Electrolyte Design for High-Voltage Lithium-Metal Batteries with Synthetic Sulfonamide-Based Solvent and Electrochemically Active Additives.

Considering practical viability, Li-metal battery electrolytes should be formulated by tuning solvent composition similar to electrolyte systems for Li-ion batteries to enable the facile salt-dissociation, ion-conduction, and introduction of sacrificial additives for building stable electrode-electrolyte interfaces. Although 1,2-dimethoxyethane with a high-donor number enables the implementation of ionic compounds as effective interface modifiers, its ubiquitous usage is limited by its low-oxidation durability and high-volatility. Regulation of the solvation structure and construction of well-structured interfacial layers ensure the potential strength of electrolytes in both Li-metal and LiNi0.8 Co0.1 Mn0.1 O2 (NCM811). This study reports the build-up of multilayer solid-electrolyte interphase by utilizing different electron-accepting tendencies of lithium difluoro(bisoxalato) phosphate (LiDFBP), lithium nitrate, and synthetic 1-((trifluoromethyl)sulfonyl)piperidine. Furthermore, a well-structured cathode-electrolyte interface from LiDFBP effectively addresses the issues with NCM811. The developed electrolyte based on a framework of highly- and weakly-solvating solvents with interface modifiers enables the operation of Li|NCM811 cells with a high areal capacity cathode (4.3 mAh cm-2 ) at 4.4 V versus Li/Li+ .

Real-Time Visualizing Nucleation and Growth of Electrodes for Post-Lithium-Ion Batteries.

ConspectusUntil recently, most studies on nucleation and growth mechanisms have employed electrochemical transient measurements, and numerous models have been established on various metal electrode elements. Contrary to the conventional tip-induced nucleation and growth model, a base-induced nucleation and growth mode was discovered not so long ago, which highlighted the importance of direct real-time observations such as visualization. As analysis techniques developed, diverse in situ/operando imaging methods have spurred the fundamental understanding of complex and dynamic battery electrochemistry. Experimental observations of alkali Li and Na metals are limited and difficult because their high reactivity makes not only the fabrication but also the analysis itself challenging. Na metal has high reactivity to electrolytes. Accordingly, it is difficult to visualize the Na deposition in real-time due to gas evolution and resolution limitation. Only a few studies have examined the Na deposition and dissolution reactions in operando. It is generally believed that the Mg anode is free from the dendrite growth of Mg metal, and Mg deposition preferentially occurs along the surface direction. However, whether the Mg anode always follows the dendrite-free growth has currently become a controversial topic and is being discussed and redefined based on real-time imaging analyses. In addition, a variety of morphological evolutions in the metal anodes are required to be systematically distinguished by key parameters. Real-time imaging analysis can directly confirm the solid-liquid-solid multiphase conversion reactions of S and Se cathodes. S and Se elements belong to the same chalcogen group, but their crystal structures and morphological changes significantly differ in each electrode during deposition and dissolution reactions. Therefore, it is necessitated to discuss the nucleation and growth behaviors by examining intrinsic properties of each element in chalcogen cathodes. Considering that a mechanistic understanding of the Se cathode is in its infancy, its nucleation and growth behaviors must be further explored through fundamental studies. In this Account, we aim to discuss the nucleation and growth behaviors of metal (Li, Na, and Mg) anodes and chalcogen (S and Se) cathodes. To elucidate their nucleation and growth mechanisms, we overview the morphological evolutions on the electrode surface and interface by in situ/operando visualizations. Our recent studies covering Li, Na, Mg, S, and Se electrodes verified by operando X-ray imaging are used as critical resources in understanding their nucleation and growth behaviors. Overall, with validation of the complex and dynamic nucleation and growth behaviors of metal and chalcogen electrodes by in situ/operando visualization methods, we hope that this Account can contribute to supporting the fundamental knowledge for the development of high-energy-density metal and chalcogen electrodes.

Visualization of Sodium Metal Anodes via Operando X-Ray and Optical Microscopy: Controlling the Morphological Evolution of Sodium Metal Plating.

