Studies of interfacial reactions on thin film electrodes of Sn during initial cycling using infrared spectroscopy

Baek, Seung Yeon; Hong, Sukhyun; Kim, D.-W.; Song, Seung‐Wan

doi:10.1016/j.jpowsour.2008.09.035

Cited by 18 publications

(31 citation statements)

References 16 publications

(17 reference statements)

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“…5a-a', the C-Si surface shows strong IR features below 900 cm , related to the reduction of organic carbonate solvents. 16,17,[22][23][24]31,32,[40][41][42] With 1-(trimethylsilyloxy)-1,3-butadiene, Fig. 5b-b', the CSi surface also shows strong IR features below 900 cm .…”

Section: Resultsmentioning

confidence: 95%

“…5b-b', the CSi surface also shows strong IR features below 900 cm . 16,17,[22][23][24]31,32 Newly appeared tiny peaks at 1307, 1153, 1016, 833 cm -1 are ascribed to stretching modes of P=O, P-O-C and P-F group from -O=PF-OR organic phosphorus-fluorine compounds. 31,32,43 They are partly overlapped with the peaks at 1108 and ~1045 cm -1 characteristic of siloxane chain, 16,31,32 in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…16,[21][22][23][24] Polymeric binder often gives interfering signals in IR spectroscopic data, which obstructs distinguishing newly formed surface species from the binder. Thin-films prepared with pulsed laser deposition (PLD), which generally possess a strong physical interfacial adherence to electronically conductive substrate, allow the observation of material's intrinsic surface structure and reaction, and inhibit a peel-off event of the film during extended cycling in lithium cells.…”

Section: Introductionmentioning

confidence: 99%

“…For the surface characterization, we focus on ex-situ IR measurement with attenuated total reflection (ATR) geometry that is very sensitive to surface species and provides direct information on the functional groups of surface molecules. [22][23][24][25][26] Here we report a surface modification approach to stabilize surface structure and cycling performance of carbon-coated Si thin-film electrode. Surface modification by self-assembly of organoalkoxysilanes with different number of organoalkoxy group and SEI layer formation resulting from electrode/electrolyte interfacial reactions were determined using ex-situ IR spectroscopy with attenuated total reflection (ATR) geometry.…”

Section: Introductionmentioning

confidence: 99%

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Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

Choi¹,

Nguyen²,

Song³

2010

Bulletin of the Korean Chemical Society

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Silane-based self-assembly was employed for the surface modification of carbon-coated Si electrodes and their surface chemistry and electrochemical performance in battery electrolyte depending on the molecular structure of silanes was studied. IR spectroscopic analyses revealed that siloxane formed from silane-based self-assembly possessed Si-O-Si network on the electrode surface and high surface coverage siloxane induced the formation of a stable solid-electrolyte interphase (SEI) layer that was mainly composed of organic compounds with alkyl and carboxylate metal salt functionalities, and PF-containing inorganic species. Scanning electron microscopy imaging showed that particle cracking were effectively reduced on the carbon-coated Si when having high coverage siloxane and thickened SEI layer, delivering > 1480 mAh/g over 200 cycles with enhanced capacity retention 74% of the maximum discharge capacity, in contrast to a rapid capacity fade with low coverage siloxane.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

Choi¹,

Nguyen²,

Song³

2010

Bulletin of the Korean Chemical Society

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“…Sn-based anode materials, however, suffer from a rapid performance fade due to a large volume change followed by particle cracking event during lithiation/delithiation and the loss of electrical contact between individual particles and between particles and current collector [1]. It has been established that interfacial instability of Sn electrode with electrolyte is due to the attack of LiPF 6 -derived acidic species (PF 5 , PF 3 O, HF) and this additionally deteriorates the electrical disintegration [3][4][5]. Interfacial stabilization and the formation of stable solid electrolyte interphase (SEI) have been suggested as one of the most effective approaches for enhancing the cycling performance of Sn-based anodes.…”

