RESUMEN
Mn-based high voltage cathodes, e.g., spinel LiMn2O4, are considered among the most promising materials for cost-effective, next generation energy storage. When paired with a Li metal anode, secondary batteries based on Li||LiMn2O4 in principle offer a straightforward, scalable approach for achieving cost-effective and high energy density storage demanded in applications. In practice, however, such batteries fail to live up to their promise. Rapid capacity fading caused by irreversible Mn dissolution at the cathode coupled with mossy/dendritic Li deposition at the anode limit their useful life. In this study, we report on the design of electrolytes based on a binary blend of two widely available salts, LiNO3 and LiTFSI, in ethylene carbonate (EC), which simultaneously overcome failure modes at both the cathode and anode of Li||LiMn2O4 batteries. The electrolyte design is motivated by a recent finding that compared with their linear counterparts (e.g., dimethyl carbonate), cyclic carbonates like EC dissolve considerably larger amount of LiNO3, which markedly improves anode reversibility. On the other hand, it is known that nonsolvolytic fluorine-containing Li salts like LiTFSI, lowers the electrolyte's susceptibility to solvolysis, which generates HF species responsible for Mn leaching at the cathode. In particular, we report instead that fluorine groups in the TFSI salt, promote formation of a favorable, fluorine-rich interphase on the Li metal anode. Electrochemical measurements show that the electrolytes enable remarkably improved charge-discharge cycling stability (>1000 charge-discharge cycles) of Li||LiMn2O4 batteries. In-depth atomic-resolution electron microscopy and X-ray/synchrotron diffraction experiments reveal the fundamental source of the improvements. The measurements show that crystallographic degradation of Mn-based cathodes (e.g., surface Mn leaching and bulk defect generation) upon cycling in conventional electrolytes is dramatically lowered in the LiNO3 + LiTFSI/EC electrolyte system. It is shown further that the reduction of Mn dissolution not only improves the cathode stability but improves the reversibility of the Li metal anode via a unique re-deposition mechanism in which Li and Mn co-deposit on the anode. Taken together, our findings show that the LiNO3 + LiTFSI/EC electrolyte system holds promise for accelerating progress towards practical Li||LiMn2O4 batteries because it stabilizes the dynamic interfaces required for long-term stability at both the Li anode and the LiMn2O4 cathode.
RESUMEN
Controlling the morphological evolution of electrochemical crystal growth in battery anodes is of fundamental and practical importance, particularly towards realizing practical, high-energy batteries based on metal electrodes. Such batteries require highly reversible plating/stripping reactions at the anode to achieve a long cycle life. While conformal electrodeposition and electrode reversibility have been demonstrated in numerous proof-of-concept experiments featuring moderate to low areal capacity (≤3 mA h/cm2) electrodes, achieving high levels of reversibility is progressively challenging at the higher capacities (e.g., 10 mA h/cm2), required in applications. Nonplanar, "3D" electrodes composed of electrically conductive, porous substrates are conventionally thought to overcome trade-offs between reversibility and capacity because they hypothetically "host" the electrodeposits in an electronically conducting framework, providing redundant pathways for electron flow. Here, we challenge this hypothesis and instead show that a nonplanar substrate with moderate electrical conductivity (ideally, with an electrical conductance similar to the ionic conductance of the electrolyte) and composed of a passivated cathode-facing surface efficiently regulates electro-crystallization. In contrast, an architecture with a high intrinsic electrical conductivity or with a high electrical conductivity coating on the front surface results in dominantly out-of-plane growth, making the 3D architecture in effect function as a 2D substrate. Using Zn as an example, we demonstrate that interconnected carbon fiber substrates coated by SiO2 on the front and Cu on the back successfully ushers electroplated Zn metal into the 3D framework at a macroscopic length scale, maximizing use of the interior space of the framework. The effective integration of electrodeposits into the 3D framework also enables unprecedented plating/stripping reversibility >99.5% at high current density (e.g., 10 mA/cm2) and high areal capacities (e.g., 10 mA h/cm2). Used in full-cell Zn||NaV3O8 batteries with stringent N/P ratios of 3:1, the substrates are also shown to enhance cycle life.
