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Lithium batteries: Improving solid-electrolyte interphases via underpotential solvent electropolymerization.

ABSTRACT: Understanding the mechanism of formation of solid-electrolyte interphases (SEI) is key to the prospects of lithium metal batteries (LMB). Here, we investigate via cyclic voltammetry, impedance spectroscopy and chronoamperometry the role of kinetics in controlling the properties of the SEI generated from the reduction of propylene carbonate (PC, a typical solvent in LMB). Our observations are consistent with the operation of a radical chain PC electropolymerization into polymer units whose complexity increases at lower initiation rates. As proof-of-concept, we show that slow initiation rates via one-electron PC reduction at underpotentials consistently yields compact, electronically insulating, Li⁺-conducting, PC-impermeable SEI films.

SUBMITTER: Kasmaee LM

PROVIDER: S-EPMC5063536 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Lithium batteries: Improving solid-electrolyte interphases via underpotential solvent electropolymerization.

Kasmaee Laleh Majari LM Aryanfar Asghar A Chikneyan Zarui Z Hoffmann Michael R MR Colussi Agustín J AJ

Chemical physics letters 20160901

Understanding the mechanism of formation of solid-electrolyte interphases (SEI) is key to the prospects of lithium metal batteries (LMB). Here, we investigate via cyclic voltammetry, impedance spectroscopy and chronoamperometry the role of kinetics in controlling the properties of the SEI generated from the reduction of propylene carbonate (PC, a typical solvent in LMB). Our observations are consistent with the operation of a radical chain PC electropolymerization into polymer units whose comple ...[more]

PMID: 27765957

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Project description:The formation of a solid electrolyte interphase (SEI) between the anode surface and the electrolyte of lithium-ion batteries (LIBs) has been considered to be the most important yet the least understood issue of LIBs. To further our understanding in this regard, the density functional theory (DFT) B3PW91/6-311++G(3df,3pd) together with the implicit solvent model and the transition state theory were used for the first time to comprehensively explore the electroreduction mechanism of a novel additive, 4-chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), and a few other solvents and additives, such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), and even ethylene sulfite (ES), for comparison. The one-electron reduction potential of Li+-coordinated compounds Li+(X) for forming decomposition precursors [c-Li+(X˙-)] decreases in the following sequence: CMDO (1.9-2.2 V vs. Li+/Li) ∼ ES(1.9 V) > FEC (0.7 V) > EC (0.47 V) > PC (0.45 V) > DMC (0.38 V); this implies that CMDO is reduced prior to other solvents or additives in the mixture. Although the ring opening of [c-Li+(CMDO˙-)] is the least kinetically favorable, as reflected by the highest energy barrier (E a), i.e., CMDO (18.8-22.9 kcal mol-1) ∼ ES (23.4) > FEC (16.2) > PC (12.5) > EC (11.2) > DMC (8.0), CMDO still shows the highest overall reaction rate constant (∼1053 s-1) for forming an open ring radical [o-Li+(CMDO˙)-]. In addition, the termination reaction of [o-Li+(CMDO˙)-] for forming LiCl is thermodynamically more favorable than that of Li2SO3 or organic disulfite (LiSO3)2-R, which supports the experimental observation that the halogen-containing LiF or LiCl additives are predominant over all other halogen-containing species in the SEI layer. Moreover, the hybrid model by including the second solvation shell of Li+ via a supercluster [(CMDO)Li+(PC)2](PC)9 and the implicit solvent model (SMD) can result in a reduction potential (∼1.7 V) that is in excellent agreement with the experimental reduction peak.

Dataset Information

Lithium batteries: Improving solid-electrolyte interphases via underpotential solvent electropolymerization.

Publications

Lithium batteries: Improving solid-electrolyte interphases via underpotential solvent electropolymerization.

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