In Situ X-ray Study of the Solid Electrolyte Interphase (SEI) Formation on Graphene as a Model Li-ion Battery Anode

Chattopadhyay, Sudeshna; Lipson, Albert L.; Karmel, Hunter J.; Emery, Jonathan D.; Fister, Timothy T.; Fenter, Paul; Hersam, Mark C.; Bedzyk, Michael J.

doi:10.1021/cm301584r

Cited by 123 publications

(92 citation statements)

References 40 publications

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“…[36][37][38] [18,42] Figure 5c is the S2p XPS spectrum of S-C particles. [41][42][43] Besides the S and N contents are nearly same, and the overwhelming types are nitro and sulfo groups therefore the difference of the property are also mainly derived from them. [39,40] In addition, according to XPS results (Table S3), we notice that the O contents are almost same in N-C and N-S samples, indicating the influence of oxygen-bearing groups in the two samples generated during hot acid treatment can be counteracted.…”

Section: Electrochemical Measurementsmentioning

confidence: 99%

Experimental and theoretical investigations of nitro-group doped porous carbon as a high performance lithium-ion battery anode

et al. 2015

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Doping is an effective solution to improve the capacity of carbon based anode material such as introducing nitrogen, boron, sulfur, phosphorus heteroatom into the graphite lattice. However, most of the previous doping methods are confined in the crystal lattice, edge doping is rarely studied. Here, using first-principle quantum chemical calculations, we studied lithium adsorption ability of various functional groups(NH2, NO2, SO3H, Cl, Br, I, OH, P) which were doped at the edge of graphene sheet. Among all the groups, nitro-group shows the best lithium adsorption property. On the basis of theoretical predictions, we successfully synthesized nitro group edge modified porous carbon through the pyrolysis of Cubased metal organic frameworks (MOFs) at 600℃ under nitrogen atmosphere and post acid treatment. As an anode material for lithium ion batteries, it retains a capacity of 588 mA/g after 1500 cycles at a high current density of 1 A/g. The lithium anodic performance of nitro-group doped carbon is superior to other edge doped carbon based materials reported in literatures such as halogen, sulfur and phosphorus. The excellent cycling performance at high current densities is ascribed to the improved lithium adsorption ability of the nitro-group doped at the edge of carbon. Figure 3. Images of N-C octahedral particles by electron microscopy. (a) FESEM and (b) TEM images of the N-C material. (c) HRTEM image of the MOF-derived mesoporous N-C polyhedrons. (d) Selected-area electron diffraction pattern of the N-C octahedron. (e-h) Scanning TEM image of the N-C octahedron and energy dispersive X-ray spectrometry elemental maps of C and N, O, repectively.

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Section: Electrochemical Measurementsmentioning

confidence: 99%

Experimental and theoretical investigations of nitro-group doped porous carbon as a high performance lithium-ion battery anode

et al. 2015

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“…[5,6] While, a stable and robust SEI film can effectively inhibit the lithium dendrite growth and thus prominently enhance the cycling performance and safety of the batteries. Various in situ techniques, for instances, in situ spectroscopic ellipsometry, [9] in situ nuclear magnetic resonance (NMR), [10] in situ X-ray diffraction, [11] in situ Fourier transform infrared (FTIR) spectroscopy, [12] and in situ electrochemical impedance spectroscopy, [13] have been employed to investigate the evolution of SEI films. [1,8] Although the importance of SEI has been widely recognized, the structure and kinetics of SEI are the less wellunderstood phenomena impacting battery technology.…”

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confidence: 99%

Operando Observations of SEI Film Evolution by Mass‐Sensitive Scanning Transmission Electron Microscopy

Hou

Han

Chen

et al. 2019

Advanced Energy Materials

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SEI films directly affect the dissolution and deposition of lithium during discharge and charge and thus are one of the key factors that determine the safety, power capability, morphology of lithium deposits, shelf life, and cycle life of LIBs. In particular, the breakdown of SEI can result in the nucleation and growth of lithium dendrites and cause the safety risk for the practical applications of LIBs in the electric vehicles and other high-energy-density electronic devices. [5,6] While, a stable and robust SEI film can effectively inhibit the lithium dendrite growth and thus prominently enhance the cycling performance and safety of the batteries. [1,7] Owing to directly growing on anode surfaces, the formation and stability of SEI films are greatly influenced by the volume variation of anodes during the charge-discharge cycling, especially at a high current density. [1,8] Although the importance of SEI has been widely recognized, the structure and kinetics of SEI are the less wellunderstood phenomena impacting battery technology. Various in situ techniques, for instances, in situ spectroscopic ellipsometry, [9] in situ nuclear magnetic resonance (NMR), [10] in situ X-ray diffraction, [11] in situ Fourier transform infrared (FTIR) spectroscopy, [12] and in situ electrochemical impedance spectroscopy, [13] have been employed to investigate the evolution of SEI films. Nevertheless, most of them are limited to the nonintuitive investigations. Several key questions on the SEI film formation, structure and failure are still elusive.Recently, in situ transmission electron microscopy (TEM) has been utilized as a power tool to explore the evolution of SEI films in LIBs. In particular, a liquid cell TEM technique can well mimic the chemical and electrochemical reactions in liquid media with controllable charge and discharge conditions of LIBs. Sacci et al. performed the first in situ TEM observations of SEI film formation on a gold electrode during cyclic voltammetry testing. [14] They found that SEI films form heterogeneously on the gold electrode and possess dendritic morphology. The formation and growth of SEI films on graphite/electrolyte interfaces were studied by Unocic et al. using in situ TEM. [15] By utilizing the liquid cell TEM, Zeng et al. monitored the structural evolution of SEI films in a cyclic voltammetry process and found that the growth of SEI films is limited by the electron transport and produces gaseous The solid electrolyte interphase (SEI) spontaneously formed on anode surfaces as a passivation layer plays a critical role in the lithium dissolution and deposition upon discharge/charge in lithium ion batteries and lithiummetal batteries. The formation kinetics and failure of the SEI films are the key factors determining the safety, power capability, and cycle life of lithium ion and lithium-metal batteries. Since SEI films evolve with the volumetric and interfacial changes of anodes, it is technically challenging in experimental study of SEI kinetics. Here operando observations are reported of SEI...

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“…The most important but still not well understood aging phenomenon is the growth of a solid film at graphite negative electrodes. [1][2][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.…”

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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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In Situ X-ray Study of the Solid Electrolyte Interphase (SEI) Formation on Graphene as a Model Li-ion Battery Anode

Cited by 123 publications

References 40 publications

Experimental and theoretical investigations of nitro-group doped porous carbon as a high performance lithium-ion battery anode

Experimental and theoretical investigations of nitro-group doped porous carbon as a high performance lithium-ion battery anode

Operando Observations of SEI Film Evolution by Mass‐Sensitive Scanning Transmission Electron Microscopy

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

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