Section: Introductionmentioning

confidence: 99%

Lithium Diffusivity of Tin-based Film Model Electrodes for Lithium-ion Batteries

Hong¹,

Jo²,

Song³

2015

Journal of Electrochemical Science and Technology

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Lithium diffusivity of fluorine-free and -doped tin-nickel (Sn-Ni) film model electrodes with improved interfacial (solid electrolyte interphase (SEI)) stability has been determined, utilizing variable rate cyclic voltammetry (CV). The method for interfacial stabilization comprises fluorine-doping on the electrode together with the use of electrolyte including fluorinated ethylene carbonate (FEC) solvent and trimethyl phosphite additive. It is found that lithium diffusivity of Sn is largely dependent on the fluorine-doping on the Sn-Ni electrode and interfacial stability. Lithium diffusivity of fluorinedoped electrode is one order higher than that of fluorine-free electrode, which is ascribed to the enhanced electrical conductivity and interfacial stabilization effect.

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Mechanisms for Stable Solid Electrolyte Interphase Formation and Improved Cycling Stability of Tin‐Based Battery Anode in Fluoroethylene Carbonate‐Containing Electrolyte

Hong

Choo

Kwon³

et al. 2016

Adv Materials Inter

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that enable to form a stable solid electrolyte interphase (SEI) layer at the surface of the alternative anode for reliable battery performance. Tin (Sn)-based anode material based on alloy formation with Li has been one of the promising candidates because of the large theoretical capacity (≈992 mAhg −1 ) of Sn compared to that of graphite (372 mAhg −1 ). Sn also holds its merits of appropriate operating voltage above Li, which prevents dendrite formation, and high electronic conductivity as metallic, and improved Li + -transport kinetics. [1][2][3][4] The Sn, however, suffers from a rapid performance fade due to large volume change (≈300%) upon repeated charge (lithiation)-discharge (delithiation) cycling, which results in mechanical and electrical disintegration (i.e., particle cracking) between Sn particles and between the particles and current collector. [1][2][3][4] Several strategies were explored to reduce or accommodate the volume change by mostly adding various carbon (e.g., graphite) and inactive matrix, [2,5,6] and by using nanostructured Sn-carbon composites [7][8][9][10] or functional binder. [11] Since the particle cracking causes the enlarged interfacial area of Sn particles to electrolyte and continuous electrolyte decomposition at the new surface, the volume change event is closely linked to anode-electrolyte interfacial reactivity and stability. Our earlier reported results showed that interfacial irreversible reaction on Sn and destabilization of SEI layer with cycling are additional origins of a rapid performance fade in the ethylene carbonate (EC)-based conventional electrolyte. [12][13][14] Electrophilic attack of LiPF 6 salt-derived acids of PF 5 and PF 3 O (LiPF 6 → PF 5 + LiF, PF 5 + H 2 O PF 3 O + 2HF) [15,16] to the anode surface were determined to be the cause for interfacial reactivity. Surface degradation can also occur by the dissolution of surface oxide by HF. The most explored approaches to improve the interfacial (SEI) stability have been the use of electrolyte additives, such as phosphite [12,13] and fluoroethylene carbonate (FEC) [17][18][19] but just few studies have focused on investigating the SEI formation on Sn-based anode. [12,13,[19][20][21][22] Despite some improvement, challenges in the improvement of performance and SEI stability still remain. Thus, a fundamental understanding of electrode-electrolyte interfacial phenomena Tin-based anode materials are promising candidates for high-energy density Li-ion batteries. Unstable anode-electrolyte interface is a critical problem that needs to be resolved for these materials. The improvement of solid electrolyte interphase (SEI) stability and cycling stability of fluorine-doped Sn-Ni film electrode is observed by the use of fluoroethylene carbonate (FEC)based electrolyte with respect to ethylene carbonate (EC)-based conventional electrolyte. Mechanisms of FEC-derived SEI formation and stabilization are investigated using state of charge-dependent ex situ attenuated total reflection FTIR combined with X-ray photoelectron spectr...

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Studies of interfacial reactions on thin film electrodes of Sn during initial cycling using infrared spectroscopy

Cited by 18 publications

References 16 publications

Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

Lithium Diffusivity of Tin-based Film Model Electrodes for Lithium-ion Batteries

Mechanisms for Stable Solid Electrolyte Interphase Formation and Improved Cycling Stability of Tin‐Based Battery Anode in Fluoroethylene Carbonate‐Containing Electrolyte

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