Enabling practical utilization of layered R3̅m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[NiCoAl]O (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface LiCO content on the magnitude and character of the dissolution reaction was studied.
The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1–xNi0.8Co0.15Al0.05O2 binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li+ extraction is driving the rise in impedance.
This paper reports new insights into structural and chemical evolution of surface phases of LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (60°C) by correlating crystal structure using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) imaging with chemistry using electron energy loss spectroscopy (EELS). We also followed the Al distribution within individual NCA particles by X-ray energy dispersive spectroscopy (EDS). The progression of these phases as a function of distance from the edge shows simultaneous evolution of crystal structures and chemistry from rocksalt to layered, forming a complete solid solution. We have also observed an extended disordered phase with rocksalt (Fm3̅ m) symmetry in which quantitative electron energy loss spectroscopy reveals it to be an oxygen deficient cation disordered phase with chemical characteristics, as determined by EELS, similar to spinel. The formation of these disordered phases with cation and oxygen vacancies has been driven by surface oxygen loss caused by reactions with the electrolyte followed by cation migration from the octahedral 3a M (M = Ni, Co, Al) layer to the octahedral 3b Li layer. These surface rocksalt phases are not fully dense as they contain Al and Li as well as a high concentration of cation and oxygen vacancies. After discharge, Li is detected within these phases indicative that Li transport has occurred through these rocksalt phases. At 60°C and 4.75 V a very large impedance rise is observed leading to complete cell irreversibility which is caused by significant metal dissolution from the cathode and formation of surface porosity. In the near surface region of some particles, a phase transformation from R3̅ m (O3) to P3̅ m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion.
Numerical groundwater flow modeling, reverse particle tracking, and environmental tracers are used to locate the source of geogenic As affecting an aquifer in West Bengal. The aquifer is hosted by point-bar sands deposited in a meandering fluvial environment. Wells tapping the aquifer exhibit As concentrations up to 531 lg/L. High-As groundwaters are recharged in ponds marking an abandoned river channel. The source of As is traced to the underlying fine-grained channel-fill sediments. Arsenic release within these sediments is accompanied by a concomitant release of Br and DOC indicating that these species may be decay products of natural organobromines codeposited along with As. Mass transfer of As to the dissolved phase and its flushing from source sediments are described using a simplified reactive solute transport model. Based on this model, a characteristic reaction time for mass transfer is estimated at 6.7 years. Average groundwater residence times in the source are estimated to have declined from 16.6 to 6.6 years with the advent of intensive irrigation pumping. The ratio of residence and reaction times, a Damk€ ohler number, has declined correspondingly from 2.49 to 0.99, indicating a shift from transport to reaction rate limited As mobilization. Greater insight into the As problem in SE Asia may be achieved by shifting the focus of field investigations from aquifers to potential contamination sources in aquitards.
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