Review—Open-Framework Structure Based Cathode Materials Coupled with Metallic Anodes for Rechargeable Multivalent Ion Batteries

Abstract

Rechargeable batteries based on multivalent chemistry represent a promising avenue in grid-scale and portable energy storage devices, especially when multivalent metal with high energy density is used as the anode. Owing to the unique advantages of large 3D diffusion channels, multiple oxidation states of metal ions, and the ability to modulate the size of the intercalation channels for multivalent ions (Zn2+, Mg2+, Al2+, Ca2+) intercalation/deintercalation, open framework materials are regarded as ideal cathodes. Herein, this review firstly provides an introduction of recent open-framework structure based cathode materials including Prussian blue and its analogs (PB/PBAs), NASICONs, Zinc vanadate (zinc pyrovanadate, e.g., Zn3V2O7(OH)2·2H2O and α-Zn2V2O7, zinc n-vanadate, e.g., Zn(OH)VO4), and Molybdenum-vanadium oxide (Mo2.5+yVO9+z) along with a presentation of their energy storage mechanisms. Afterwards, representative examples of such intercalated materials applied to multivalent ion batteries are considered. Some strategies to further improve the electrochemical performances of open-framework structure based cathode materials are also presented. Finally, the challenges and development directions of these materials in rechargeable multivalent ion battery systems are discussed.

Recent progress on carbon materials for emerging zinc-ion hybrid capacitors

“…1a shows the ionic radius, standard reduction potential, theoretical specic capacity, volumetric capacity, and metal cost of different metal electrodes. 13,14 Among the promising candidates, zinc-ion hybrid capacitors (ZHCs) show attractive priority given that zinc possesses a high theoretical capacity (820 mA h g −1 or 5855 mA h cm −3 ) and low redox potential (−0.76 V vs. SHE, standard hydrogen electrode), as well as low cost, environmental friendliness and high safety of electrolytes. [16][17][18][19][20][21] Fig.…”

How Prussian Blue Analogues Can Be Stable in Concentrated Aqueous Electrolytes

“…Solid electrodes, with the active units hosting charge carriers, play a dominant part in battery chemistry. As well-known organic/inorganic hybrid electrodes, Prussian blue analogues (PBAs) with general formula A x M 1 [M 2 (CN) 6 ] y · n H 2 O (A is a mobile metal and M 1 and M 2 are transition metals) possess open frameworks consisting of M 2 –CN–M 1 . − The cyanide ligands that link M 1 or M 2 provide a perovskite-like face-centered cubic crystal structure, with a spacious channel along the ⟨100⟩ direction, where the diverse ions (monovalent, divalent, trivalent) can be reliably stored. − Especially, the spacious frameworks make PBAs a promising candidate for storing various appealing charge carriers “beyond Li ion”. ,, For example, PBAs have been widely investigated as cathodes for the multivalent ions (Zn 2+ , Mg 2+ , or Ca 2+ ) with high charge density. ,, More recently, PBAs have also been demonstrated as promising hosts for ammonium ions (NH 4 + ) that possess a larger ionic volume than common Li and Na ions (Li + = 0.60 Å, Na + = 0.95 Å, NH 4 + = 1.48 Å). − Although PBA-based electrodes have offered new opportunities for developing next-generation energy storage beyond traditional lithium-ion batteries, they generally suffer from severe capacity fading during long-term operation. A similar instability process also occurs in traditional transition-metal-containing cathodes for aqueous Li-ion batteries. , This has been an inherent problem that severely limited the practical operation of aqueous batteries. , …”

“…4,7,8 For example, PBAs have been widely investigated as cathodes for the multivalent ions (Zn 2+ , Mg 2+ , or Ca 2+ ) with high charge density. 7,9,10 More recently, PBAs have also been demonstrated as promising hosts for ammonium ions (NH 4 + ) that possess a larger ionic volume than common Li and Na ions (Li + = 0.60 Å, Na + = 0.95 Å, NH 4 + = 1.48 Å). 11−14 Although PBA-based electrodes have offered new opportunities for developing next-generation energy storage beyond traditional lithium-ion batteries, they generally suffer from severe capacity fading during long-term operation.…”