Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

Shadike, Zulipiya; Lee, Hongkyung; Borodin, Oleg; Cao, Xia; Fan, Xiulin; Wang, Xuelong; Lin, Ruoqian; Bak, Seong‐Min; Ghose, Sanjit; Xu, Kang; Wang, Chunsheng; Li, Jun; Xiao, Jie; Yang, Xiao‐Qing; Hu, Enyuan

doi:10.1038/s41565-020-00845-5

Cited by 190 publications

(144 citation statements)

References 40 publications

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“…S16), but its formation still increases with cycling, which brings uncertainties in quantifying dead Li metal. Because the lithium in LiH is in the ionic state, we ascribe it to the SEI species, similar to recent few reports on this topic ( 17 , 18 ). We believe the unambiguous identification of LiH implies important battery chemistry behind and needs further detailed study.…”

Section: Resultssupporting

confidence: 75%

“…Another possible source for such gap is the presence of LiH, which has been first proposed by Aurbach et al ( 14 ), and then was observed at the surface of Li metal during plating by Kourkoutis and co-workers ( 15 ) using electron energy loss spectroscopy. Recently, the presence of LiH in inactive Li was further confirmed by both mass spectrometer titration ( 16 , 17 ) and synchrotron XRD ( 18 ) techniques. However, the influence of LiH on the accuracy of single TGC technique when quantifying dead lithium has not been compared and discussed yet, which is critical for evaluating the accuracy and applicability of a quantitatively analytical technique.…”

Section: Resultsmentioning

confidence: 94%

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Quantitatively analyzing the failure processes of rechargeable Li metal batteries

et al. 2021

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 94%

Quantitatively analyzing the failure processes of rechargeable Li metal batteries

et al. 2021

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“…Experimentally, LiH was first characterized by IR spectroscopy on Li metal with wet electrolyte solutions, 76 and later observed as a main dendritic product in the Li-anode-SEI by cryo-STEM mapping 15 and XRD experiments. 77 Examining this hypothetical path more carefully, we obtain a mechanism that resembles the black path in Figure 4 (a). Note that the overall charge state for the structures in the energy profile in Figure 4 (a) is neutral, whereas in Figure 4 (b), the overall charge is -1.…”

Section: Resultsmentioning

confidence: 99%

Data-Driven Prediction of Formation Mechanisms of Lithium Ethylene Monocarbonate with an Automated Reaction Network

Xie¹,

Spotte-Smith²,

Patel³

et al. 2021

Preprint

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<div><div><div><p>Interfacial reactions are notoriously difficult to characterize and robust prediction of the chemical evolution and associated functionality of the resulting surface film is one of the grand challenges of materials chemistry. The solid–electrolyte interphase (SEI), critical to the operation of Li-ion batteries (LIB), exemplifies such a surface film and despite decades of work, considerable controversy remains regarding the major components of the SEI as well as their formation mechanisms. In this work, we present pioneering results of a newly developed data-driven reaction network addressing the recent question whether lithium ethylene monocarbonate (LEMC) or lithium ethylene dicarbonate (LEDC) is the major organic component of the LIB SEI. Our data-driven, automated methodology is based on a systematic generation of relevant species using a general fragmentation/recombination procedure which provides the basis for our vast thermodynamic reaction landscape, calculated with density functional theory (DFT). The graph implementation of the reaction landscape is subsequently explored using shortest pathfinding algorithms, identifying reactions to LEMC from EC, Li+ and H2O under the electron chemical potential of Li metal. Confirming the viability of our approach, the reaction network automatically recovers previously-proposed formation mechanisms of LEMC from EC and LEDC through hydrolysis, among which the direct hydrolysis of EC under basic conditions is found to be the most kinetically favorable. We also identify several other new reaction pathways to LEMC, illustrating the complex and competitive landscape of possible electrochemical electrolyte decomposition reactions. For example, we recover a LEMC formation mechanism that generates lithium hydride as a by-product and a radical mechanism through breaking the (CH2)O–C(–O)OLi bond in LEDC, neither of which has been proposed previously. Most importantly, we find that all identified paths, which are also kinetically favorable under the explored conditions, require water as a reactant. This condition severely limits the amount of LEMC that can form, as compared to LEDC, a conclusion that has direct impact on our understanding of SEI formation in Li-ion energy storage systems. Finally, we emphasize that our framework demonstrates robust, automated, data-driven predictions of novel interfacial reaction mechanisms and this framework is generally applicable to other reactive systems.</p></div></div></div>

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“…with partial soluble degraded carbonates (alkoxides, semicarbonates, and nonconducting polymers) in the light of spectral analysis. [ 43–46 ]…”

Section: The Fundamental Understanding Of Seimentioning

confidence: 99%

The Functions and Applications of Fluorinated Interface Engineering in Li‐Based Secondary Batteries

Guo

et al. 2021

Small Science

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Past few years have witnessed great progress in energy storage technology and material characterization methods, which stimulated the development of novel energy storage devices suitable for largescale industrial applications. [1][2][3][4] Among all the energy conversion avenues, electrochemical means have the advantages of environmental benignity, high transforming efficiency, and long lifespan, which are expected to overcome the intrinsic shortcomings of directly unavailable renewable energy sources such as wind power, tidal power, and solar energy, whose defects often lie in distribution inhomogeneity and space-time limitations across the world. [5] So, a large variety of electrochemical energy storage devices emerges as urgently demanded in reality during the past two centuries to meet different requirements in social production and residential lives. Particularly, secondary battery technology, also called rechargeable battery, is a reliable type of electrochemical system with ability to charge and discharge repeatedly taking advantage of reversible chemical reactions. [6,7] In contrast to primary battery first designed by Alessandro Volta in 1799, rechargeable battery systems such as nickel-metal hydride batteries, [8] nickel-cadmium batteries, [9] lead-acid batteries, [10] lithium-ion batteries (LIB), and polymer LIBs [11] have huge potential to apply in portable electronic devices, electric vehicles (EV), implantable medical equipments, and static smart power grid due to their distinct advantages of durability, energy density, and cost performance. Accordingly, many of these have achieved great success in market during the past few decades. Specially, LIB, served as a milestone in electrochemical energy storage technology history for humankind and first commercialized by Sony in 1991 with a configuration of cobalt oxide cathodes and graphite anodes, [12] has been widely deployed in 3C (Computer, Communication, Consumer electronics products) fields to revolutionize our modern life so far.As shown in Figure 1, the working mechanism of LIBs usually follows a typical "rocking chair" style, which is featured by the reversible charge-carrier (alkali metal ion) separation and recombination at the electrode/electrolyte interface in host materials including cathodes and anodes. [7] To be specific, when exerted

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Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

Cited by 190 publications

References 40 publications

Quantitatively analyzing the failure processes of rechargeable Li metal batteries

Quantitatively analyzing the failure processes of rechargeable Li metal batteries

Data-Driven Prediction of Formation Mechanisms of Lithium Ethylene Monocarbonate with an Automated Reaction Network

The Functions and Applications of Fluorinated Interface Engineering in Li‐Based Secondary Batteries

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