K-Ion Slides in Prussian Blue Analogues

Cattermull, John; Roth, Nikolaj; Cassidy, Simon J.; Pasta, Mauro; Goodwin, Andrew L.

doi:10.1021/jacs.3c08751

Cited by 10 publications

(3 citation statements)

References 61 publications

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“…This effect is consistent with the experimental observation of pressure-driven structural distortions in some PBAs. , The effect of temperature is formally given by the balance of entropic terms in the free energies, but one simplification is to consider the effective radii of eq to be temperature-dependent. Since one expects the thermal volume of A- and X-site ions to grow more quickly than that of the B-site, α should increase with temperature, rationalizing the thermal quenching of distortions observed experimentally. , …”

mentioning

confidence: 72%

“…For example, Mn[Pt(CN) 6 ], which with no A-site cations at all has a tolerance factor well below 1, nonetheless adopts a cubic crystal structure in which the BX 3 framework is undistorted . Instead it is by filling the A-site (i.e., increasing α) that distortions are switched on. , This behavior contrasts with that of conventional perovskites but is conceptually similar to the activation of tilts in halide hybrid perovskites through hydrogen-bonding interactions between organic A-site cations and the anionic framework . An additional complication that we will address is that PBAs are highly nonstoichiometric frameworks, and one might expect partial site occupancies to play a nontrivial role in the activation or otherwise of collective distortions.…”

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confidence: 99%

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Predicting Distortion Magnitudes in Prussian Blue Analogues

Cattermull,

Pasta,

Goodwin

2023

J. Am. Chem. Soc.

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Based on simple electrostatic and harmonic potential considerations, we derive a straightforward expression linking the composition of a Prussian blue analogue (PBA) to its propensity to undergo collective structural distortions. We demonstrate the existence of a threshold value, below which PBAs are undistorted and above which PBAs distort by a degree that is controlled by a geometric tolerance factor. Our analysis rationalizes the presence, absence, and magnitude of distortions in a wide range of PBAs and distinguishes their structural chemistry from that of other hybrid perovskites.

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confidence: 72%

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confidence: 99%

Predicting Distortion Magnitudes in Prussian Blue Analogues

Cattermull,

Pasta,

Goodwin

2023

J. Am. Chem. Soc.

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“…Further, Rietveld refinement revealed that a near identical structure and higher potassium concentration (1.871(3) per formula unit) compared to previous studies was produced (Supplementary Note 2). 5,59,60 Elemental analysis by inductively coupled plasma mass spectrometry (ICP-MS) also indicated a low-vacancy/high potassium content from the Fe:Mn ratio of 0.98 (5), giving a chemical formula of K 1.871(3) Mn[Fe(CN) 6 ] 0.98 (5) from the combined XRD/ICP-MS analysis. The material was synthesised to have as large particles as possible while maintaining performance to minimise finite-size effects and ensure D limitation in the Kang-Chueh GITT measurements.…”

Section: Potassium Manganese Hexacyanoferrate Cathodementioning

confidence: 99%

Characterisation and Modelling of Potassium-ion Batteries

Dhir,

Cattermull,

Jagger

et al. 2024

Preprint

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Potassium-ion batteries (KIBs) are emerging as a promising alternative technology to lithium-ion batteries (LIBs) due to their significantly reduced dependency on critical minerals. KIBs may also present an opportunity for superior fast-charging compared to LIBs, with significantly faster K-ion electrolyte transport properties already demonstrated. In the absence of a viable K-ion electrolyte, a full-cell KIB rate model in commercial cell formats is required to determine the fast-charging potential for KIBs. However, a thorough and accurate characterisation of the critical electrode material properties determining rate performance---the solid state diffusivity and exchange current density---has not yet been conducted for the leading KIB electrode materials. Here, for the first time, we accurately characterise the effective solid state diffusivities and exchange current densities of the graphite anode and potassium manganese hexacyanoferrate KMn[Fe(CN)6] (KMF) cathode, through a combination of optimised material design and state-of-the-art analysis. Finally, we present the first Doyle-Fuller-Newman model of a KIB full cell in a hypothetical commercial cylindrical cell format, identifying the critical materials properties that limit their rate capability.

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Electrolyte Design Enables Stable and Energy‐Dense Potassium‐Ion Batteries

Zhang,

Wang,

Zhu

et al. 2024

Angewandte Chemie

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Free from strategically important elements such as lithium, nickel, cobalt, and copper, potassium‐ion batteries (PIBs) are heralded as promising low‐cost and sustainable electrochemical energy storage systems that complement the existing lithium‐ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low‐voltage anode and high‐voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (> 3 mAh cm‐2) to achieve an initial CE of 91.14% (with an average cycling CE around 99.94%), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high‐voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full‐cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg‐1‐(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01% capacity retention after 2000 cycles.

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K-Ion Slides in Prussian Blue Analogues

Cited by 10 publications

References 61 publications

Predicting Distortion Magnitudes in Prussian Blue Analogues

Predicting Distortion Magnitudes in Prussian Blue Analogues

Characterisation and Modelling of Potassium-ion Batteries

Electrolyte Design Enables Stable and Energy‐Dense Potassium‐Ion Batteries

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