided into insertion-type materials (such as graphite and other carbonaceous materials, TiO2, etc.), alloying-type materials (such as Bi, As, Si), and conversion-type materials (such as various transition metal compounds). Insertion-type anodes have low volume change but low specific capacity, alloying-type materials have high capacity but significant volume change (volume expansion even higher than 400%), and conversion-type materials are just in between and have received a lot of attention [11,14,15]. As a representative of the transition metal chalcogenide with large layer spacing, a narrow band gap (exhibiting metal-like behavior and high conductivity when narrow enough) and a high theoretical capacity (transferring multiple electrons per metal center; the capacity of selenide can reach 500–1000 mAh g−1), they are currently the hot spot in the research of negative electrode materials [16,17,18,19,20,21,22,23]. Transition metal chalcogenides (TMXs) are located in the VIA group of the periodic table, containing the elements O, S, Se, Te, and Po. Due to the large difference in physical and chemical properties between oxygen and other chalcogen elements and the low abundance of Te in the crust, only transition metal sulfides and transition metal selenides are considered in this review. TMXs have the structure of lamellar (M generally IVB–VI