39 research outputs found
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How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox.
Sensitivity to the "bulk" oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes-Li2MnO3, Li-rich NMC, and NMC 442-that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer
Revisiting metal fluorides as lithium-ion battery cathodes.
Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/β-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.X.H. is supported by funding from EPSRC Doctoral Prize, Adolphe Merkle and the Swiss National Science Foundation (Program NRP70 No. 153990) and European Commission via MSCA (Grant 798169). A.S.E. acknowledges financial support from the Royal Society. E.C.M. acknowledges funding from European Commission via MSCA (Grant 747449) and RTI2018-094550-A-100 from MICINN. Z. L. acknowledges funding from the Faraday Institution via the FutureCat consortium. C.J.P. is supported by the Royal Society through a Royal Society Wolfson Research Merit award, and EPSRC grant EP/P022596/1. A.L.G. acknowledges funding from the ERC (Grant 788144). This research was supported as part of the North Eastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0001294. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. Work done at Diamond Light Source was under Proposal EE17315-1. The authors are grateful to Prof. G. Ceder and other NECCES members for many stimulating discussions concerning fluoride-based conversion reactions and on the origins of structural hysteresis. The authors also acknowledge the help from S. Dutton, T. Dean, A. Docker, M. Leskes and D. Keeble
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Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi 0.8 Co 0.2− y Al y O 2 Cathodes
Abstract: Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2−yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes
Investigation of Physical and Electrochemical Properties of β‑Ta<sub><i>x</i></sub>Nb<sub>1–<i>x</i></sub>PO<sub>5</sub> as an Electrode Material for Lithium Batteries
The
effect of intrinsic phase transitions and substitutions on the structural
and electrochemical properties of monoclinic β-NbPO<sub>5</sub> as an electrode material for lithium or lithium-ion batteries is
explored for the first time. Isolation of lower voltage phase transitions
of the pure β-NbPO<sub>5</sub> was found to be highly effective
in improving the long-term cycling stability of the material. An analogous
impact to cycling stability was identified through the use of effective
solid solutions based on cations such as Ta<sup>5+</sup>. Resulting
materials exhibited excellent cycling stability, exceptionally low
first cycle irreversible loss, and excellent 20C rate capability without
the need for carbonaceous nanocomposites