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A nonsolvolytic fluorine/LiNO3-containing electrolyte for stabilizing dynamic interfaces in Li||LiMn2O4 batteries.
Tang, Tian; Utomo, Nyalaliska W; Zheng, J X Kent; Archer, Lynden A.
Afiliación
  • Tang T; Department of Materials Science and Engineering, Cornell University Ithaca NY 14853 USA.
  • Utomo NW; Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University Ithaca NY 14853 USA laa25@cornell.edu.
  • Zheng JXK; Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University Ithaca NY 14853 USA laa25@cornell.edu.
  • Archer LA; McKetta Department of Chemical Engineering, The University of Texas at Austin Austin Texas 78712 USA.
RSC Adv ; 14(21): 14964-14972, 2024 May 02.
Article en En | MEDLINE | ID: mdl-38737648
ABSTRACT
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.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: RSC Adv Año: 2024 Tipo del documento: Article

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: RSC Adv Año: 2024 Tipo del documento: Article
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