RESUMEN
Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behaviour and stability at solid-solid interfaces remains limited compared to at solid-liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth and volumetric changes determines cell behaviour. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur owing to partial molar volume mismatches at either electrode. These results provide insight into how chemo-mechanical phenomena can affect cell performance, thus facilitating the development of solid-state batteries.
RESUMEN
Lithium alloy anodes in the form of dense foils offer significant potential advantages over lithium metal and particulate alloy anodes for solid-state batteries (SSBs). However, the reaction and degradation mechanisms of dense alloy anodes remain largely unexplored. Here, we investigate the electrochemical lithiation/delithiation behavior of 12 elemental alloy anodes in SSBs with Li6PS5Cl solid-state electrolyte (SSE), enabling direct behavioral comparisons. The materials show highly divergent first-cycle Coulombic efficiency, ranging from 99.3% for indium to â¼20% for antimony. Through microstructural imaging and electrochemical testing, we identify lithium trapping within the foil during delithiation as the principal reason for low Coulombic efficiency in most materials. The exceptional Coulombic efficiency of indium is found to be due to unique delithiation reaction front morphology evolution in which the high-diffusivity LiIn phase remains at the SSE interface. This study links composition to reaction behavior for alloy anodes and thus provides guidance toward better SSBs.
RESUMEN
Metal negative electrodes that alloy with lithium have high theoretical charge storage capacity and are ideal candidates for developing high-energy rechargeable batteries. However, such electrode materials show limited reversibility in Li-ion batteries with standard non-aqueous liquid electrolyte solutions. To circumvent this issue, here we report the use of non-pre-lithiated aluminum-foil-based negative electrodes with engineered microstructures in an all-solid-state Li-ion cell configuration. When a 30-µm-thick Al94.5In5.5 negative electrode is combined with a Li6PS5Cl solid-state electrolyte and a LiNi0.6Mn0.2Co0.2O2-based positive electrode, lab-scale cells deliver hundreds of stable cycles with practically relevant areal capacities at high current densities (6.5 mA cm-2). We also demonstrate that the multiphase Al-In microstructure enables improved rate behavior and enhanced reversibility due to the distributed LiIn network within the aluminum matrix. These results demonstrate the possibility of improved all-solid-state batteries via metallurgical design of negative electrodes while simplifying manufacturing processes.
RESUMEN
Solid-state batteries (SSBs) with lithium metal anodes offer higher specific energy than conventional lithium-ion batteries, but they must utilize areal capacities >3 mAh cm-2 and cycle at current densities >3 mA cm-2 to achieve commercial viability. Substantial research effort has focused on increasing the rate capabilities of SSBs by mitigating detrimental processes such as lithium filament penetration and short circuiting. Less attention has been paid to understanding how areal capacity impacts lithium plating/stripping behavior in SSBs, despite the importance of areal capacity for achieving high specific energy. Here, we investigate and quantify the relationships among areal capacity, current density, and plating/stripping stability using both symmetric and full-cell configurations with a sulfide solid-state electrolyte (Li6PS5Cl). We show that unstable deposition and short circuiting readily occur at rates much lower than the measured critical current density when a sufficient areal capacity is passed. A systematic study of continuous plating under different electrochemical conditions reveals average "threshold capacity" values at different current densities, beyond which short circuiting occurs. Cycling cells below this threshold capacity significantly enhances cell lifetime, enabling stable symmetric cell cycling at 2.2 mA cm-2 without short circuiting. Finally, we show that full cells with LiNi0.8Mn0.1Co0.1O2 also exhibit threshold capacity behavior, but they tend to short circuit at lower current densities and areal capacities. Our results quantify the effects of transferred capacity and demonstrate the importance of using realistic areal capacities in experiments to develop viable solid-state batteries.