No abstract

Rechargeable lithium-ion batteries (LIBs) have attracted tremendous attention over the past two decades. [1][2][3][4][5] Given their relatively high cost, as well as their high energy and power densities, LIBs have been considered the most promising technology in small/mid-size applications such as portable devices and electric vehicles (EVs). They are not favourable power options for large-scale stationary energy storage, however, such as in electrical grids. [6][7][8] Various emerging energy storage systems, including lithium-air batteries, [9][10][11][12][13][14][15][16] lithium-sulfur (Li/S) batteries, [11,[17][18][19][20][21][22][23] vanadium redox batteries, [24][25][26][27][28][29][30][31] sodium-ion batteries (SIBs), [32][33][34][35][36][37][38][39][40] and room-temperature sodium-sulfur Room temperature sodium-sulfur (RT-Na/S) batteries have recently regained a great deal of attention due to their high theoretical energy density and low cost, which make them promising candidates for application in large-scale energy storage, especially in stationary energy storage, such as with electrical grids. Research on this system is currently in its infancy, and it is encountering severe challenges in terms of low electroactivity, limited cycle life, and serious self-charging. Moreover, the reaction mechanism of S with Na ions varies with the electrolyte that is applied, and is very complicated and hard to detect due to the multi-step reactions and the formation of various polysulfides. Therefore, understanding the chemistry and optimizing the nanostructure of electrodes for RT-Na/S batteries are critical for their advancement and practical application in the future. In the present review, the electrochemical reactions between Na and S are reviewed, as well as recent progress on the crucial cathode materials. Furthermore, attention also is paid to electrolytes, separators, and cell configuration. Additionally, current challenges and future perspectives for the RT-Na/S batteries are discussed, and potential research directions toward improving RT-Na/S cells are proposed at the end.

The low-cost room-temperature sodium-sulfur battery system is arousing extensive interest owing to its promise for large-scale applications. Although significant efforts have been made, resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging. Here, a sulfur host comprised of atomic cobalt-decorated hollow carbon nanospheres is synthesized to enhance sulfur reactivity and to electrocatalytically reduce polysulfide into the final product, sodium sulfide. The constructed sulfur cathode delivers an initial reversible capacity of 1081 mA h g−1 with 64.7% sulfur utilization rate; significantly, the cell retained a high reversible capacity of 508 mA h g−1 at 100 mA g−1 after 600 cycles. An excellent rate capability is achieved with an average capacity of 220.3 mA h g−1 at the high current density of 5 A g−1. Moreover, the electrocatalytic effects of atomic cobalt are clearly evidenced by operando Raman spectroscopy, synchrotron X-ray diffraction, and density functional theory.

Room‐temperature sodium–sulfur (RT‐Na/S) batteries hold significant promise for large‐scale application because of low cost of both sodium and sulfur. However, the dissolution of polysulfides into the electrolyte limits practical application. Now, the design and testing of a new class of sulfur hosts as transition‐metal (Fe, Cu, and Ni) nanoclusters (ca. 1.2 nm) wreathed on hollow carbon nanospheres (S@M‐HC) for RT‐Na/S batteries is reported. A chemical couple between the metal nanoclusters and sulfur is hypothesized to assist in immobilization of sulfur and to enhance conductivity and activity. S@Fe‐HC exhibited an unprecedented reversible capacity of 394 mAh g−1 despite 1000 cycles at 100 mA g−1, together with a rate capability of 220 mAh g−1 at a high current density of 5 A g−1. DFT calculations underscore that these metal nanoclusters serve as electrocatalysts to rapidly reduce Na2S4 into short‐chain sulfides and thereby obviate the shuttle effect.