Electrochemical Reactivity and Passivation of Silicon Thin-Film Electrodes in Organic Carbonate Electrolytes

Hasa, Ivana; Haregewoin, Abebe; Zhang, Liang; Tsai, Wan‐Yu; Guo, Jinghua; Veith, Gabriel M.; Ross, Philip N.; Kostecki, Robert

doi:10.1021/acsami.0c09384

Cited by 59 publications

(83 citation statements)

References 74 publications

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“…The thin and largely inorganic SEI formed on a-AlSiMn differs substantially from the thicker and more organic SEI typically formed on Si electrodes in comparable electrolytes (33,37). A comparison of XPS data collected on a-AlMnSi and 50 nm amorphous Si thin films that were galvanostatically lithiated in the same electrolyte is given in Fig.…”

Section: Sei Compositionmentioning

confidence: 95%

“…Aluminum and copper were purchased as foils from Alfa Aesar and used without further preparation. Amorphous silicon electrodes were prepared by sputtering a 50 nm film onto Cu foil as described elsewhere (33). The as-prepared Si thin films exhibited a 3 nm native SiO 2 surface layer, and a density of 2.1 g/cm 3 (33) .…”

Section: Electrochemical Cell Assembly and Testingmentioning

confidence: 99%

“…It has been proposed that LiEDC is responsible (33) for the "breathing" effect often observed in Si anodes (43,51,52), when the SEI thickens with each lithiation and becomes thinner with each delithiation, leading to an inherent SEI instability. The absence of unstable LiEDC on a-AlSiMn may arise either from a lack of EC or EMC reduction on a-AlSiMn electrodes -perhaps because a surface oxide together with LiPF 6 decomposition products, which form earlier, has already passivated the electrode (43,45) -or from the formation of EC or EMC reduction products that do not attach to the a-AlSiMn electrode and thus do not become part of the SEI.…”

Section: Sei Compositionmentioning

confidence: 99%

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Stable SEI Formation on Al-Si-Mn Metallic Glass Li-Ion Anode

Schnabel¹,

Lin²,

Arca³

et al. 2021

Meet. Abstr.

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Alloying anodes such as silicon are of great interest for lithium-ion batteries due to their high lithium-ion storage capacities, but have only seen minimal commercial deployment due to their limited calendar life. This has been attributed to an intrinsically unstable solid electrolyte interphase (SEI) that is aggravated by mechanical failure. An amorphous structure can mitigate lithiation strains, and amorphous alloys, or metallic glasses, often exhibit exceptional fracture toughness. Additional elements can be added to metallic glasses to improve passivation. Splat quenching was utilized to prepare an amorphous Al 64 Si 25 Mn 11 Li-ion anode with a specific capacity >900 mAh/g that remains amorphous upon cycling. On this metallic glass electrode, parasitic electrolyte reduction is found to be much reduced in comparison to pure Si or Al, and comparable to that on Cu. The SEI is much thinner, more stable, and richer in fluorinated inorganic phases than the SEI formed on Si, while organic carbonate compounds such as lithium ethylene decarbonate (LiEDC) are notably absent. This study indicates that metallic glasses can become a viable new class of Li-ion anode materials with improved surface passivity. This work explores LIB anodes consisting of splat-quenched Si-based metallic glasses(17-19). These maintain Si, which can alloy with up to 3.75 Li(13,19), as the main Li-binding element, but distribute it homogeneously within an amorphous matrix. Alloying elements can be selected to maintain the amorphous structure, store more Li, or improve SEI stability. An additional consideration is that new LIB anode materials ought to have a viable large-scale synthesis route. Scalable manufacturing of amorphous alloys requires rapid solidification from the melt. Two common methods are melt spinning(20) and splat quenching(21-24), which have been used commercially in the production of amorphous Fe-Si-B based magnetic alloys(25-28), demonstrating that they can produce rapidly solidified material at scale.To facilitate freezing in the amorphous structure upon cooling, the melt should remain liquid down to as low a temperature as possible, and have a composition that does not crystallize readily. The lowest melt temperatures occur at eutectic alloy compositions, such as the Al-Si eutectic at 577°C and 12.2 at% Si(29). In this eutectic, the Al can also lithiate(30), increasing its specific capacity. The Al-Si eutectic alloy has been successfully employed as an LIB anode(31), but crystallizes and phase-separates on cooling. Addition of a third metal M impedes phase separation(16) and enables the formation of Al-Si-M metallic glasses (17,18). Prior studies on sputtered amorphous Al-Si-Mn(19) and Al-Si-Sn(13) thin films have established a region of amorphous compositions with good LIB cycling performance. Based on those studies, the Al 64 Si 25 Mn 11 composition was selected for this work. The composition was confirmed by energydispersive x-ray spectroscopy (EDX). Utilizing splat quenching, which enables cooling rates up

