Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries

Gomez-Ballesteros, Jose L.; Balbuena, Perla B.

doi:10.1021/acs.jpclett.7b01183

Cited by 14 publications

(12 citation statements)

References 41 publications

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“…Electron transfer to the Li + (EC) complex, which has the minimum binding energy, yields the most stable complexes. Our simulation result agrees with the experimental findings reported earlier [45][46][47].…”

Section: Simulation Resultssupporting

confidence: 92%

Experimental and Modeling Analysis of Holey Graphene Electrodes for High-Power-Density Li-Ion Batteries

Huang

Chen

et al. 2020

Crystals

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The performances of lithium-ion batteries (LIBs) using holey graphene (HGNS) as the anode material are compared with those using non-holey graphene (GNS). The effects of graphene holes on ion transport are analyzed with a combined experiment/modeling approach involving molecular dynamics (MD) simulations. The large aspect ratio of GNS leads to long transport paths for Li ions, and hence a poor rate capability. We demonstrate by both experiments and simulations that the holey structure can effectively improve the rate capability of LIBs by providing shortcuts for Li ion diffusion through the holes in fast charge/discharge processes. The HGNS anode exhibits a high specific capacity of 745 mAh/g at 0.1 A/g (after 80 cycles) and 141 mAh/g at a large current density of 10 A/g, which are higher than the capacity values of the GNS counterpart by 75% and 130%, respectively. MD simulations also reveal the difference in lithium ion transport between GNS and HGNS anodes. The calculations indicate that the HGNS system has a higher diffusion coefficient for lithium ions than the GNS system. In addition, it shows that the holey structure can improve the uniformity and quality of the solid electrolyte interphase (SEI) layer, which is important for Li ion conduction across this layer to access the electrode surface. Moreover, quantum chemistry (QC) computations show that ethylene carbonate (EC), a cyclic carbonate electrolyte with five-membered-ring molecules, has the lowest electron binding energy of 1.32 eV and is the most favorable for lithium-ion transport through the SEI layer. A holey structure facilitates uniform dispersion of EC on graphene sheets and thus enhances the Li ion transport kinetics.

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Section: Simulation Resultssupporting

confidence: 92%

Experimental and Modeling Analysis of Holey Graphene Electrodes for High-Power-Density Li-Ion Batteries

Huang

Chen

et al. 2020

Crystals

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“…Besides oxides, carbonbased and alucone coatings can all be lithiated. 227 Upon lithiation, the electronic, ionic transport and mechanical properties of these coating materials may change accordingly. 225,227 Therefore, the design of SEI chemical compositions should consider its properties after lithiation.…”

Section: In Vitro Design Of the Seimentioning

confidence: 99%

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

et al. 2018

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A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li + transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multiscale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

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“…It is essential to highlight that the electrolyte/electrode interfacial chemistry is unique in different battery systems. For example, the decomposition mechanisms of electrolyte additives on lithium metal anode are not the same as Si or graphite anodes, and an electrolyte additive that works in one cell system may not work in another . Researchers in this field have made remarkable progress in describing electrolyte decompositions and SEI formations.…”

Section: Introductionmentioning

confidence: 99%

“…Researchers in this field have made remarkable progress in describing electrolyte decompositions and SEI formations. Various experimental techniques have been applied to characterize the electrochemical and chemical responses of the SEI. ,,,− Using computational approaches with quantum chemistry accuracy, “watching the SEI form” has been investigated by ab initio molecular dynamics (AIMD) , and density functional theory (DFT). ,− DFT compared to AIMD simulates a smaller system, limited largely to structural relaxation and no dynamics. However, it has significantly higher computational efficiency, thus allowing exploring a much larger variety of electrochemical and chemical feature spaces that are not accessible in AIMD.…”

Section: Introductionmentioning

confidence: 99%

Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries

Zhang

Viswanathan

2020

Langmuir

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Li metal batteries (LMBs) are crucial for electrifying transportation and aviation. Engineering electrolytes to form desired solid-electrolyte interphase (SEI) is one of the most promising approaches to enable stable long-lasting LMBs. Among the liquid electrolytes explored, fluoroethylene carbonate (FEC) has seen great success in leading to desirable SEI properties for enabling stable cycling of LMBs. Given the many facets to desirable SEI properties, numerous descriptors and mechanisms have been proposed. To build a detailed mechanistic understanding, we analyze varying degrees of fluorination of the same prototype molecule, chosen to be ethylene carbonate (EC) to tease out the interfacial reactivity at the Li metal/electrolyte. Using density functional theory (DFT) calculations, we study the effect of mono-, di-, tri-, and tetra-fluorine substitutions of EC on its reactivity with Li surface facets in the presence and absence of Li salt. We find that the formation of LiF at the early stage of SEI formation, posited as a desirable SEI component, depends on the F-abstraction mechanism rather than the number of fluorine substitution. The best illustrations of this are cis- and trans-difluoro ECs, where F-abstraction is spontaneous with the trans case, while the cis case needs to overcome a nonzero energy barrier. Using a Pearson correlation map, we find that the extent of initial chemical decomposition quantified by the associated reaction free energy is linearly correlated with the charge transferred from the Li surface and the number of covalent-like bonds formed at the surface. The effect of salt and the surface facet have a much weaker role in determining the decompositions at the immediate electrolyte/electrode interfaces. Putting all of this together, we find that tetra-FEC could act as a high-performing SEI modifier as it leads to a more homogeneous, denser LiF-containing SEI. Using this methodology, future investigations will explore −CF3 functionalization and other backbone molecules (linear carbonates).

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Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries

Cited by 14 publications

References 41 publications

Experimental and Modeling Analysis of Holey Graphene Electrodes for High-Power-Density Li-Ion Batteries

Experimental and Modeling Analysis of Holey Graphene Electrodes for High-Power-Density Li-Ion Batteries

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries

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