(Digital Presentation) The Influence of Alkali Metal Cations on the Redox Processes of Copper Hexacyanoferrate in Rechargeable Aqueous Zinc-Ion Batteries
Authors: Gorlin Mikaela , Naylor Andrew J. , Ojwang Dickson O. , Shao-Horn Yang , Valvo Mario 
Published: November 2022

Rechargeable aqueous batteries are of high interest for future stationary grid-scale energy storage applications where high safety is needed (1). Copper hexacyanoferrate (CuHCF), a Prussian Blue Analogue (PBA) material, has recently gained interest as positive electrode for aqueous Zn-ion batteries (ZIBs) (2,3). Reversible Zn2+ ion insertion is facilitated by its open-framework with large channels that can host a variety of monovalent and divalent cations. Recent studies have shown that the charge compensation process takes place via Zn2+ ions swapping position between tunnel sites and vacancy sites (4).
Among aqueous ZIBs, the Zn/CuHCF cell has attracted noticeable attention, as it can combine abundant and inexpensive materials with a good trade-off between capacity and performance. Zinc can supply a high capacity (820 mAh g-1), while CuHCF typically provides a moderate capacity of ca. 60-80 mAh g-1.However, it exhibits one of the highest operating voltages among PBA-type cathodes (1.7 V vs. Zn2+/Zn) and exhibits a cubic-type structure with wide channels. In comparison to many other materials, CuHCF undergoes minimal volume and structural changes during ion insertion/de-insertion, exhibits a high Coulombic efficiency of ca. 99%, and can be cycled at high rates without compromising the capacity, which makes it an interesting material for high-power applications.
Nevertheless, CuHCF suffers from capacity fade owing to instabilities of Cu, which we have demonstrated in details in a recent investigation (5). In that study, we also highlighted that the characteristic aging effect, observed as a growth of a two-phase plateau in the charge/discharge profiles and associated with capacity loss (6), can be explained by Cu dissolution and thereby a displacement of the two Cu2+/Cu+ and Fe3+/Fe2+ redox-couples (5). Alkali metal cations (Li+, Na+, K+, Rb+, Cs+) have recently been shown to impact the capacity of the Zn/CuHCF cell along with a modulation of the characteristic redox-features in the voltammetric profiles (7). Cycling of large cations (Rb+, Cs+) was linked to a reduced capacity, while moderately sized cations (K+) resulted in optimal capacity and higher charge retention. This has motivated us to investigate the effect of the alkali metal cations on the charge compensation and redox processes in CuHCF in more detail in this study.
By employing X-ray photoelectron spectroscopy (XPS), we show that small cations (Li+) have negligible impact on the Cu and Fe redox processes, while moderately sized cations (K+) suppress Cu redox and enhance Fe redox, which optimizes the capacity and improves the cycling stability, accordingly. Large cations (Cs+), on the other hand, prevent reversible redox and lock both metal centers in their most reduced states (Cu+, Fe2+), which impedes the charge compensation process and reduces the capacity. Our study unveils how alkali metal cations influence the performance of ZIBs by affecting the synergy of the Cu2+/Cu+ and Fe3+/Fe2+ redox couples in CuHCF and demonstrates how tailoring the electrolyte formulation can conveniently impact the capacity retention of this compound in PBA-type ZIBs.

Figure 1. The aqueous Zn/CuHCF cell. (a) Schematic figures illustrating the structure of the CuHCF cathode and its wide channels that can host ions. (b) Cyclic voltammograms (CV) of the Zn/CuHCF cell in pure 1M ZnSO4 and in presence of 0.2 M alkali metal cation additives (Li+, K+, Cs+). (c) X-ray photoelectron spectroscopy (XPS) showing the Cu 2p3/2 and Fe 2p3/2 spectra of the same electrolytes as shown in (b).

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Figure 1