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Section: Sei Compositionmentioning

confidence: 95%

Section: Electrochemical Cell Assembly and Testingmentioning

confidence: 99%

Section: Sei Compositionmentioning

confidence: 99%

See 1 more Smart Citation

Stable SEI Formation on Al-Si-Mn Metallic Glass Li-Ion Anode

Schnabel¹,

Lin²,

Arca³

et al. 2021

Meet. Abstr.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The chemical composition and thickness of the SEI film continuously change during the charging/discharging cycles. [ 80 ] This SEI film continuously change is directly related to the formation of lithium ethylene dicarbonate (LiEDC) and LiPF 6 decomposition products during silicon lithiation, and the products subsequent disappear upon delithiation.…”

Section: Efficient Strategies Toward Si Anodesmentioning

confidence: 99%

“…In Figure 12c, it illustrates the detailed procedure for recycling industrial waste and preparation of Si/SiO 2 . [ 80 ] The Si/SiO 2 are derived from Si loss slurry in solar industry and quartz sand waste, and used for anodes. By inheriting the intrinsic advantage of Si and SiO 2 , the composites exhibit 992.8 mAh g −1 after 400 cycles at 0.5 A g −1 without capacity decay.…”

Section: Toward Practical Applicationsmentioning

confidence: 99%

Challenges and Recent Progress on Silicon‐Based Anode Materials for Next‐Generation Lithium‐Ion Batteries

et al. 2021

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The electrode materials are the most critical content for lithium‐ion batteries (LIBs) with high energy density for electric vehicles and portable electronics. Considering the high abundance, environmental friendliness, low cost, high capacity, and low operation potential of silicon‐based anode, it has been intensively studied as one of the most promising anode materials for high‐energy LIBs. However, the widespread application of silicon anode is impeded by the poor electrical conductivity, large volume variation, and unstable solid–electrolyte interfaces films. In the past decade, significant efforts have been demonstrated to tackle these major challenges toward industrial applications. Herein, the focus is on combining with advanced structure like nanostructure and composite with other materials, exploring various new polymer binders, improving electrolyte, different prelithiation strategies, and Si/graphite design to meet commercialization requirements, particularly summarized the progress on areal capacity, initial Coulombic efficiency, and cost. Finally, the guidelines and trends for practical silicon electrodes are presented based on the recent reports.

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Pre‐Lithiation of Silicon Anodes by Thermal Evaporation of Lithium for Boosting the Energy Density of Lithium Ion Cells

Adhitama

Brandao

Dienwiebel

et al. 2022

Adv Funct Materials

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Silicon (Si) is one of the most promising anode candidates to further push the energy density of lithium ion batteries. However, its practical usage is still hindered by parasitic side reactions including electrolyte decomposition and continuous breakage and (re‐)formation of the solid electrolyte interphase (SEI), leading to consumption of active lithium. Pre‐lithiation is considered a highly appealing technique to compensate for active lithium losses. A critical parameter for a successful pre‐lithiation strategy by means of Li metal is to achieve lithiation of the active material/composite anode at the most uniform lateral and in‐depth distribution possible. Despite extensive exploration of various pre‐lithiation techniques, controlling the lithium amount precisely while keeping a homogeneous lithium distribution remains challenging. Here, the thermal evaporation of Li metal as a novel pre‐lithiation technique for pure Si anodes that allows both, that is, precise control of the degree of pre‐lithiation and a homogeneous Li deposition at the surface is reported. Li nucleation, mechanical cracking, and the ongoing phase changes are thoroughly evaluated. The terms dry‐state and wet‐state pre‐lithiation (without/with electrolyte) are revisited. Finally, a series of electrochemical methods are performed to allow a direct correlation of pre‐SEI formation with the electrochemical performance of pre‐lithiated Si.

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Electrochemical Reactivity and Passivation of Silicon Thin-Film Electrodes in Organic Carbonate Electrolytes

Cited by 59 publications

References 74 publications

Stable SEI Formation on Al-Si-Mn Metallic Glass Li-Ion Anode

Stable SEI Formation on Al-Si-Mn Metallic Glass Li-Ion Anode

Challenges and Recent Progress on Silicon‐Based Anode Materials for Next‐Generation Lithium‐Ion Batteries

Pre‐Lithiation of Silicon Anodes by Thermal Evaporation of Lithium for Boosting the Energy Density of Lithium Ion Cells

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