Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase

Shi, Siqi; Lü, Peng; Liu, Zhongyi; Qi, Yue; Hector, Louis G.; Li, Hong; Harris, Stephen J.

doi:10.1021/ja305366r

Cited by 539 publications

(546 citation statements)

References 54 publications

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“…Finally, one may conclude that the AEI likely consists of Li 2 CO 3 domains in a complex amorphous organic matrix, which is similar to those reported for graphite anode materials [44][45][46][47] .…”

Section: Morphology and Electronic Structure Of Nio Nanosheetssupporting

confidence: 80%

“…Firstly, the chemical environment of AEI at the surface of NiO nanosheets is determined to be Li 2 CO 3 nanoscale domains imbedded in an amorphous organic matrix and its thickness exhibits dependence on the SOC. The chemical environment of AEI on NiO nanosheets is similar to that at the surface of graphite anode materials 44,46,47 . Therefore, these observations represent a step towards leveraging AEI on transition metal oxide materials with the conventional concept of solid-electrolyte interphase on graphite materials 28,45 .…”

Section: Discussionmentioning

confidence: 85%

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Phase evolution for conversion reaction electrodes in lithium-ion batteries

et al. 2014

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The performance of battery materials is largely governed by structural and chemical evolutions during electrochemical reactions. Therefore, resolving spatially dependent reaction pathways could enlighten mechanistic understanding, and enable rational design for rechargeable battery materials. Here, we present a phase evolution panorama via spectroscopic and three-dimensional imaging at multiple states of charge for an anode material (that is, nickel oxide nanosheets) in lithium-ion batteries. We reconstruct the threedimensional lithiation/delithiation fronts and find that, in a fully electrolyte immersion environment, phase conversion can nucleate from spatially distant locations on the same slab of material. In addition, the architecture of a lithiated nickel oxide is a bent porous metallic framework. Furthermore, anode-electrolyte interphase is found to be dynamically evolving upon charging and discharging. The present study has implications for resolving the inhomogeneity of the general electrochemically driven phase transition (for example, intercalation reactions) and for the origin of inhomogeneous charge distribution in large-format battery electrodes.

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Section: Morphology and Electronic Structure Of Nio Nanosheetssupporting

confidence: 80%

Section: Discussionmentioning

confidence: 85%

Phase evolution for conversion reaction electrodes in lithium-ion batteries

et al. 2014

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“…We assume that intermediate As can be seen in Figure 3, net reactions considered in the continuum model are direct pathways from the reactants EC, Li + , and e − to the products C 2 H 4 , LC, LEDC, and the desorbed intermediate species Solid components.-The assumed solid products are LC and LEDC, which have been reported as being the main SEI film components. 6,7,12,31,35,36 LC is reported to be the most important component for SEI functionality 13,37 and formed with ECbased electrolytes. 7 A two-layer structure of the SEI is commonly reported, 13,38 with a dense inner film and a porous outer film.…”

Section: Mathematical Modelingmentioning

confidence: 99%

“…DFT has been applied to determine energy barriers and standard state potentials 12 and transport processes in the solid film. 13,14 Methekar et al 15 proposed the application of kMC to simulate heterogeneous passivation of the interface. Several macroscopic electrode models are available based on PDEs to simulate film growth and resistance 16,17 and for detailed analysis of transport processes and reactions in the SEI.…”

