Electrochemical Alloying of Lead in Potassium-Ion Batteries.

The electrochemical alloying of lead-based electrodes with potassium was investigated by galvanostatic measurements as well as by ex situ and operando X-ray diffraction. The electrochemical reduction must be activated by an initial high current pulse which prevents the passivation of the lead electrode. The alloying process leads to the formation of crystalline KPb. During the discharge, two intermediate phases are observed, K10Pb48 and K4Pb9, whereas only K4Pb9 seems to form during the charge. High capacity retention is observed, with, however, a limited specific capacity value because of high weight of lead.

Paving the Way for K-Ion Batteries: Role of Electrolyte Reactivity through the Example of Sb-Based Electrodes.

Developing potassium-ion batteries remains a challenge so far due to the lack of efficient electrolytes. Moreover, the high reactivity of K metal and the use of half-cells may greatly alter both the electrochemical performance and the solid electrolyte interphase formation. Here, it is shown that in K metal/Sb half-cells, Coulombic efficiency improvement is achieved by the addition of fluoroethylene carbonate + vinylene carbonate to propylene carbonate (PC), the replacement of PC by ethylene carbonate/diethyl carbonate, and the replacement of KPF6 by potassium bis(fluorosulfonyl)imide. Surprisingly, however, storage of cells containing K metal leads to the coloration of K metal, separators, and Sb electrodes, whereas no change occurs for cells prepared without K metal. These results demonstrate that for all electrolytes, the high electrolyte reactivity with K metal also influences the Sb/electrolyte interface via a cross-talk mechanism. This observation is supported by gas chromatography/mass spectrometry analysis of electrolytes and X-ray photoelectron spectroscopy analysis of Sb electrodes. In summary, these results indicate that the search for efficient electrolytes for potassium-ion batteries must be carried out in full cells if one wants to obtain meaningful correlations between electrochemical performance and electrode/electrolyte interfacial properties. Overall, the results presented here are also likely to benefit the development of other emerging Na- and Mg-ion cell chemistries.