Preferential decomposition of the major anion in a dual-salt electrolyte facilitates the formation of organic-inorganic composite solid electrolyte interphase.

The performance of a lithium metal battery (LMB) with liquid electrolytes depends on the realization of a stable solid electrolyte interphase (SEI) on the Li anode surface. According to a recent experiment, a high-concentrated (HC) dual-salt electrolyte is effective in modulating the SEI formation and improving the battery performance. However, the underlying reaction mechanism between this HC dual-salt electrolyte and the lithium metal anode surface remains unknown. To understand the SEI formation mechanism, we first performed 95 ps ab initio Molecular Dynamics (AIMD) simulation and then extend this AIMD simulation to another 1 ns by using Hybrid ab Initio and Reactive Molecular Dynamics (HAIR) to investigate the deep reactions of such dual-salt electrolytes consists of lithium difluorophosphate and lithium bis(trifluoromethanesulfonyl)imide in dimethoxyethane (DME) solvent at lithium metal anode surface. We observed the detailed reductive decomposition processes of DFP- and TFSI-, which include the formation pathway of CF3 fragments, LiF, and LixPOFy, the three main SEI components observed experimentally. Furthermore, after extending the simulation to 1.1 ns via the HAIR scheme, the decomposition reactions of DME solvent molecules were also observed, producing LiOCH3, C2H4, and precursors of organic oligomers. These microscopic insights provide important guidance in designing the advanced dual-salt electrolytes for developing high-performance LMB.

DFT-ReaxFF hybrid molecular dynamics investigation of the decomposition effects of localized high-concentration electrolyte in lithium metal batteries: LiFSI/DME/TFEO.

Due to its low electrochemical potential and high theoretical specific energy, lithium-metal batteries (LMBs) have been considered as a promising advanced energy storage system for portable applications such as electric vehicles (EVs). However, the uncontrolled growth of lithium dendrites during cycling has remained a challenge. By utilizing an inert solvent to "dilute" the high concentration electrolytes, the concept of localized high-concentration electrolytes (LHCEs) has recently been demostrated as an effective solution to enable the dendrite-free cycling of LMBs. In this work, we investigated the reactions of 2 M lithium bis(fluorosulfonyl)imide (LiFSI) in a mixture of dimethoxyethane (DME)/tris(2,2,2-trifluoroethyl) orthoformate (TFEO) electrolyte at a Li metal anode. The SEI formation mechanism is investigated using a hybrid ab initio and reactive force field (HAIR) method. The 1n reactive HAIR trajectory reveals the important initial reduction reactions of LiFSI, TFEO, and DME. Particularly, both FSI anions and TFEO decompose quickly to release a considerable amount of F-, which leads to a LiF-rich SEI inorganic inner layer (IIL). Furthermore, TFEO produces a significant amount of unsaturated carbon products, such as thiophene, which can potentially increase the conductivity of SEI to increase the battery performance. Meanwhile, XPS analysis is utilized to further investigate the evolution of the atomic environment in SEI. Future designs of better electrolytes can be greatly aided by these results.

Multiscale Simulation of Solid Electrolyte Interface Formation in Fluorinated Diluted Electrolytes with Lithium Anodes.

Lithium metal batteries (LMBs) hold great promise in facilitating high-energy batteries due to their merits such as high specific capacity, low reduction potential, and so forth. However, the realizations of practical LMBs are hindered by severe problems such as undesirable dendrite growth, poor Coulombic efficiency, and so forth. A recently proposed fluorinated electrolyte based on 1 M lithium bis(fluorosulfonyl)imide (LiFSI) dissolved in designed fluorinated 1,4-dimethoxybutane (FDMB) solvent has attracted significant attention because of its excellent electrochemical performance that origins from its superior physical and chemical properties, especially its unique ability in forming a robust, stable solid electrolyte interphase (SEI). However, the detailed structure and reaction mechanism of the SEI formation in such a novel electrolyte remains unclear. In this work, we carry out a hybrid ab initio and reactive molecular dynamics (HAIR) simulation to investigate the elementary reactions that regulate the formation of the primitive SEI, paying special attention to the process that involves FDMB, the fluorinated solvent. HAIR simulation reveals that both FSI- anion and FDMB provide F that is adequate to form a uniformed LiF layer that resembles the inorganic inner layer (IIL) of the SEI. N and S radicals from the FSI- anion, which do not deposit on the electrode interface to form lithium-containing inorganic substances, promote the polymerization reaction of unsaturated carbon chains produced by FDMB defluorination, forming the organic outer layer (OOL) of the SEI. The combination of the LiF-rich IIL and polymer-rich organic OOL explains the superior performance of the FDMB-based electrolyte in the device. The detailed reaction mechanism and SEI observed in this work provide insights into the atomic scale for the rational design of F-rich electrolytes in the near future.

