Identification of Li-Based Electrolyte Degradation Products Through DEI and ESI High-Resolution Mass Spectrometry

Laruelle, Stéphane; Pilard, Serge; Guénot, Pierre; Grugeon, Sylvie; Tarascon, Jean‐Marie

doi:10.1149/1.1760992

Cited by 100 publications

(106 citation statements)

References 35 publications

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“…LiOCH 3 ), R-CH 2 OCO 2 Li and R-CH 2 OLi, and fluorinated carbons -CF 2 -in agreement with previous studies [Fong et al, 1990;Aurbach et al, 1995;Laruelle et al, 2004;Andersson et al, 2001;Peled et al, 2001;. The formation of some SEI products like the fluorinated carbon results from reaction between the PVDF binder of the graphite and the electrolyte [Stjerndahl et al, 2007].…”

Section: Sei Formation On Lithium Carbonaceous Electrodes Conversiosupporting

confidence: 88%

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Chagnes¹,

Światowska²

2012

Lithium Ion Batteries - New Developments

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Section: Sei Formation On Lithium Carbonaceous Electrodes Conversiosupporting

confidence: 88%

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Chagnes¹,

Światowska²

2012

Lithium Ion Batteries - New Developments

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“…13 Diverse sources of ROH (3) formed in chemical reactions can be conceived and have been proposed in the literature. 10,39 They range from decomposition reactions involving either auxiliary cell components (e.g. conductive carbon additives) or other secondary decomposition products (e.g.…”

Section: Resultsmentioning

confidence: 99%

Decomposition of LiPF₆in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry

Guéguen

Streich

et al. 2016

J. Electrochem. Soc.

213

169

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The chemical and electrochemical instabilities of LiPF 6 in carbonate electrolytes for Li-ion batteries were studied with online electrochemical mass spectrometry (OEMS). Decomposition of carbonate electrolytes based on LiPF 6 eventually results in the formation of POF 3 , which is readily detected and followed in situ during operation of Li-rich HE-NCM-based Li-ion cells. Electrode potentials above ∼4.2 V leads to carbonate solvent oxidation and presumably the formation of ROH species, which subsequently hydrolyze the LiPF 6 salt and initiate a thermally activated autocatalytic electrolyte decomposition cycle involving POF 3 as a reactive intermediate. Activation of the Li 2 MnO 3 domains of the Li-rich cathode contributes along with electrolyte and separator impurities to further POF 3 generation. Electrode potentials below ∼2.5 V vs. Li + /Li impede POF 3 formation and presumably also further electrolyte decomposition by scavenging reactive intermediate species. As a result, much less POF 3 gas was detected upon the 2 nd charge when using Li metal counter electrode, contrary to delithiated LiFePO 4 . In situ OEMS confirm that the parasitic reactions involving LiPF 6 constitute an intricate reaction scheme, but more importantly, provide further evidence about what the components of this scheme are and how these may interact with each other. Rechargeable Li-ion batteries are nowadays extensively used to power electronics and are entering the transportation sector by powering electric vehicles (EV). A wide range of both negative (e.g. graphite) and positive electrode materials (e.g. layered cobalt oxides, spinel-type manganese oxides, and olivine-type iron phosphates) have been thoroughly investigated and are now in widespread use in commercial batteries. The specific energy of Li-ion batteries is limited mainly by the positive electrode materials, having typical practical specific charges of ∼150 mAh/g and average operating potentials of ∼3.8 V vs. Li + /Li, which significantly inhibits the introduction of Li-ion batteries as power source in new applications. In recent years, the layered Li-rich cobalt-nickel-manganese oxides xLi 2 MnO 3 (1−x)(LiMO 2 ) (x ∼ 0.5, M = Co, Ni, Mn), hereafter called HE-NCM, have been shown to exhibit a high and reversible specific charge (∼250 mAh/g) and a competitive average operating potential (∼3.75 V vs. Li + /Li). [1][2][3][4] The origin of such a high specific charge is not yet completely understood, as the exact structure of the HE-NCM materials is highly dependent on the synthesis conditions and models coming from structural characterization are still under debate. Several reports have shown the presence of so-called Li 2 MnO 3 domains in the compound 5,6 whereas other groups demonstrated the monophasic character of their materials.7 However, during the first charge, a long potential plateau at ∼4.5 V vs. Li + /Li, not observed for conventional layered oxides, results from the delithiation process of the Li 2 MnO 3 domains accompanied by oxygen extraction. The extracted oxy...

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“…3c using C 1s reference). The new peak at 290.0 eV, assigned to carbon bonded to three oxygen atoms, is typical of carbonate-like species: Li 2 CO 3 (from DMC reduction), alkyl carbonates (ROCO 2 Li with R CH 3 , C 2 H 5 or C 3 H 7 arising from the electrochemical reduction of DMC, EC or PC) or semicarbonate species (R(OCO2) 2 Li 2 with R (CH 2 ) 2 or CH 3 (CH 2 ) 2 originating from the electrochemical reduction of EC or PC) [41][42][43][44][45]. The inorganic Li 2 CO 3 and the organic ROCO 2 Li and R(OCO 2 )Li 2 species can be distinguished by their C O bonding as the former contains a C atom attached to three O atoms, while the later has an additional R(C) O bond besides the carbon bonded to the three O atoms [41].…”

Section: Xps Characterisation Of Pristine and (De)lithiated Silicon Ementioning

confidence: 99%

Interphase chemistry of Si electrodes used as anodes in Li-ion batteries

Pereira-Nabais

Światowska

Chagnes

et al. 2013

Applied Surface Science

144

178

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a b s t r a c tThe effect of the Si electrode morphology (amorphous hydrogenated silicon thin films -a-Si:H as a model electrode and Si nanowires -SiNWs electrode) on the interphase chemistry was thoroughly investigated by the surface science techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS analysis shows a strong attenuation and positive shift of the Si 2p peaks after a complete charge/discharge performed in PC-and EC:DMC-based electrolytes for both electrodes (a-Si:H and SiNW), confirming a formation of a passive film (called solid electrolyte interphase -SEI layer). As evidenced from the XPS analysis performed on the model electrode, the thicker SEI layer was formed after cycling in PC-based electrolyte as compared to EC:DMC electrolyte. XPS and ToF-SIMS investigations reveal the presence of organic carbonate species on the outer surface and inorganic salt decomposition species in the inner part of the SEI layer. Significant modification of the surface morphology for the both electrodes and a full surface coverage by the SEI layer was confirmed by the scanning electron microscopy (SEM) analysis.

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Identification of Li-Based Electrolyte Degradation Products Through DEI and ESI High-Resolution Mass Spectrometry

Cited by 100 publications

References 35 publications

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Decomposition of LiPF₆in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry

Interphase chemistry of Si electrodes used as anodes in Li-ion batteries

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Identification of Li-Based Electrolyte Degradation Products Through DEI and ESI High-Resolution Mass Spectrometry

Cited by 100 publications

References 35 publications

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Electrolyte and Solid-Electrolyte Interphase Layer in Lithium-Ion Batteries

Decomposition of LiPF6in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry

Interphase chemistry of Si electrodes used as anodes in Li-ion batteries

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Decomposition of LiPF₆in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry