Emerging Intercalation Cathode Materials for Multivalent Metal‐Ion Batteries: Status and Challenges

Abstract

Multivalent metal‐ion (Mg2+, Zn2+, Ca2+, Al3+) batteries emerge as promising alternatives to current lithium‐ion batteries (LIBs) for grid‐scale energy storage applications because of their high safety and low cost. The bright prospect of these batteries encourages increasing research interests in recent years, hence inspirational achievements have been made over the years. Like in LIB, cathode is the most important component that determines the performance of multivalent metal‐ion batteries. Nevertheless, the development of cathode materials still faces realistic challenges, including sluggish solid‐state diffusion and slow desolvation process at the cathode/electrolyte interface. Herein, recent progresses in intercalation cathode materials for multivalent metal‐ion batteries, including vanadium and manganese oxides and their derivatives, chalcogenides, polyanions frameworks, carbon materials, MOFs (or COFs) and Mxenes are summarized. The discussions focus on the rational design and engineering of structure, morphology, and surface texture of these cathodes with the aim of revealing the material design principles for multivalent metal‐ion storage. We hope this critical review will provide the readers with a clear understanding of current status and future research directions of intercalation cathodes for multivalent metal‐ion batteries.

2022 Roadmap on aqueous batteries

“…Based on the initial positive KCuFe [CN] 6 (CuHCF) and negative TiO 2 electrode materials, many half-cell materials have now been reported in the literature [90]. Figure 12 provides an overview of the electrode materials and electrolytes currently reported (Negative electrodes: Al [91], C [92], TiO 2 [89] and MoO 3 [93]; Positive electrodes: Bi 2 O 3 [94], bronze-VO 2 [95], CuHCF [96], K 2 CuFe(CN) 6 [97], KNHCF [98], FeVO 4 [99], FeFe(CN) 6 [100], graphite [101], MnO 2 [102], Na 3 V 2 (PO 4 ) 3 [103], V 2 O 5 [104], VOPO 4 [105], WO 3 [106] and Al x MnO 2 [107]; Electrolytes: AlCl 3 [108], Al(CF 3 SO 3 ) 3 [105], Al 2 (SO 4 ) 3 [106], Al(NO 3 ) 3 [109], gelatin-polyacrylamide hydrogel [110], KCl [111], Mn(CF 3 SO 3 ) 2 [112], MnSO 4 [113] and PVA-Al(NO 3 ) 3 hydrogel [114]). We suggest that higher specific capacities (above 200 mAh g −1 ) are achievable using vanadium-based electrodes,.…”

The origin of capacity fluctuation and rescue of dead Mn-based Zn–ion batteries: a Mn-based competitive capacity evolution protocol

“…[13][14][15][16][17][18] However, in practice, the desired charge storage advantages of the layered structure have not been materialized, which instead embody low specific capacity and poor structural stability. [18][19][20][21] Dissolution of manganese oxide in the discharge/charge process has been considered to be another critical factor for the unsatisfactory electrochemical performance of ZIBs. In order to address this issue, adding a certain amount of Mn 2+ ions into the electrolyte has been widely demonstrated as an effective approach to suppress the Jahn-Teller effect of manganese oxides.…”

Amphipathic Molecules Endowing Highly Structure Robust and Fast Kinetic Vanadium‐Based Cathode for High‐Performance Zinc‐Ion Batteries

“…[ 5,6 ] Moreover, multivalent ions such as Zn 2+ , Mg 2+ , Ca 2+ are more promising for aqueous batteries due to their more charge carrying than that of monovalent Li + or Na + . [ 7,8 ] Particularly, zinc‐ion batteries (ZIBs) exhibit high theoretical capacity (820 mAh g −1 and 5855 mAh cm −3 ) [ 9 ] and a more stable Zn metal anode in the ambient, which makes it a promising energy storage system. [ 10 ]…”

“…[5,6] Moreover, multivalent ions such as Zn 2þ , Mg 2þ , Ca 2þ are more promising for aqueous batteries due to their more charge carrying than that of monovalent Li þ or Na þ . [7,8] Particularly, zinc-ion batteries (ZIBs) exhibit high theoretical capacity (820 mAh g À1 and 5855 mAh cm À3 ) [9] and a more stable Zn metal anode in the ambient, which makes it a promising energy storage system. [10] Various cathode materials including manganese oxides, [11] vanadium oxides, [12,13] Prussian blue analogs, [14] and organic compounds [15,16] have been developed for high-performance ZIBs.…”