15 research outputs found
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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
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Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi<sub>0.8</sub>Co<sub>0.2-y</sub>Al<sub>y</sub>O<sub>2</sub> Cathodes.
Electrochemical and Thermal Stress of Electrodes: Evolution of Aluminum Surface Environments
For layered oxide cathodes, aluminum doping has widely been shown to improve performance, particularly at high degrees of delithiation. While this has led to increased interest in Al-doped systems, including (NCA), the aluminum surface environment has not been thoroughly investigated. Using hard x-ray photoelectron spectroscopy measurements of the Al 1s core region for NCA electrodes, we examined the evolution of the surface aluminum environment under electrochemical and thermal stress. By correlating the aluminum environment to transition metal reduction and electrolyte decomposition, we provide further insight into the cathode-electrolyte interface layer. A remarkable finding is that Al-O coatings in LiPF electrolyte mimic the evolution observed for the aluminum surface environment in doped layered oxides
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Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.
Enabling practical utilization of layered R3Ì…m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni0.8Co0.15Al0.05]O2 (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 Li2CO3 content on the magnitude and character of the dissolution reaction was studied
Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.
Enabling practical utilization of layered R3Ì…m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni0.8Co0.15Al0.05]O2 (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 Li2CO3 content on the magnitude and character of the dissolution reaction was studied
Evolution of the Electrode–Electrolyte Interface of Electrodes Due to Electrochemical and Thermal Stress
For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode–electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of LiCO, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for (NCA) particle electrodes using a LiPF ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface LiCO and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling
Conversion Reaction Mechanisms in Lithium Ion Batteries:Study of the Binary Metal Fluoride Electrodes
Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF2: 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., FeF2) while others are not (e.g., CuF2). In this study, we investigated the conversion reaction of binary metal fluorides, FeF2 and CuF2, 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 FeF2 and CuF2 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 FeF2, 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 FeF2. In contrast to FeF2, no continuous Cu network was observed in the lithiated CuF2; 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 CuF2 electrode
Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi<sub>0.8</sub>Co<sub>0.15</sub>Al<sub>0.05</sub>O<sub>2</sub>
Enabling practical utilization of
layered <i>R</i>3Ì…<i>m</i> positive electrodes
near full delithiation requires an
enhanced understanding of the complex electrode–electrolyte
interactions that often induce failure. Using LiÂ[Ni<sub>0.8</sub>Co<sub>0.15</sub>Al<sub>0.05</sub>]ÂO<sub>2</sub> (NCA) as a model layered
compound, the chemical and structural stability in a strenuous thermal
and electrochemical environment was explored. <i>Operando</i> 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<sub>2</sub>CO<sub>3</sub> content on the magnitude and character of the dissolution
reaction was studied