Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces

Leung, Kevin; Soto, Fernando; Hankins, Kie; Balbuena, Perla B.; Harrison, Katharine L.

doi:10.1021/acs.jpcc.5b11719

Cited by 151 publications

(159 citation statements)

References 99 publications

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“…60 DFT predictions recently revealed that Li 2 CO 3 and (CH 2 OCO 2 Li) 2 are electrochemically stable but thermodynamically unstable near the equilibrium Li/Li + potential. 61 The C 1s spectra of lithiated graphite (Li x C 6 ) in contact with the various electrolytes containing LiPF 6 , LiTFSI, LiTDI, LiFSI, and LiFTFSI are given in Figure 2a−e. C 1s spectra are complex by nature due to contributions from several components, such as electrolyte residues (i.e., solvents, and salts), SEI products, graphite active material, and carbon additive, all contributing to the carbon peaks.…”

Section: Research Articlementioning

confidence: 99%

In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes

Eshetu

Diemant

Grugeon

et al. 2016

ACS Appl. Mater. Interfaces

182

197

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A comparative and in-depth investigation on the reactivity of various Li-based electrolytes and of the solid electrolyte interface (SEI) formed at graphite electrode is carried out using X-ray photoelectron spectroscopy (XPS), chemical simulation test, and differential scanning calorimetry (DSC). The electrolytes investigated include LiX (X = PF6, TFSI, TDI, FSI, and FTFSI), dissolved in EC-DMC. The reactivity and SEI nature of electrolytes containing the relatively new imide (LiFSI and LiFTFSI) and imidazole (LiTDI) salts are evaluated and compared to those of well-researched LiPF6(-) and LiTFSI-based electrolytes. The thermal reactivity of LixC6 in the various electrolytes is found to be in the order of LiFSI > LiTDI > LiTFSI > LiFTFSI > LiPF6 and LiFSI > LiFTFSI > LiPF6 > LiTFSI > LiTDI in terms of onset exothermic temperature and total heat generated, respectively. Surface and depth-profiling XPS analysis of the SEI formed with the diverse electrolyte formulations provide insight into the differences and similarities (composition, thickness, and evolution, etc.) emanating from the structure of the various salt anions.

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Section: Research Articlementioning

confidence: 99%

In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes

Eshetu

Diemant

Grugeon

et al. 2016

ACS Appl. Mater. Interfaces

182

197

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“…It is known that SEI species are to some degree unstable, especially at low potentials. 41 Therefore, aside from solvent molecules, SEI compounds can be reduced as well, forming new compounds and by-products. Lithium oxide (Li 2 O) has been reported as SEI compound which is mostly found close to the electrode surface.…”

Section: E3134mentioning

confidence: 99%

Revealing SEI Morphology: In-Depth Analysis of a Modeling Approach

Single

Horstmann

Latz

2017

J. Electrochem. Soc.

107

134

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In this article, we present a novel theory for the long term evolution of the solid electrolyte interphase (SEI) in lithium-ion batteries and propose novel validation measurements. Both SEI thickness and morphology are predicted by our model as we take into account two transport mechanisms, i.e., solvent diffusion in the SEI pores and charge transport in the solid SEI phase. We show that a porous SEI is created due to the interplay of these transport mechanisms. Different dual layer SEIs emerge from different electrolyte decomposition reactions. We reveal the behavior of such dual layer structures and discuss its dependence on system parameters. Model analysis enables us to interpret SEI thickness fluctuations and link them to the rate-limiting transport mechanism. Our results are general and independent of specific modeling choices, e.g., for charge transport and reduction reactions. In the near future, automotive and mobile applications demand power storage with large energy and power density. Currently, lithiumion batteries (LIBs) are the technology of choice for devices with these demands. They operate at high cell potentials and offer high specific capacities while providing long lifetimes. The latter is a consequence of the stable chemistry of modern LIB systems. A significant part of this stability can be attributed to the passivation ability of the solid electrolyte interphase (SEI). This thin layer forms between the negative electrode and the electrolyte. Hence contact between these phases is prevented and the continuous reduction of electrolyte molecules is suppressed. These reduction processes occur because the operating potential of the negative electrode lies well below the stability window of the electrolyte.1 They are suppressed because reduction products quickly form the SEI during the first charge of a pristine electrode. The self passivating ability is one of the most important distinctions between a well and a badly performing lithium-ion battery chemistry. It is of such importance because the reduction reactions consume lithium-ions, directly reducing battery capacity. However, a real SEI is not perfectly passivating and electrolyte reduction is never completely suppressed. Consequently, the lifetime of a battery is directly related to the long-term passivating ability of the SEI.Numerous studies on SEI have been conducted since Peled reported on this correlation in 1979.2 Most of these studies are experimental, investigating cycling stability as well as SEI impedance and composition. Theoretical studies are scarce in comparison, despite established methods such as DFT and DFT/MD derivatives. This can be partially explained with the chemical diversity of SEI, which has been investigated by Aurbach et al. for decades. Results are summarized in Refs. 3, 4 and include the study of SEI formation on graphite electrodes in organic solvent mixtures. The most significant finding of this time is that ethylene carbonate (EC) forms a stable SEI on graphite as opposed to propylene carbonate (PC). Another...

