Lithium‐Ion Desolvation Induced by Nitrate Additives Reveals New Insights into High Performance Lithium Batteries

Abstract

Electrolyte additives have been widely used to address critical issues in current metal (ion) battery technologies. While their functions as solid electrolyte interface forming agents are reasonably well‐understood, their interactions in the liquid electrolyte environment remain rather elusive. This lack of knowledge represents a significant bottleneck that hinders the development of improved electrolyte systems. Here, the key role of additives in promoting cation (e.g., Li+) desolvation is unraveled. In particular, nitrate anions (NO3−) are found to incorporate into the solvation shells, change the local environment of cations (e.g., Li+) as well as their coordination in the electrolytes. The combination of these effects leads to effective Li+ desolvation and enhanced battery performance. Remarkably, the inexpensive NaNO3 can successfully substitute the widely used LiNO3 offering superior long‐term stability of Li+ (de‐)intercalation at the graphite anode and suppressed polysulfide shuttle effect at the sulfur cathode, while enhancing the performance of lithium–sulfur full batteries (initial capacity of 1153 mAh g−1 at 0.25C) with Coulombic efficiency of ≈100% over 300 cycles. This work provides important new insights into the unexplored effects of additives and paves the way to developing improved electrolytes for electrochemical energy storage applications.

Bismuth-based mixed-anion compounds for anode materials in rechargeable batteries

“…[9][10][11][12][13][14][17][18][19][20][21][22] Importantly, the class of ternary bismuth-based materials, such as in Bi-S-I in this work and previously reported BiSbS 3 , 11 suggest an outstanding performance as battery electrodes over the binary bismuth-based materials as well as the state-of-theart graphite anode (theoretical capacity of 372 mAh g -1 ). 23,24 Furthermore, these materials merit further investigations of which include applications in other type of batteries such as multivalent metal ions (e.g., Zn 2+ , Mg 2+ , and Al 3+ ) battery systems. In summary, we report a controlled synthesis of Bi 13 S 18 I 2 and BiSI by simply tuning the sulfur concentration in a nonaqueous medium and demonstrate their potential as anode materials for rechargeable batteries.…”

“…9–14,17–22 Importantly, the class of ternary bismuth-based materials, such as Bi–S–I in this study and previously reported BiSbS 3 , 11 suggest outstanding performance as battery electrodes over the binary bismuth-based materials and the state-of-the-art graphite anode (theoretical capacity of 372 mA h g −1 ). 23,24 Furthermore, these materials merit further investigations, which include applications in other types of batteries, such as multivalent metal ion ( e.g. , Zn 2+ , Mg 2+ , and Al 3+ ) battery systems.…”

Mechanism understanding for stripping electrochemistry of Li metal anode

“…Numerous methods have been proposed to address these problems including electrolyte additives, [34][35][36][37][38][39][40][41][42][43][44][45] artificial SEI, [46][47][48][49][50][51][52][53][54][55][56] superconcentrated electrolyte, [57][58][59][60][61][62][63][64][65][66][67][68][69][70] solid-state electrolyte (SSE), [71][72][73][74][75][76][77][78][79][80] functional membrane, [81][82][83][84]…”

Controlled Lithium Deposition

“…The electrolyte additives such as fluorinated ethylene carbonate (FEC) (Zhang X.-Q. et al, 2017;Hou et al, 2019;Lin and Zhao, 2020), LiNO 3 (Zhang et al, 2021a;May et al, 2021;Piao et al, 2021;Wahyudi et al, 2021) and vinylene carbonate (VC) (Kuwata et al, 2016; are beneficial for forming stable SEI layers and inhibiting the growth of the lithium dendrites. The application of the gel electrolytes with high conductivity or solid electrolytes with high mechanical strength to replace the conventional liquid electrolytes also reached great achievements in improving the cycling stability.…”