Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries.

Lithium metal batteries represent a promising technology for next-generation energy storage, but they still suffer from poor cycle life due to lithium dendrite formation and cathode cracking. Fluorinated solvents can improve battery longevity by improving LiF content in the solid-electrolyte interphase; however, the high cost and environmental concerns of fluorinated solvents limit battery viability. Here we designed a series of fluorine-free solvents through the methylation of 1,2-dimethoxyethane, which promotes inorganic LiF-rich interphase formation through anion reduction and achieves high oxidation stability. The anion-derived LiF interphases suppress lithium dendrite growth on the lithium anode and minimize cathode cracking under high-voltage operation. The Li+-solvent structure is investigated through in situ techniques and simulations to draw correlations between the interphase compositions and electrochemical performances. The methylation strategy provides an alternative pathway for electrolyte engineering towards high-voltage electrolytes while reducing dependence on expensive fluorinated solvents.

High voltage electrolytes for lithium-ion batteries with micro-sized silicon anodes.

Micro-sized silicon anodes can significantly increase the energy density of lithium-ion batteries with low cost. However, the large silicon volume changes during cycling cause cracks for both organic-inorganic interphases and silicon particles. The liquid electrolytes further penetrate the cracked silicon particles and reform the interphases, resulting in huge electrode swelling and quick capacity decay. Here we resolve these challenges by designing a high-voltage electrolyte that forms silicon-phobic interphases with weak bonding to lithium-silicon alloys. The designed electrolyte enables micro-sized silicon anodes (5 µm, 4.1 mAh cm-2) to achieve a Coulombic efficiency of 99.8% and capacity of 2175 mAh g-1 for >250 cycles and enable 100 mAh LiNi0.8Co0.15Al0.05O2 pouch full cells to deliver a high capacity of 172 mAh g-1 for 120 cycles with Coulombic efficiency of >99.9%. The high-voltage electrolytes that are capable of forming silicon-phobic interphases pave new ways for the commercialization of lithium-ion batteries using micro-sized silicon anodes.

Speciation of Transition Metal Dissolution in Electrolyte from Common Cathode Materials.

Significant capacity loss has been observed across extended cycling of lithium-ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid-electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. In this work, X-ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn2 O4 (LMO), LiNi0.5 Mn1.5 O4 (LNMO), LiNi0.8 Mn0.1 Co0.1 O2 (NMC811), and (x Li2 MnO3 *(1-x) LiNia Mnb Coc O2 , with a+b+c=1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma-mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.

Revealing the Anion-Solvent Interaction for Ultralow Temperature Lithium Metal Batteries.

Anion solvation in electrolytes can largely change the electrochemical performance of the electrolytes, yet has been rarely investigated. Herein, three anions of bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and derived asymmetric (fluorosulfonyl)(trifluoro-methanesulfonyl)imide (FTFSI) are systematically examined in a weakly Li+ cation solvating solvent of bis(3-fluoropropyl)ether (BFPE). In-situ liquid secondary ion mass spectrometry demonstrates that FTFSI- and FSI- anions are associated with BFPE solvent, while weak TFSI- /BFPE cluster signals are detected. Molecular modeling further reveals that the anion-solvent interaction is accompanied by the formation of H-bonding-like interactions. Anion solvation enhances the Li+ cation transfer number and reduces the organic component in solid electrolyte interphase, which enhances the Li plating/stripping Coulombic efficiency at a low temperature of -30 °C from 42.4% in TFSI-based electrolytes to 98.7% in 1.5 m LiFTFSI and 97.9% in LiFSI-BFPE electrolytes. The anion-solvent interactions, especially asymmetric anion solvation also accelerate the Li+ desolvation kinetics. The 1.5 m LiFTFSI-BFPE electrolyte with strong anion-solvent interaction enables LiNi0.8 Mn0.1 Co0.1 O2 (NMC811)||Li (20 µm) full cell with stable cyclability even under -40 °C, retaining over 92% of initial capacity (115 mAh g-1 , after 100 cycles). The anion-solvent interactions insights allow to rational design the electrolyte for lithium metal batteries and beyond to achieve high performance.

High-Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential.

Electrolyte engineering is crucial for developing high-performance lithium metal batteries (LMB). Here, we synthesized two cosolvents methyl bis(fluorosulfonyl)imide (MFSI) and 3,3,4,4-tetrafluorotetrahydrofuran (TFF) with significantly different reduction potentials and add them into LiFSI-DME electrolytes. The LiFSI/TFF-DME electrolyte gave an average Li Coulombic efficiency (CE) of 99.41 % over 200 cycles, while the average Li CEs for MFSI-based electrolyte is only 98.62 %. Additionally, the TFF-based electrolytes exhibited a more reversible performance than the state-of-the-art fluorinated 1,4-dimethoxylbutane electrolyte in both Li||Cu half-cell and anode-free Cu||LiNi0.8 Mn0.1 Co0.1 O2 full cell. More importantly, the decomposition product from bis(fluorosulfonyl)imide anion could react with ether solvent, which destroyed the SEI, thus decreasing cell performance. These key discoveries provide new insights into the rational design of electrolyte solvents and cosolvents for LMB.