Lithium reduction reaction for interfacial regulation of lithium metal anode

Abstract

Lithium metal anode (LMA) is regarded as a great promising candidate for next-generation lithium batteries. The interfacial issue plays a pivotal role in affecting the lithium plating/stripping behavior, Coulombic efficiency...

Stable Li Metal–Electrolyte Interface Enabled by SEI Improvement and Cation Shield Functionality of the Azamacrocyclic Ligand in Carbonate Electrolytes

“…The Li 3 N component is reported as an adequate Li-ion conductor, although electronic conduction is extremely slow, which demonstrates desirable SEI characteristics. 11 As a result, the SEI derived from the nitrate anion is appropriate for passivating the deposited Li metal. Furthermore, the Li 1s signal from the tmCyclam-added and LiNO 3 /tmCyclam-added electrolytes exhibits an intense Li metal peak from the topmost of the deposited Li surface, indicating that additive application properly protects the deposited Li metal surface.…”

“…Lithium nitrate forms a Li 3 N-based SEI on the Li metal surface, allowing for Li-ion conduction while inhibiting electron transfer to the solvent molecules. 11,13,30,31 However, the maximum solubility of lithium nitrate in carbonate-based electrolytes is quite low, making it unsuitable for use as an electrolyte additive in an LMB system. 13,30 The limited solubility of lithium nitrate in carbonate electrolytes was a factor that motivated this research.…”

“…A significant obstacle in improving the energy density of commercial lithium-ion batteries (LIBs) is the low specific capacity of the active materials used; hence, replacing the graphite negative electrode with a Li metal electrode is a promising approach to increase the energy density of LIBs because the specific capacity of the Li metal can reach up to 3861 mA h g –1 . − However, the reversibility of the Li metal electrode is limited due to the dendritic growth of lithium during extended cycling, which causes continuous electrolyte decomposition on the newly formed interface and hazardous failure, ultimately resulting in internal shortage by the Li-penetrated separator. ,− Hence, manipulating the deposition morphology of the Li metal is crucial to realize a stable chemistry of lithium metal batteries (LMBs) for practical applications. Electrolyte formulation, − lithiophilic nucleation seed introduction, − and functional separators − have been proposed as mitigation strategies for controlling the deposition morphology of the Li metal during continuous cycling. A highly concentrated electrolyte using ether-based solvents has been a significant advancement in the development of electrolyte systems .…”

“…Owing to the intrinsic anodic stability of carbonate solvents, a carbonate-based electrolyte is regaining prominence for LMBs. ,,− Although a carbonate electrolyte has moderate anodic stability on the positive electrode surface, the severe cathodic decomposition and the subsequent formation of a solid electrolyte interphase (SEI) on the Li metal are significant drawbacks of a carbonate-based electrolyte system. − Moreover, enhancement in the SEI on the Li metal in an ether electrolyte system is critical for improving the cell performance of LMBs, and lithium nitrate is a typical example. Lithium nitrate forms a Li 3 N-based SEI on the Li metal surface, allowing for Li-ion conduction while inhibiting electron transfer to the solvent molecules. ,,, However, the maximum solubility of lithium nitrate in carbonate-based electrolytes is quite low, making it unsuitable for use as an electrolyte additive in an LMB system. , The limited solubility of lithium nitrate in carbonate electrolytes was a factor that motivated this research. If a sufficient amount of lithium nitrate additive is added to a carbonate electrolyte, the reversibility of the Li metal negative electrode in the carbonate electrolyte system may be increased, enabling the practical application of carbonate electrolytes.…”

Lithiophilic Sn–Co nano-seeds sealed in a hollow carbon shell to stabilize lithium metal anodes

“…It is important to guide homogeneous Li deposition in the initial Li nucleation stage to construct highly efficient and dendrite-free Li anodes. 10,11 This can be achieved by decorating the substrate with lithiophilic materials (such as noble metals and heteroatom doping). [12][13][14] For instance, it was found that Li metal could form Li x Au solid solution on an Au substrate, and its lower nucleation barrier could induce preferential deposition of Li on Au.…”