Insight on lithium metal anode interphasial chemistry: Reduction mechanism of cyclic ether solvent and SEI film formation

Liu, Qi; Cresce, Arthur v.; Schroeder, Marshall A.; Xu, Kang; Mu, Daobin; Wu, Borong; Shi, Libo; Wu, Feng

doi:10.1016/j.ensm.2018.09.024

Cited by 113 publications

(94 citation statements)

References 54 publications

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“…The XPS spectra of C 1s also supported a reversible intercalation/deintercalation of Ca‐G 4 . While the peak intensity at 290.0 eV was negligible in discharged graphite, a charged sample showed an intense peak that was believed to be due to the ethereal carbon of G 4 . It is worth mentioning here that the XPS spectrum of discharged graphite that was cycled in Ca(TFSI) 2 /G 2 showed an intense calcium peak, in contrast to that cycled in Ca(TFSI) 2 /G 4 , due to Ca 2+ ‐entrapment (Figure S6, Supporting Information).…”

Section: Resultsmentioning

confidence: 92%

Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

et al. 2019

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Herein, graphite is proposed as a reliable Ca2+‐intercalation anode in tetraglyme (G4). When charged (reduced), graphite accommodates solvated Ca2+‐ions (Ca‐G4) and delivers a reversible capacity of 62 mAh g−1 that signifies the formation of a ternary intercalation compound, Ca‐G4·C72. Mass/volume changes during Ca‐G4 intercalation and the evolution of in operando X‐ray diffraction studies both suggest that Ca‐G4 intercalation results in the formation of an intermediate phase between stage‐III and stage‐II with a gallery height of 11.41 Å. Density functional theory calculations also reveal that the most stable conformation of Ca‐G4 has a planar structure with Ca2+ surrounded by G4, which eventually forms a double stack that aligns with graphene layers after intercalation. Despite large dimensional changes during charge/discharge (C/D), both rate performance and cyclic stability are excellent. Graphite retains a substantial capacity at high C/D rates (e.g., 47 mAh g−1 at 1.0 A g−1 s vs 62 mAh g−1 at 0.05 A g−1) and shows no capacity decay during as many as 2000 C/D cycles. As the first Ca2+‐shuttling calcium‐ion batteries with a graphite anode, a full‐cell is constructed by coupling with an organic cathode and its electrochemical performance is presented.

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Section: Resultsmentioning

confidence: 92%

Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

et al. 2019

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“…Wu's group employed both computational (DFT) and experimental (in-depth XPS) means to investigate the reduction chemistry of DME and DOL on the surface of Li metal anode. [59] It is determined that ether-based SEIs are layer-structured, with an outer organic/polymeric layer consisting of ROLi-(CH 3 OLi) (originated from reduction of DME), CH 3 CH 2 OCH 2 OLi and HCO 2 Li (originated from reduction of DOL) and an inner layer of a simple inorganic oxide (Li 2 O). Liu et al utilized the quantitative and in situ electrochemical quartz crystal microbalance (EQCM) coupled with the atomically precise AFM to study the SEI formation process of graphitic electrode (electrolyte: 1.0 m LiPF 6 dissolved in 1:1 EC/ DMC).…”

Section: Component Analysismentioning

confidence: 99%

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

Zhai

Liu

et al. 2020

Advanced Energy Materials

288

194

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Interfacial chemistry between lithium metal anodes and electrolytes plays a vital role in regulating the Li plating/stripping behavior and improving the cycling performance of Li metal batteries. Constructing a stable solid electrolyte interphase (SEI) on Li metal anodes is now understood to be a requirement for progress in achieving feasible Li‐metal batteries. Recently, the application of novel analytical tools has led to a clearer understanding of composition and the fine structure of the SEI. This further promoted the development of interface engineering for stable Li metal anodes. In this review, the SEI formation mechanism, conceptual models, and the nature of the SEI are briefly summarized. Recent progress in probing the atomic structure of the SEI and elucidating the fundamental effect of interfacial stability on battery performance are emphasized. Multiple factors including current density, mechanical strength, operating temperature, and structure/composition homogeneity that affect the interfacial properties are comprehensively discussed. Moreover, strategies for designing stable Li‐metal/electrolyte interfaces are also reviewed. Finally, new insights and future directions associated with Li‐metal anode interfaces are proposed to inspire more revolutionary solutions toward commercialization of Li metal batteries.

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“…The electrolyte used in these symmetric cells is commercial carbonate based electrolyte with 10 wt% FEC as additive which is more incompatible to metallic Li compared with ether‐based electrolyte. [ 43 ] Under the harsh electrolyte environment, the LSNP‐Li electrode exhibits a stable cycling for 500 cycles without short circuit at 1.0 mA cm −2 /1.0 mAh cm −2 ( Figure a). However, the bare Li electrode can only sustain less than 100 cycles (about 75 cycles).…”

Section: Resultsmentioning

confidence: 99%

A Facile Way to Construct Stable and Ionic Conductive Lithium Sulfide Nanoparticles Composed Solid Electrolyte Interphase on Li Metal Anode

Cui

Liu

Wang

et al. 2020

Adv Funct Materials

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Due to the high theoretical capacity and low reduction potential, metallic lithium is a promising anode material for the next generation of high-energydensity batteries. However, the dynamic Li plating/stripping process can easily destroy the unstable solid electrolyte interphase (SEI) and cause dendrite growth. Here, an artificial lithium sulfide nanoparticle composed SEI layer with superior stability and high ionic conductivity is designed by a spray quenching method. The artificial SEI layer on Li surface can effectively minimize the side reactions and suppress Li dendrite growth, and the metal electrode delivers stable cycling for 500 cycles in the symmetrical cell with carbonate electrolyte. Moreover, when this SEI-modified Li anode is coupled with a LiFePO 4 cathode, the full cell shows promoted cycling stability and rate capability. This work provides a broadly applicable and facile strategy to address the intrinsic issues of lithium metal anodes.

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Insight on lithium metal anode interphasial chemistry: Reduction mechanism of cyclic ether solvent and SEI film formation

Cited by 113 publications

References 54 publications

Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

A Facile Way to Construct Stable and Ionic Conductive Lithium Sulfide Nanoparticles Composed Solid Electrolyte Interphase on Li Metal Anode

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Insight on lithium metal anode interphasial chemistry: Reduction mechanism of cyclic ether solvent and SEI film formation

Cited by 113 publications

References 54 publications

Graphite as a Long‐Life Ca2+‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

Graphite as a Long‐Life Ca2+‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

A Facile Way to Construct Stable and Ionic Conductive Lithium Sulfide Nanoparticles Composed Solid Electrolyte Interphase on Li Metal Anode

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Product

Resources

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Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries

Graphite as a Long‐Life Ca²⁺‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries