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DataBank, Bodleian Libraries, University of Oxford
Doctoral thesis . 2024
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Characterisation and modelling of potassium-ion batteries

Authors: Dhir, S;

Characterisation and modelling of potassium-ion batteries

Abstract

Lithium-ion batteries (LIBs) are critical to decarbonisation, yet the future supply of of lithium-ion (Li-ion) critical minerals such as lithium, nickel, and copper face significant uncertainty and risk. Potassium-ion batteries (KIBs) are emerging as a promising alternative to LIBs due to their reduced dependency on critical minerals, and ability of K+ to intercalate into graphite unlike sodium ions. KIBs may also present an opportunity for superior fast-charging due to the larger K+ size and lower charge density, being speculated to result in faster electrolyte ionic transport. Since there is no current viable potassium-ion (K-ion) electrolyte, a full-cell KIB rate model in commercial cell format is required to determine the fast-charging potential for KIBs and facilitate K-ion electrolyte and materials development. However, accurate characterisation of the fundamental electrolyte and material properties that determine rate performance has not yet been conducted. In this thesis the fundamental rate-determining properties of a K-ion electrolyte and leading K-ion electrode materials are characterised, and the first KIB Doyle-Fuller-Newman model is developed. First, the ionic transport and thermodynamic properties of a K-ion electrolyte is fully characterised for the first time using state-of-the-art methods, characterising potassium bis(fluorosulfonyl)imide (KFSI) in 1,2-dimethoxyethane (DME) and comparing to the Li-ion equivalent. A K metal preparation protocol was developed enabling sufficient K metal stability for electrolyte characterisation. The results show the K-ion electrolyte displays significantly higher salt diffusivities and transference numbers than the Li-ion equivalent. Second, the effective solid-state diffusivities and exchange current densities of the leading K-ion electrode materials—the graphite anode and potassium manganese hexacyanoferrate K2Mn[Fe(CN)6] (KMF) cathode—are characterised, through a combination of optimised material design and state-of-the-art analysis. The results show both the ionic transport and particularly the charge-transfer kinetics are slower for the KMF compared to the graphite. Finally, the first Doyle-Fuller-Newman model of a KIB full cell is presented in a hypothetical commercial cylindrical cell format, demonstrating ionic transport in the current leading K-ion electrolyte is too slow for even moderate rate performance using realistic electrode loading. Should a viable electrolyte be developed, the modelling shows K-ion could be competitive with the lithium iron phosphate (LFP) LIB in fast-charging capability.

Country
United Kingdom
Keywords

Batteries, Chemistry, Engineering, Energy storage, Techno-economics, Electrochemistry, Multiscale modeling, Materials

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
0
Average
Average
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Green