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Lithium batteries with solid-state electrolytes are an appealing alternative to state-of-the-art non-aqueous lithium-ion batteries with liquid electrolytes because of safety and energy aspects. However, engineering development at the cell level for lithium batteries with solid-state electrolytes is limited. Here, to advance this aspect and produce high-energy lithium cells, we introduce a cell design based on advanced parametrization of microstructural and architectural parameters of electrode and electrolyte components. To validate the cell design proposed, we assemble and test (applying a stack pressure of 3.74 MPa at 45 °C) 10-layer and 4-layer solid-state lithium pouch cells with a solid polymer electrolyte, resulting in an initial specific energy of 280 Wh kg-1 (corresponding to an energy density of 600 Wh L-1) and 310 Wh kg-1 (corresponding to an energy density of 650 Wh L-1) respectively.
RESUMO
Li- and Mn-rich layered oxides (LMRs) have emerged as practically feasible cathode materials for high-energy-density Li-ion batteries due to their extra anionic redox behavior and market competitiveness. However, sluggish kinetics regions (<3.5 V vs Li/Li+ ) associated with anionic redox chemistry engender LMRs with chemical irreversibility (first-cycle irreversibility, poor rate properties, voltage fading), which limits their practical use. Herein, the structural origin of this chemical irreversibility is revealed through a comparative study involving Li1.15 Mn0.51 Co0.17 Ni0.17 O2 with relatively localized and delocalized excess-Li in its lattice system. Operando fine-interval X-ray absorption spectroscopy is used to simultaneously observe the interplay between transition-metal-oxygen (TM-O) redox chemistry and TM migration behavior in real time. Density functional theory calculations show that excess-Li localization in the LMR structure attenuates TM-O covalency and stability, leading to overall chemical irreversibility. Hence, the delocalized excess-Li system is proposed as an alternative design for practically feasible LMR cathodes with restrained TM migration and sustainable O-redox chemistry.
RESUMO
Oxygen vacancies (OV) are native defects in transition metal (TM) oxides and their presence has a critical effect on the physicochemical properties of the oxide. Metal oxides are commonly used in lithium-ion battery (LIB) cathodes and there is still a lack of understanding of the role of OVs in LIB research field. Here, we report on the behavior of OVs in a single-crystal LIB cathode during the non-equilibrium states of charge and discharge. We found that microcrack evolution in a single crystal occurs due to OV condensation in specific crystallographic orientations generated by the continuous migration of OVs and TM ions. Moreover, understanding the effects of the presence and diffusion of OVs in metal oxides enables the elucidation of most of the conventional mechanisms of capacity fading in LIBs and provides new insights for new electrochemical applications.
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OBJECTIVE: Minimal data exist regarding non-operative management of suspected pseudarthrosis after pedicle subtraction osteotomy (PSO). This study reports radiographic and clinical outcomes of non-operative management for post-PSO pseudarthrosis at a minimum 5 years post-detection. METHODS: Nineteen consecutive patients with implant breakage indicating probable pseudarthrosis after PSO surgery (13 women/ six men; mean age at surgery, 58 years) without severe pain and disability were treated with non-operative management (mean follow-up, 5.8 years; range, 5-10 years). Non-operative management included medication, intermittent brace wearing and avoidance of excessive back strain. Radiographic and clinical outcomes analysis was performed. RESULTS: Sagittal vertical axis (SVA), proximal junctional angle, thoracic kyphosis achieved by a PSO were maintained after detection of pseudarthrosis through ultimate follow-up. Lumbar lordosis and PSO angle decreased at final follow-up. There was no significant change in Oswestry Disability Index (ODI) scores and Scoliosis Research Society (SRS) total score, or subscales of pain, self-image, function, satisfaction and mental health between detection of pseudarthrosis and ultimate follow-up. SVA greater than 11 cm showed poorer ODI and SRS total score, as well as the pain, self-image, and function subscales (p<0.05). CONCLUSION: Non-operative management of implant failure of probable pseudarthrosis after PSO offers acceptable outcomes even at 5 years after detection of implant breakage, provided SVA is maintained. As SVA increased, outcome scores decreased in this patient population.
RESUMO
Lithium-excess 3d-transition-metal layered oxides (Li1+xNiyCozMn1-x-y-zO2, >250 mAh g-1) suffer from severe voltage decay upon cycling, which decreases energy density and hinders further research and development. Nevertheless, the lack of understanding on chemical and structural uniqueness of the material prevents the interpretation of internal degradation chemistry. Here, we discover a fundamental reason of the voltage decay phenomenon by comparing ordered and cation-disordered materials with a combination of X-ray absorption spectroscopy and transmission electron microscopy studies. The cation arrangement determines the transition metal-oxygen covalency and structural reversibility related to voltage decay. The identification of structural arrangement with de-lithiated oxygen-centred octahedron and interactions between octahedrons affecting the oxygen stability and transition metal mobility of layered oxide provides the insight into the degradation chemistry of cathode materials and a way to develop high-energy density electrodes.