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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 LiNi 0.8 Co 0.2-y AlyO 2 (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 LiPF 6 salt with the more thermally stable LiBF 4 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 LiPF 6 (LiBF 4 ). 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 LiPF 6 and LiBF 4 , 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.

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[Ni 0.8 Co 0.15 Al 0.05 ]O 2 (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 Li 2 CO 3 content on the magnitude and character of the dissolution reaction was studied.

Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.

A new type of positive electrode for Li-ion batteries has been developed recently based on FeF3/C and FeF2/C nanocomposites. The microstructural and redox evolution during discharge and recharge processes was followed by electron energy loss spectroscopy (EELS) to determine the valence state of Fe by measuring the Fe L3 line energy shift and from Fe L3/L2 line intensity ratios. In addition, transition metal fluorides were found to be electron beam sensitive, and the effect of beam exposure on EELS spectra was also investigated. The EELS results indicate that for both FeF3/C and FeF2/C nanocomposite systems, a complete reduction of iron to FeO is observed upon discharge to 1.5 V with the formation of a finer FeO/LiF subnanocomposite ( approximately 7 nm). Upon complete recharging to 4.5 V, EELS data reveal a reoxidation process to a Fe2+ state with the formation of a carbon metal fluoride nanocomposite related to the FeF2 structure.