Diffusion Kinetics in Multi-Phase K-Ion Cathodes
Authors: Cattermull John , Dhir Shobhan , Jagger Ben , Goodwin Andrew , Pasta Mauro 
Published: February 2024

Prussian blue analogues (PBAs) are a framework material that are of great interest for use as cathode materials in Na- and K-ion batteries. Na-ion PBA batteries have been commercialized for use in stationary storage and are now in development for use in electric vehicles. The high operating potential of K-ion PBAs and their compatibility with pre-existing graphite anodes offer the exciting prospect of use in electric vehicles where high specific energy density is necessary [1].

The leading cathode material is the Manganese/Iron PBA – K
x
Mn[Fe(CN)6]
y
(0<x<2, 0.67<y<1.00). Attempts to maximise the specific capacity of PBA cathodes have been made by eliminating [Fe(CN)6] vacancies (y=1) which incorporates a full x = 2 formula units of K+ ions in the structure through electronic balancing [2]. Whilst making these low-vacancy materials has been made possible by altering the synthesis, optimising the electrochemical performance has proved more challenging [3]. Accessing the full capacity with high retention on cycling is one problem, and achieving the same excellent rate capability of the previously studied high-vacancy PBAs is also non-trivial [3,4] .

High-vacancy PBAs have an apparent simple cubic structure, and cycle electrochemically in a solid-solution [4]. Conversely, the low-vacancy PBAs with high K-ion content have coherent structural distortions and undergo phase transitions on cycling [3,5]. The phase transitions are believed to be responsible for poor capacity retention and rate capability [2]. There is also the theory that vacancies provide additional diffusion pathways for K+ ions [Fig. 1] [2]. For the development of this material as a cathode for K-ion batteries to be successful, it is vital that the diffusion kinetics and structural changes on electrochemical cycling are well-understood from a fundamental perspective.

For the first time we report diffusion coefficients by using Potentiostatic Intermittent Titration across multiple states of charge of a PBA cathode [6]. Linking the ionic diffusion in the material with the structural phase(s) present from operando X-ray diffraction gives us a mechanistic insight into the cathode’s charge/discharge behaviour. This informs materials design for tuning the structure of the pristine material to optimise its electrochemical performance in a K-ion battery.

References:

[1] Hurlbutt, K.; Wheeler, S.; Capone, I.; Pasta, M. Prussian Blue Analogs as Battery Materials. Joule
2018, 2 (10), 1950–1960.

[2] Cattermull, J.; Pasta, M.; Goodwin, A. L. Structural Complexity in Prussian Blue Analogues. Mater. Horiz.
2021, 8 (12), 3178–3186.

[3] Bie, X.; Kubota, K.; Hosaka, T.; Chihara, K.; Komaba, S. A Novel K-Ion Battery: Hexacyanoferrate(II)/Graphite Cell. J. Mater. Chem. A
2017, 5 (9), 4325–4330.

[4] Wessells, C. D.; Huggins, R. A.; Cui, Y. Copper Hexacyanoferrate Battery Electrodes with Long Cycle Life and High Power. Nat. Commun.
2011, 2 (1), 2–6.

[5] Cattermull, J.; Sada, K.; Hurlbutt, K.; Cassidy, S. J.; Pasta, M.; Goodwin, A. L. Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6]. Chem. Mater.
2022, 34 (11), 5000–5008.

[6] Cattermull, J.; Dhir S.; Jagger B.; Goodwin, A. L.; Pasta, M. Manuscript in preparation.

Figure 1