The increased energy density in Li-ion batteries is particularly dependent on the cathode materials that so far have been limiting the overall battery performance. A new class of materials, Li-rich disordered rock salts, has recently been brought forward as promising candidates for next-generation cathodes because of their ability to reversibly cycle more than one Li-ion per transition metal. Several variants of these Li-rich cathode materials have been developed recently and show promising initial capacities, but challenges concerning capacity fade and voltage decay during cycling are yet to be overcome. Mechanisms behind the significant capacity fade of some materials must be understood to allow for the design of new materials in which detrimental reactions can be mitigated. In this study, the origin of the capacity fade in the Li-rich material Li2VO2F is investigated, and it is shown to begin with degradation of the particle surface that spreads inward with continued cycling.
Lithium-rich transition metal disordered rock salt (DRS) oxyfluorides have the potential to lessen one large bottleneck for lithium ion batteries by improving the cathode capacity. However, irreversible reactions at the electrode/electrolyte interface have so far led to fast capacity fading during electrochemical cycling. Here, we report the synthesis of two new Li-rich transition metal oxyfluorides Li 2 V 0.5 Ti 0.5 O 2 F and Li 2 V 0.5 Fe 0.5 O 2 F using the mechanochemical ball milling procedure. Both materials show substantially improved cycling stability compared to Li 2 VO 2 F. Rietveld refinements of synchrotron X-ray diffraction patterns reveal the DRS structure of the materials. Based on density functional theory (DFT) calculations, we demonstrate that substitution of V 3+ with Ti 3+ and Fe 3+ favors disordering of the mixed metastable DRS oxyfluoride phase. Hard X-ray photoelectron spectroscopy shows that the substitution stabilizes the active material electrode particle surface and increases the reversibility of the V 3+ /V 5+ redox couple. This work presents a strategy for stabilization of the DRS structure leading to improved electrochemical cyclability of the materials. † Electronic supplementary information (ESI) available: PXRD pattern of ceramic synthesis attempts; structural parameters of the Rietveld renements; PXRD pattern of Li 2 VO 2 F with Rietveld renement; Williamson-Hall-plots; TEM and EDX analysis; SQS of Li 2 TMO 2 F and Li 2 TM1 0.5 TM2 0.5 O 2 F; ordered structures of Li 2 TM1 0.5 TM2 0.5 O 2 F; table of energy difference between the ordered/decomposed state and disordered state; table of oxidation states of TMs; voltage proles of Li 2 VO 2 F, Li 2 V 0.5 Ti 0.5 O 2 F and Li 2 V 0.5 Fe 0.5 O 2 F half-cells cycled up to 4.1 V; PXRD pattern of cycled electrodes; HAXPES Fe 2p peak tting; HAXPES survey of Li 2 V 0.5 Fe 0.5 O 2 F and Li 2 VO 2 F and uorine plasmon overlaps with the Fe 2p 3/2 peak; core level photoelectron spectra of Fe 2p and Ti 2p; cycling performance of Li 2 VO 2 F, Li 2 V 0.5 Ti 0.5 O 2 F and Li 2 V 0.5 Fe 0.5 O 2 F half-cells cycled up to 4.5 V. See
Operando ambient pressure photoelectron spectroscopy in realistic battery environments is a key development towards probing the functionality of the electrode/electrolyte interface in lithium-ion batteries that is not possible with conventional photoelectron spectroscopy. Here, we present the ambient pressure photoelectron spectroscopy characterization of a model electrolyte based on 1M bis(trifluoromethane)sulfonimide lithium salt in propylene carbonate. For the first time, we show ambient pressure photoelectron spectroscopy data of propylene carbonate in the liquid phase by using solvent vapor as the stabilizing environment. This enables us to separate effects from salt and solvent, and to characterize changes in electrolyte composition as a function of probing depth. While the bulk electrolyte meets the expected composition, clear accumulation of ionic species is found at the electrolyte surface. Our results show that it is possible to measure directly complex liquids such as battery electrolytes, which is an important accomplishment towards true operando studies.
HIPPIE is a soft X-ray beamline on the 3 GeV electron storage ring of the MAX IV Laboratory, equipped with a novel ambient-pressure X-ray photoelectron spectroscopy (APXPS) instrument. The endstation is dedicated to performing in situ and operando X-ray photoelectron spectroscopy experiments in the presence of a controlled gaseous atmosphere at pressures up to 30 mbar [1 mbar = 100 Pa] as well as under ultra-high-vacuum conditions. The photon energy range is 250 to 2200 eV in planar polarization and with photon fluxes >1012 photons s−1 (500 mA ring current) at a resolving power of greater than 10000 and up to a maximum of 32000. The endstation currently provides two sample environments: a catalysis cell and an electrochemical/liquid cell. The former allows APXPS measurements of solid samples in the presence of a gaseous atmosphere (with a mixture of up to eight gases and a vapour of a liquid) and simultaneous analysis of the inlet/outlet gas composition by online mass spectrometry. The latter is a more versatile setup primarily designed for APXPS at the solid–liquid (dip-and-pull setup) or liquid–gas (liquid microjet) interfaces under full electrochemical control, and it can also be used as an open port for ad hoc-designed non-standard APXPS experiments with different sample environments. The catalysis cell can be further equipped with an IR reflection–absorption spectrometer, allowing for simultaneous APXPS and IR spectroscopy of the samples. The endstation is set up to easily accommodate further sample environments.
Photoelectron spectroscopy (PES) is an important technique for tracing and understanding the side reactions responsible for decreasing performance of Li-ion batteries. Interpretation of different spectral components is dependent on correct binding energy referencing, and for battery electrodes, this is highly complex. In this work, we investigate the effect on binding energy reference points in PES in correlation to solid electrolyte interphase (SEI) formation, changing electrode potentials, and state of charge variations in Li-ion battery electrodes. The results show that components in the SEI have a significantly different binding energy reference point relative to the bulk electrode material (i.e., up to 2 eV). It is also shown that electrode components with electronically insulating/semiconducting nature are shifted as a function of electrode potential relative to highly conducting materials. Further, spectral changes due to lithiation are highly depending on the nature of the active material and its lithiation mechanism. Finally, a strategy for planning and evaluating PES experiments on battery electrodes is proposed where some materials require careful choice of one or more internal reference points while others may be treated essentially without internal calibration.
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