Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism
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 Zn...
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doaj-6c4e165e539f49b2931ab8ba78426d352020-11-25T00:51:50ZengMDPI AGMaterials1996-19442017-12-011114910.3390/ma11010049ma11010049Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage MechanismGabriele Giuli0Tobias Eisenmann1Dominic Bresser2Angela Trapananti3Jakob Asenbauer4Franziska Mueller5Stefano Passerini6School of Science and Technology-Geology Division, University of Camerino, Via gentile III da Varano, 62032 Camerino, ItalyHelmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, GermanyHelmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, GermanySchool of Science and Technology-Physics Division, University of Camerino, Via Madonna delle Carceri, 62032 Camerino, ItalyHelmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, GermanyHelmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, GermanyHelmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, GermanyIn 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.https://www.mdpi.com/1996-1944/11/1/49lithium-ion batteryanodecrystal chemistryelectrochemistry |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Gabriele Giuli Tobias Eisenmann Dominic Bresser Angela Trapananti Jakob Asenbauer Franziska Mueller Stefano Passerini |
spellingShingle |
Gabriele Giuli Tobias Eisenmann Dominic Bresser Angela Trapananti Jakob Asenbauer Franziska Mueller Stefano Passerini Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism Materials lithium-ion battery anode crystal chemistry electrochemistry |
author_facet |
Gabriele Giuli Tobias Eisenmann Dominic Bresser Angela Trapananti Jakob Asenbauer Franziska Mueller Stefano Passerini |
author_sort |
Gabriele Giuli |
title |
Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism |
title_short |
Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism |
title_full |
Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism |
title_fullStr |
Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism |
title_full_unstemmed |
Structural and Electrochemical Characterization of Zn1−xFexO—Effect of Aliovalent Doping on the Li+ Storage Mechanism |
title_sort |
structural and electrochemical characterization of zn1−xfexo—effect of aliovalent doping on the li+ storage mechanism |
publisher |
MDPI AG |
series |
Materials |
issn |
1996-1944 |
publishDate |
2017-12-01 |
description |
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. |
topic |
lithium-ion battery anode crystal chemistry electrochemistry |
url |
https://www.mdpi.com/1996-1944/11/1/49 |
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