16 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
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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
Surface Structural and Chemical Evolution of Layered LiNi \u3c inf\u3e 0.8 Co \u3c inf\u3e 0.15 Al \u3c inf\u3e 0.05 O \u3c inf\u3e 2 (NCA) under High Voltage and Elevated Temperature Conditions
© Copyright 2018 American Chemical Society. This paper reports new insights into structural and chemical evolution of surface phases of LiNi0.8Co0.15Al0.05O2 (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 (Fm3m) 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 R3m (O3) to P3m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion
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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.
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Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.
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[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
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Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2.
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[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
Origin of Rapid Delithiation In Secondary Particles Of LiNi0.8Co0.15Al0.05O2 and LiNiyMnzCo(1-y-z)O2 Cathodes
Most research on the electrochemical dynamics in materials for high-energy Li-ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two-phase transformation within LiNi 0.8Co0.15Al0.05O2 . Here, we use nano-focused X-ray probes to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X-ray microdiffraction (µ-XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li-site fraction (xLi) ~0.9 and ~0.4 for LiNi0.8Co0.15Al0.05O2 . Physics-based modeling shows that, to reproduce the experimental results, the exchange current density (i0) must depend on xLi , and that i0 should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump in i0 are crucial to understanding the charge-storage reaction of Li-ion battery cathodes
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
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Origin of Rapid Delithiation In Secondary Particles Of LiNi0.8Co0.15Al0.05O2 and LiNiyMnzCo1−y−zO2 Cathodes
Most research on the electrochemical dynamics in materials for high-energy Li-ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two-phase transformation within LiNi0.8Co0.15Al0.05O2. Here, nano-focused X-ray probes are used to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X-ray microdiffraction ((Formula presented.) -XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li-site fraction (xLi) ≈0.9 and ≈0.5 for LiNi0.8Co0.15Al0.05O2. Physics-based modeling shows that, to reproduce the experimental results, the exchange current density (i0) must depend on xLi, and that i0 should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump in i0 are crucial to understanding the charge-storage reaction of Li-ion battery cathodes