Facet-Selective Deposition of Ultrathin Al2 O3 on Copper Nanocrystals for Highly Stable CO2 Electroreduction to Ethylene.

Catalysts based on Cu nanocrystals (NCs) for electrochemical CO2 -to-C2+ conversion with high activity have been a subject of considerable interest, but poor stability and low selectivity for a single C2+ product remain obstacles for realizing sustainable carbon-neutral cycles. Here, we used the facet-selective atomic layer deposition (FS-ALD) technique to selectively cover the (111) surface of Cu NCs with ultrathin Al2 O3 to increase the exposed facet ratio of (100)/(111), resulting in a faradaic efficiency ratio of C2 H4 /CH4 for overcoated Cu NCs 22 times higher than that for pure Cu NCs. Peak performance of the overcoated catalyst (Cu NCs/Al2 O3 -10C) reaches a C2 H4 faradaic efficiency of 60.4 % at a current density of 300 mA cm-2 in 5 M KOH electrolyte, when using a gas diffusion electrode flow cell. Moreover, the Al2 O3 overcoating effectively suppresses the dynamic mobility and the aggregation of Cu NCs, which explains the negligible activity loss and selectivity degradations of Cu NCs/Al2 O3 -10C shown in stability tests.

Effects of High and Low Salt Concentrations in Electrolytes at Lithium-Metal Anode Surfaces Using DFT-ReaxFF Hybrid Molecular Dynamics Method.

Due to creating a passivated solid electrolyte interphase (SEI), high concentration (HC) electrolytes demonstrate peculiar physicochemical properties and outstanding electrochemical performance. However, the structures of such SEI remains far from clear. In this work, a hybrid ab initio and reactive molecular dynamics (HAIR) scheme is employed to investigate the concentration effect of SEI formation by simulating the reductive degradation reactions of lithium bis(fluorosulfonyl)imide (LiFSI) in 1,3 dioxalane (DOL) electrolytes at concentrations of 1 M, 4 M, and 10 M. The efficient HAIR scheme allows the simulations to reach 1 ns to predict electrolytes' deep products at different concentrations. The simulation findings show that the most critical distinction between HC and its low concentration (LC) analogue is that anion decomposition in HC is much more incomplete when only S-F breaking is observed. These insights are important for the future development of advanced electrolytes by rational design of electrolytes.

The DFT-ReaxFF Hybrid Reactive Dynamics Method with Application to the Reductive Decomposition Reaction of the TFSI and DOL Electrolyte at a Lithium-Metal Anode Surface.

The high energy density and suitable operating voltage make rechargeable lithium ion batteries (LIBs) promising candidates to replace such conventional energy storage devices as nonrechargeable batteries. However, the large-scale commercialization of LIBs is impeded significantly by the degradation of the electrolyte, which reacts with the highly reactive lithium metal anode. Future improvement of the battery performance requires a knowledge of the reaction mechanism that is responsible for the degradation and formation of the solid-electrolyte interphase (SEI). In this work, we develop a hybrid computational scheme, Hybrid ab initio molecular dynamics combined with reactive force fields, denoted HAIR, to accelerate Quantum Mechanics-based reaction dynamics (QM-MD or AIMD, for ab initio RD) simulations. The HAIR scheme extends the time scale accessible to AIMD by a factor of 10 times through interspersing reactive force field (ReaxFF) simulations between the AIMD parts. This enables simulations of the initial chemical reactions of SEI formation, which may take 1 ns, far too long for AIMD. We apply the HAIR method to the bis(trifluoromethanesulfonyl)imide (TFSI) electrolyte in 1,3-dioxolane (DOL) solvent at the Li metal electrode, demonstrating that HAIR reproduces the initial reactions of the electrolyte (decomposition of TFSI) previously observed in AIMD simulation while also capturing solvent reactions (DOL) that initiate by ring-opening to form such stable products as CO, CH2O, and C2H4, as observed experimentally. These results demonstrate that the HAIR scheme can significantly increase the time scale for reactive MD simulations while retaining the accuracy of AIMD simulations. This enables a full atomistic description of the formation and evolution of SEI.