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Lithiation Mechanisms in High Entropy Oxides as Anode Materials for Li-Ion Batteries

30 Pages Posted: 11 Feb 2020 Sneak Peek Status: Review Complete

See all articles by Paolo Ghigna

Paolo Ghigna

University of Pavia - Dipartimento di Chimica

Lorenzo Airoldi

University of Pavia - Dipartimento di Chimica

Martina Fracchia

University of Pavia - Dipartimento di Chimica

Umberto Anselmi-Tamburini

University of Pavia - Dipartimento di Chimica

Paola D'angelo

University of Rome La Sapienza - Department of Chemistry

Nicolò Pianta

Università degli Studi di Milano-Bicocca - Department of Materials Science

Riccardo Ruffo

Università degli Studi di Milano-Bicocca - Department of Materials Science

Giannantonio Cibin

Diamond Light Source - Harwell Science and Innovation Campus

Danilo Oliveira de Souza

Elettra-Sincrotrone Trieste

Eliana Quartarone

University of Pavia - Dipartimento di Chimica

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Abstract

High entropy oxides based on transition metals, as Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O (TM-HEO), have recently drawn special attention as potential anodes in lithium-ion batteries, due to high specific capacity and cycling reversibility. However, the lithiation/delithiation mechanism of such systems is still controversial and not clearly addressed. Here, we report on an operando XAS investigation on TM-HEO based anodes for lithium-ion cells during the first lithiation/delithiation cycle. This material showed high specific capacity exceeding 600 mAh g-1 at C/10 and Coulombic efficiency very close to unit. The combination of functional and advanced spectroscopic study revealed complex charging mechanisms, developing through an initial Li intercalation reaction during the first charging cycle, followed by the reduction of transition metal (TM) cations, which triggers the conversion reaction below 1.0 V. The conversion is irreversible and not completed, leading to the final collapse of the HEO rock-salt structure. Other redox processes are therefore discussed and called to account the observed cycling behavior of the TM-HEO based anode. Despite the irreversible phenomena, the HEO cubic structure remains intact for ~ 60% of lithiation delivered capacity, so proving the beneficial role of the configuration entropy to enhance the stability of the HEO rock-salt structure during the redox phenomena.

Keywords: high entropy oxides, anodes, lithium ion batteries, operando XAS

Suggested Citation

Ghigna, Paolo and Airoldi, Lorenzo and Fracchia, Martina and Anselmi-Tamburini, Umberto and D'angelo, Paola and Pianta, Nicolò and Ruffo, Riccardo and Cibin, Giannantonio and Oliveira de Souza, Danilo and Quartarone, Eliana, Lithiation Mechanisms in High Entropy Oxides as Anode Materials for Li-Ion Batteries. Available at SSRN: https://ssrn.com/abstract=3535696 or http://dx.doi.org/10.2139/ssrn.3535696
This is a paper under consideration at Cell Press and has not been peer-reviewed.

Paolo Ghigna

University of Pavia - Dipartimento di Chimica

Italy

Lorenzo Airoldi

University of Pavia - Dipartimento di Chimica ( email )

Italy

Martina Fracchia

University of Pavia - Dipartimento di Chimica ( email )

Italy

Umberto Anselmi-Tamburini

University of Pavia - Dipartimento di Chimica ( email )

Italy

Paola D'angelo

University of Rome La Sapienza - Department of Chemistry ( email )

Italy

Nicolò Pianta

Università degli Studi di Milano-Bicocca - Department of Materials Science ( email )

Italy

Riccardo Ruffo

Università degli Studi di Milano-Bicocca - Department of Materials Science ( email )

Italy

Giannantonio Cibin

Diamond Light Source - Harwell Science and Innovation Campus ( email )

United Kingdom

Danilo Oliveira de Souza

Elettra-Sincrotrone Trieste ( email )

Italy

Eliana Quartarone (Contact Author)

University of Pavia - Dipartimento di Chimica ( email )

Italy

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