Novel Synthesis of Anhydrous and Hydroxylated CuF2 Nanoparticles and Their Potential for Lithium Ion Batteries

Chemistry : a European Journal
Thoralf KrahlErhard Kemnitz

Abstract

Anhydrous nanoscopic CuF2 is synthesized from alkoxides Cu(OR)2 (R=Me, tBu) by their reaction either in pure liquid HF at -70 °C, or under solvothermal conditions at 150 °C using excess HF and THF as solvent. Depending on the synthesis method, nanoparticles of sizes between 10 and 100 nm are obtained. The compound is highly hygroscopic and forms different hydrolysis products under moist air, namely CuF2 ⋅2 H2 O, Cu2 (OH)F3 , and Cu(OH)F, of which only the latter is stable at room temperature. CuF2 exhibits an electrochemical plateau at a potential of ≈2.7 V when cycled versus Li in half cell Li-ion batteries, which is attributed to a non-reversible conversion mechanism. The cell capacity in the first cycle depends on the particle size, being 468 mAh g-1 for ≈8 nm crystallite diameter, and 353 mAh g-1 for ≈12 nm crystallite diameter, referred to CuF2 . However, such a high capacity cannot be sustained for several cycles and the capacity rapidly fades out. The cell voltage decreases to ≈2.0 V for CuF2 ⋅2 H2 O, Cu2 (OH)F3 , and Cu(OH)F. As all the compounds studied in this work show irreversible conversion reactions, it can be concluded that copper-based fluorides are unsuitable for Li-ion battery applications.

References

Sep 8, 2011·Journal of the American Chemical Society·Feng WangJason Graetz
Nov 22, 2013·Chemical Communications : Chem Comm·Lidia Di CarloNicola Pinna
May 9, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Erhard Kemnitz, Johannes Noack

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Citations

Feb 20, 2019·Chemistry : a European Journal·Nicolas Goubard-BreteschéNicola Pinna
Jun 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Kévin LemoineVincent Maisonneuve
Aug 21, 2019·ACS Applied Materials & Interfaces·Andréa MartinNicola Pinna

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