mentioning

confidence: 99%

Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion Batteries

Röder

Braatz

Krewer

2017

J. Electrochem. Soc.

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A quantitative description of the formation process of the solid electrolyte interface (SEI) on graphite electrodes requires the description of heterogeneous surface film growth mechanisms and continuum models. This article presents such an approach, which uses multi-scale modeling techniques to investigate multi-scale effects of the surface film growth. The model dynamically couples a macroscopic battery model with a kinetic Monte Carlo algorithm. The latter allows the study of atomistic surface reactions and heterogeneous surface film growth. The capability of this model is illustrated on an example using the common ethylene carbonatebased electrolyte in contact with a graphite electrode that features different particle radii. In this model, the atomistic configuration of the surface film structure impacts reactivity of the surface and thus the macroscopic reaction balances. The macroscopic properties impact surface current densities and overpotentials and thus surface film growth. The potential slope and charge consumption in graphite electrodes during the formation process qualitatively agrees with reported experimental results. A long lifetime for lithium-ion batteries is key to reducing battery cost and increasing acceptance for new applications. The most important but still not well understood aging phenomenon is the growth of a solid film at graphite negative electrodes.1-3 Graphite is the common negative electrode and operates at conditions outside the electrochemical stability window of the electrolyte.2,4 Its decomposition takes place at the surface of the electrode particles and leads to the formation of a surface film, i.e. solid electrolyte interface (SEI). The SEI is mainly built during the first cycles prior to use and is considered to be part of the manufacturing process. 5 The aim of the formation process is to create an interface that is a good lithium-ion conductor but insulating for electrons and prohibits direct contact between electrode and electrolyte in order to provide good performance and long lifetime.4 Different compositions of the film have been proposed by different research groups. 6,7 Since the composition and structure and so the film characteristic is determined during the first cycles, 7 a detailed understanding of this growth mechanism is needed to improve cycling performance.The SEI is formed by a complex mechanism. 5 An atomistic reaction mechanism involves lithium salt and solvent as reactants as well as a variety of different organic and inorganic intermediates and solid products. 7,8 The observation of the formation process is challenging, because of the film's thickness of only several nanometers. Additionally, macroscopic properties such as particle size or operating conditions, e.g. C-rate and environmental temperature, have an important impact on the formation process.3,4 Although SEI film formation has been studied for decades using experimental and simulation-based methods, the exact mechanism of chemical and electrochemical reactions and the growth of the solid fi...

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“…A new Li knock-off mechanism, rather than isolated vacancy hopping, is proposed for Li 2 CO 3 , which accounts for the fast Li diffusion in this material. 153 By incorporating the atomistic diffusivity in mesoscale diffusion equations, good agreement was achieved with experiments. The diffusion barrier and formation energy of various defects in LiF at different potentials have also been investigated using NEB and other computational methods.…”

Section: Silicon and Other Anodesmentioning

confidence: 80%

Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

Deng

Ong

2016

NPG Asia Mater

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The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. The scope of this review includes the monovalent lithium-and sodium-ion chemistries that are currently of the most commercial interest. NPG Asia Materials (2016) 8, e254; doi:10.1038/am.2016.7; published online 25 March 2016 INTRODUCTIONThe facile conduction of alkali ions in a crystal is of critical importance in energy storage. Today, the dominant form of energy storage in consumer electronics is the rechargeable lithium-ion (Li-ion) battery, 1-5 a device that functions entirely on the basis of the reversible transport of Li + ions. With one of the highest energy densities of known energy storage technologies, Li-ion batteries are finding increasingly large-scale applications in electrified transportation and grid storage. In recent years, there has also been a resurgence of interest in rechargeable sodium-ion (Na-ion) batteries, 6-12 which function on the same basic principle but with Na + instead of Li + because of concerns regarding the abundance and cost of lithium. Figure 1 shows a representation of a rechargeable alkali-ion battery. The typical electrode in an alkali-ion battery is an intercalation compound, which, as the name implies, stores alkali ions by inserting them into its crystal structure in a topotactic manner. During discharge, A + ions are transported from the anode, through the electrolyte and into the cathode. The reverse happens during charge. Throughout this review, we will adopt the customary terminology of defining the 'cathode' as the positive electrode during discharge, even though the formal definition of the cathode changes depending on whether the charging or discharging process is being referred to. Current cathodes are typically transition metal oxides, and the insertion/removal of each A + in the cathode is accompanied by the concomitant reduction/oxidation of a transition metal ion to accommodate the compensating insertion/removal of an electron. Graphitic carbon is the most common anode.The performance of a rechargeable alkali-ion battery depends crucially on the ease with which alkali ions move in the host crystal of the cathode and anode, in the electrolyte, and in the electrodeelectrolyte interface. Poor alkali transport in any part of the battery

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Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase

Cited by 539 publications

References 54 publications

Phase evolution for conversion reaction electrodes in lithium-ion batteries

Phase evolution for conversion reaction electrodes in lithium-ion batteries

Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion Batteries

Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

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