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“…Instead, DFT calculations may focus on understanding thermodynamic limits of chemical and electrochemical stability of the CEI components and solid electrolytes. 82,83 Interestingly, some CEI components may be kinetically stable due to large barriers for their decomposition, 82 and such kinetic stabilization may be effectively utilized in the cell designs.…”

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confidence: 99%

In situ surface protection for enhancing stability and performance of conversion-type cathodes

Borodin

Yushin

2017

MRS Energy & Sustainability

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Lithium and lithium-ion batteries (LBs and LIBs) are the most popular battery systems for electrochemical energy storage technologies. Commercial LIBs utilize intercalation-type cathode materials, mostly nickel (Ni)-based and cobalt (Co)-based cathodes, showing specific capacities of up to ∼200 mA h/g (theoretical capacity below 300 mA h/g), which limit the specific energy of batteries, and are additionally expensive and toxic. An EPA study showed that the Ni-and Co-containing batteries that use solvent-based electrode processing have the highest potential for negative environmental impacts. 1 These impacts include resource depletion, global warming, ecological toxicity, and human health impacts with the largest contributing processes include those associated with the production, processing, and use of cobalt and nickel metal compounds, which may cause adverse respiratory, pulmonary, and neurological effects in those exposed. 1 The study suggested cathode material substitution and solvent-less electrode processing to reduce these impacts. 1 The uneven distribution of Co in the earth crust 2 and the insufficient use of suitable personal protection equipment in many Co mining developing countries 3,4 created a major concern. For example, Amnesty International findings of major exploitations of children in Co mines and the related child sickness and deaths 3,4 demonstrate some of the most horrific examples of child labor, which international community should not tolerate and certainly should not encourage through growing market demands for Co. The growing Co contained-electronic waste ABSTRACTThe use of in situ formed protective layer on conversion cathodes was introduced as a cheap and simple strategy to shield these materials from undesirable interactions with liquid electrolytes.Conversion-type cathodes have been viewed as promising candidates to replace Ni-and Co-based intercalation-type cathodes for next-generation lithium (Li) and Li-ion batteries with higher specific energy, lower cost, and potentially longer cycle life. Typically, in conversion reactions two or three Li ions may be stored per just one atom of chalcogen (e.g., S or Se) or transition metal (e.g., Fe or Cu used in halides). Unfortunately, in conversion chemistries the active materials or intermediate charge/discharge products suffer from various unfavorable interactions and dissolution in organic electrolytes. In this mini-review article, we discuss the current interfacial challenges and focus on the protective layers in situ formed on the cathode surface to effectively shield conversion materials from undesirable interactions with liquid electrolytes. We further explore the mechanisms and current progress of forming such protective layers by using various salts, solvents, and additives together with the insight from molecular modeling. Finally, we discuss future opportunities and perspectives of in situ surface protection.Keywords: Li; S; F; coating; energy storage Review DiSCUSSiON POiNTS• Conversion-type cathodes have been viewed as promi...

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Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces

Cited by 151 publications

References 99 publications

In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes

In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes

Revealing SEI Morphology: In-Depth Analysis of a Modeling Approach

In situ surface protection for enhancing stability and performance of conversion-type cathodes

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