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Open AccessFeature PaperArticle

Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism

School of Science and Technology-Geology Division, University of Camerino, Via gentile III da Varano, 62032 Camerino, Italy
Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, Germany
Karlsruhe Institute of Technology (KIT), P.O. Box 3640, 76021 Karlsruhe, Germany
School of Science and Technology-Physics Division, University of Camerino, Via Madonna delle Carceri, 62032 Camerino, Italy
Authors to whom correspondence should be addressed.
Materials 2018, 11(1), 49;
Received: 5 December 2017 / Revised: 22 December 2017 / Accepted: 27 December 2017 / Published: 29 December 2017
(This article belongs to the Special Issue Zinc Oxide Nanostructures: Synthesis and Characterization)
In order to further improve the energy and power density of state-of-the-art lithium-ion batteries (LIBs), new cell chemistries and, therefore, new active materials with alternative storage mechanisms are needed. Herein, we report on the structural and electrochemical characterization of Fe-doped ZnO samples with varying dopant concentrations, potentially serving as anode for LIBs (Rechargeable lithium-ion batteries). The wurtzite structure of the Zn1−xFexO samples (with x ranging from 0 to 0.12) has been refined via the Rietveld method. Cell parameters change only slightly with the Fe content, whereas the crystallinity is strongly affected, presumably due to the presence of defects induced by the Fe3+ substitution for Zn2+. XANES (X-ray absorption near edge structure) data recorded ex situ for Zn0.9Fe0.1O electrodes at different states of charge indicated that Fe, dominantly trivalent in the pristine anode, partially reduces to Fe2+ upon discharge. This finding was supported by a detailed galvanostatic and potentiodynamic investigation of Zn1−xFexO-based electrodes, confirming such an initial reduction of Fe3+ to Fe2+ at potentials higher than 1.2 V (vs. Li+/Li) upon the initial lithiation, i.e., discharge. Both structural and electrochemical data strongly suggest the presence of cationic vacancies at the tetrahedral sites, induced by the presence of Fe3+ (i.e., one cationic vacancy for every two Fe3+ present in the sample), allowing for the initial Li+ insertion into the ZnO lattice prior to the subsequent conversion and alloying reaction. View Full-Text
Keywords: lithium-ion battery; anode; crystal chemistry; electrochemistry lithium-ion battery; anode; crystal chemistry; electrochemistry
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MDPI and ACS Style

Giuli, G.; Eisenmann, T.; Bresser, D.; Trapananti, A.; Asenbauer, J.; Mueller, F.; Passerini, S. Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism. Materials 2018, 11, 49.

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