Because of the abundance and cost effectiveness of sodium, rechargeable sodium metal batteries have been widely studied to replace current lithium-ion batteries. However, there are some critical unresolved issues including the high reactivity of sodium, an unstable solid-electrolyte interphase (SEI), and sodium dendrite formation. While several studies have been conducted to understand sodium plating/stripping processes, only a very limited number of studies have been carried out under operando conditions. We have employed operando X-ray and optical imaging techniques to understand the mechanistic behavior of Na metal plating. The morphology of sodium metal plated on a copper electrode depends strongly on the salts and solvents used in the electrolyte. The addition of a fluorine-containing additive to a carbonate-based electrolyte, NaClO4 in propylene carbonate (PC):fluoroethylene carbonate (FEC), results in uniform sodium plating processes and much more stable cycling performance, compared to NaClO4 in PC, because of the formation of a stable SEI containing NaF. A NaF layer, on top of the sodium metal, leads to a much more uniform deposition of sodium and greatly enhanced cyclability.

Understanding the Effects of Interfacial Lithium Ion Concentration on Lithium Metal Anode.

Despite the development of multidimensional state-of-the-art electrode materials for constructing better lithium metal anodes (LMAs), the key factors influencing the electrochemical performance of LMAs are still poorly understood. Herein, it is demonstrated that the local lithium ion concentration at the interface between the electrode and electrolyte exerts significant influence on the electrochemical performance of LMAs. The local ion concentration is multiplied by introducing pseudocapacitive nanocarbons (PNCs) containing numerous heteroatoms, because PNCs can store large numbers of lithium ions in a pseudocapacitive manner, and promote the formation of an electrochemical double layer. The high interfacial lithium ion concentration induces the formation of lithium-rich inorganic solid-electrolyte-interface layers with high ionic conductivities, and facilitates sustainable and stable supplies of lithium ion charge carriers on the overall active surfaces of the PNCs. Accordingly, the PNC-induced LMA exhibits high Coulombic efficiencies, high rate capabilities, and stable cycling performance.

Three Dimensional Measurement of Ideal Trajectory of Pedicle Screws of Subaxial Cervical Spine Using the Algorithm Could Be Applied for Robotic Screw Insertion.

OBJECTIVE: To define optimal method that calculate the safe direction of cervical pedicle screw placement using computed tomography (CT) image based three dimensional (3D) cortical shell model of human cervical spine. METHODS: Cortical shell model of cervical spine from C3 to C6 was made after segmentation of in vivo CT image data of 44 volunteers. Three dimensional Cartesian coordinate of all points constituting surface of whole vertebra, bilateral pedicle and posterior wall were acquired. The ideal trajectory of pedicle screw insertion was defined as viewing direction at which the inner area of pedicle become largest when we see through the biconcave tubular pedicle. The ideal trajectory of 352 pedicles (eight pedicles for each of 44 subjects) were calculated using custom made program and were changed from global coordinate to local coordinate according to the three dimensional position of posterior wall of each vertebral body. The transverse and sagittal angle of trajectory were defined as the angle between ideal trajectory line and perpendicular line of posterior wall in the horizontal and sagittal plane. The averages and standard deviations of all measurements were calculated. RESULTS: The average transverse angles were 50.60º±6.22º at C3, 51.42º ±7.44º at C4, 47.79º ±7.61º at C5, and 41.24º ±7.76º at C6. The transverse angle becomes more steep from C3 to C6. The mean sagittal angles were 9.72º ±6.73º downward at C3, 5.09º±6.39º downward at C4, 0.08º ±6.06º downward at C5, and 1.67º ±6.06º upward at C6. The sagittal angle changes from caudad to cephalad from C3 to C6. CONCLUSION: The absolute values of transverse and sagittal angle in our study were not same but the trend of changes were similar to previous studies. Because we know 3D address of all points constituting cortical shell of cervical vertebrae. we can easily reconstruct 3D model and manage it freely using computer program. More creative measurement of morphological characteristics could be carried out than direct inspection of raw bone. Furthermore this concept of measurement could be used for the computing program of automated robotic screw insertion.