117469 20240319081000.0 doi 10.1016/j.mtener.2022.100979 sideral 128772 ART-2022-128772 eng Siller, V. Safe extended-range cycling of Li4Ti5O12-based anodes for ultra-high capacity thin-film batteries 2022 Access copy available to the general public Unrestricted Lithium titanium oxide thin films are increasingly popular anode materials in microbatteries and hybrid supercapacitors, due to their improved safety, cost, and cycle lifetime. So far, research efforts have mainly focused on the pure spinel phase Li4Ti5O12 (LTO) and only a small fraction is dedicated to a broader spectrum of titanium-based metal oxide thin films. In this work, pulsed laser deposition is used in a multilayer approach by alternating LTO and Li2O ablations to create a heterogeneous landscape in the titania-based micro-anodes. This rich microstructure enables the safe extension of the accessible electrochemical window down to 0.2 V. This leads to extraordinary high specific capacities of 250–300 mAh/g at 1 C, maintaining a stable discharge capacity of 180 mAh/g at 16 C. Operando spectroscopic ellipsometry and Raman spectroscopy are used to track optical and structural changes as a function of the discharge voltage down to 0.01 V. A kinetically limited degradation mechanism based on the effective trapping of Li-ions at the octahedral 16c positions is proposed when cycling in the range of 0.2–0.01 V. In essence, our work contributes to titania-based nanoshapes as anodes of increased specific capacity due to a higher Li-site occupation, while maintaining their good stability and safety. © 2022 The Author(s) info:eu-repo/grantAgreement/ES/DGA/E13-20R info:eu-repo/grantAgreement/EC/H2020/801342/EU/ACCIÓ programme to foster mobility of researchers with a focus in applied research and technology transfer/TECNIOspringINDUSTRY This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 801342-801342-TECNIOspringINDUSTRY info:eu-repo/grantAgreement/EC/H2020/823717/EU/Enabling Science and Technology through European Electron Microscopy/ESTEEM3 This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 823717-ESTEEM3 info:eu-repo/grantAgreement/EC/H2020/824072/EU/Energy HarveStorers for Powering the Internet of Things/HARVESTORE This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 824072-HARVESTORE info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/PID2019-104739GB-I00-AEI-10.13039-501100011033 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 9.3 2022 CHEMISTRY, PHYSICAL 35 / 161 = 0.217 2022 Q1 T1 MATERIALS SCIENCE, MULTIDISCIPLINARY 58 / 343 = 0.169 2022 Q1 T1 ENERGY & FUELS 20 / 119 = 0.168 2022 Q1 T1 2.046 2022 Energy Engineering and Power Technology 2022 Q1 Fuel Technology 2022 Q1 Renewable Energy, Sustainability and the Environment 2022 Q1 Nuclear Energy and Engineering 2022 Q1 Materials Science (miscellaneous) 2022 Q1 12.5 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Gonzalez-Rosillo, J. Nuñez Eroles, M. Stchakovsky, M. Arenal, R. (orcid)0000-0002-2071-9093 Morata, A. Tarancón, A. 25, 100979 (2022), [11 pp] Materials Today Energy 2468-6069 2690513 http://zaguan.unizar.es/record/117469/files/texto_completo.pdf Versión publicada 2744879 http://zaguan.unizar.es/record/117469/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:117469 articulos driver 2024-03-18-14:05:41 ARTICLE