<i>In situ</i> formation of circular and branched oligomers in a localized high concentration electrolyte at the lithium-metal solid electrolyte interphase: a hybrid <i>ab initio</i> and reactive molecular dynamics study

Liu, Yue; Sun, Qingzhu; Yu, Peiping; Ma, Biao; Yang, Hao; Zhang, Jiayi; Xie, Miao; Cheng, Tao

doi:10.1039/d1ta08182a

Cited by 18 publications

(10 citation statements)

References 53 publications

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“…At the same time, fundamental acceleration algorithms or models are supposed to be investigated due to the great complexity of battery electrolyte systems. For instance, a pioneering combination of AIMD and CMD based on ReaxFF, namely the hybrid ab initio and reactive molecular dynamics (HAIR), has been recently developed by Cheng and co-workers to simulate the decomposition mechanisms of electrolyte species and the subsequent formation of an SEI. ,− The calculation can be sped up 10 times compared with conventional AIMD simulations. The modeling of bulk/interfacial structures and interfacial reactions . Interfacial structures and reactions are directly related to the formation of the SEI and CEI, the (de)solvation of working ions, and the intercalation, deposition, or conversion of working ions, which codetermine the performance and lifetime of rechargeable batteries.…”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries

et al. 2022

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Rechargeable batteries have become indispensable implements in our daily life and are considered a promising technology to construct sustainable energy systems in the future. The liquid electrolyte is one of the most important parts of a battery and is extremely critical in stabilizing the electrode–electrolyte interfaces and constructing safe and long-life-span batteries. Tremendous efforts have been devoted to developing new electrolyte solvents, salts, additives, and recipes, where molecular dynamics (MD) simulations play an increasingly important role in exploring electrolyte structures, physicochemical properties such as ionic conductivity, and interfacial reaction mechanisms. This review affords an overview of applying MD simulations in the study of liquid electrolytes for rechargeable batteries. First, the fundamentals and recent theoretical progress in three-class MD simulations are summarized, including classical, ab initio, and machine-learning MD simulations (section 2). Next, the application of MD simulations to the exploration of liquid electrolytes, including probing bulk and interfacial structures (section 3), deriving macroscopic properties such as ionic conductivity and dielectric constant of electrolytes (section 4), and revealing the electrode–electrolyte interfacial reaction mechanisms (section 5), are sequentially presented. Finally, a general conclusion and an insightful perspective on current challenges and future directions in applying MD simulations to liquid electrolytes are provided. Machine-learning technologies are highlighted to figure out these challenging issues facing MD simulations and electrolyte research and promote the rational design of advanced electrolytes for next-generation rechargeable batteries.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries

et al. 2022

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“…The successful hybrid method has been verified, and the LiTFSI‐related ReaxFF parameters have been developed in our previous work. [ 38–41 ] In this work, LiTFSI with EC solvents are used to clarify the reduction mechanism, formation process, and main components of the SEI layer. Further investigation is conducted with different LiTFSI concentrations to achieve the controlled SEI layer formation process along with radial distribution function (RDF), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS) analysis method.…”

Section: Introductionmentioning

confidence: 99%

Formation of Linear Oligomers in Solid Electrolyte Interphase via Two‐Electron Reduction of Ethylene Carbonate

Liu

Sun

et al. 2022

Advcd Theory and Sims

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Solid electrolyte interphase (SEI) plays a significant role in enhancing the stability and durability of lithium metal batteries (LMBs) by separating highly reactive lithium metal anode (LMA) from the electrolyte to avoid continuous degradation. However, the underlying reaction mechanism is still far from clear. Herein, a hybrid ab initio and reactive force field (HAIR) method is employed to extend the ab initio molecular dynamics (AIMD) to 1 ns, which provides crystal information about the reaction mechanism of elementary reactions that can explain the components and morphology evolution of SEI formation. Specifically, HAIR simulation confirms the two‐electron (2e–) reduction of ethylene carbonate (EC) by releasing CO and CO2, agreeing with phenomenal experiment observation. As the unsaturated intermediates accumulate, polymerization reactions occur, producing linear polyethylene oxide (PEO), Li2OCO2CH2CH2, Li2OCO2(CH2)4, etc., which regulate the formation of outer organic layer (OOL) that consists of linear polyethylene oxide (PEO), Li2OCO2CH2CH2, Li2OCO2(CH2)4, etc., and the inner inorganic layer (IIL) mainly consists of LiF and Li2O. Simulations at low concentration (LC, 1M) and high concentration (HC, 5M) reveal significantly different reaction pathways when HC electrolyte can significantly promote the formation of homogenous LiF that has been regarded as an important component to facilitate robust SEI.

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“…The SEI consisting of organic oligomers and inorganic LiF exhibits outstanding Li + ion transport/ transfer, electronic insulation, and mechanical properties. 48,49 The LFP cathode cycled 200 times is also investigated by XPS as shown in Fig. S5.…”

Section: Resultsmentioning

confidence: 99%

“…The SEI consisting of organic oligomers and inorganic LiF exhibits outstanding Li + ion transport/transfer, electronic insulation, and mechanical properties. 48,49…”

Section: Resultsmentioning

confidence: 99%

New nonflammable tributyl phosphate based localized high concentration electrolytes for lithium metal batteries

Feng

Zhang

et al. 2022

Sustainable Energy Fuels

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In situ formation of circular and branched oligomers in a localized high concentration electrolyte at the lithium-metal solid electrolyte interphase: a hybrid ab initio and reactive molecular dynamics study

Abstract: Developing advanced electrolytes has been considered as a promising approach to stabilize lithium (Li) metal anode via the formation of stable solid electrolyte interphase (SEI) that can protect Li anode...

Cited by 18 publications

References 53 publications

Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries

Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries

Formation of Linear Oligomers in Solid Electrolyte Interphase via Two‐Electron Reduction of Ethylene Carbonate

New nonflammable tributyl phosphate based localized high concentration electrolytes for lithium metal batteries

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