3 research outputs found
Physical Delithiation of Epitaxial LiCoO2 Battery Cathodes as a Platform for Surface Electronic Structure Investigation
We report a novel delithiation process for epitaxial thin films of LiCoO2(001) cathodes using only physical methods,
based on ion sputtering and annealing cycles. Preferential Li sputtering followed by annealing produces a surface layer with a Li
molar fraction in the range 0.5 < x < 1, characterized by good crystalline quality. This delithiation procedure allows the unambiguous
identification of the effects of Li extraction without chemical byproducts and experimental complications caused by electrolyte
interaction with the LiCoO2 surface. An analysis by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy
(XAS) provides a detailed description of the delithiation process and the role of O and Co atoms in charge compensation. We
observe the simultaneous formation of Co4+ ions and of holes localized near O atoms upon Li removal, while the surface shows a (2
Ă 1) reconstruction. The delithiation method described here can be applied to other crystalline battery elements and provide
information on their properties that is otherwise difficult to obtainThis work was supported by the Spanish MICINN (grant nos.
PID2021-123295NB-I00 and PID2020-117024GB-C43),
MAT2017-83722-R, âMarĂa de Maeztuâ Programme for
Units of Excellence in R&D (CEX2018-000805-M), within
the framework of UE M-ERA.NET 2018 program under
StressLIC Project (grant no. PCI2019-103594) and by the
Comunidad AutĂłnoma de Madrid (contract no. PEJD-2019-
PRE/IND-15769 and S2108-NMT4321). The authors acknowledge Elettra Sincrotrone Trieste for providing access to
its synchrotron radiation facilities. They thank Ignacio
Carabias from the Diffraction Unit CAI UCM for his
experimental support and helpful comments. The research
leading to this result has been supported by the project
CALIPSOplus under Grant Agreement 730872 from the EU
Framework Programme for Research and Innovation HORIZON 2020. M.J., P.M., I.P., and F.B. acknowledge funding
from EUROFEL (RoadMap Esfri). The work at the University
of Maryland was supported by ONR MURI (Award No.
N00014-17-1-2661). The work at Sandia National Laboratories was supported by the Laboratory-Directed Research and
Development (LDRD) Program and the DOE Basic Energy
Sciences Award number DE-SC0021070. Sandia National
Laboratories is a multimission laboratory managed and
operated by National Technology and Engineering Solutions
of Sandia, LLC, a wholly owned subsidiary of Honeywell
International, Inc., for the US Department of Energyâs National
Nuclear Security Administration under contract DE-NA 000352
Physical Delithiation of Epitaxial LiCoO<sub>2</sub> Battery Cathodes as a Platform for Surface Electronic Structure Investigation
We report a novel delithiation process for epitaxial
thin films
of LiCoO2(001) cathodes using only physical methods, based
on ion sputtering and annealing cycles. Preferential Li sputtering
followed by annealing produces a surface layer with a Li molar fraction
in the range 0.5 x < 1, characterized by
good crystalline quality. This delithiation procedure allows the unambiguous
identification of the effects of Li extraction without chemical byproducts
and experimental complications caused by electrolyte interaction with
the LiCoO2 surface. An analysis by X-ray photoelectron
spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) provides
a detailed description of the delithiation process and the role of
O and Co atoms in charge compensation. We observe the simultaneous
formation of Co4+ ions and of holes localized near O atoms
upon Li removal, while the surface shows a (2 Ă 1) reconstruction.
The delithiation method described here can be applied to other crystalline
battery elements and provide information on their properties that
is otherwise difficult to obtain