Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O

Plakhotnyk, Andriy V.; Ernst, Ludger; Schmutzler, Reinhard

doi:10.1016/j.jfluchem.2004.09.027

Cited by 320 publications

(359 citation statements)

References 19 publications

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“…the HF concentration is initially too low to etch the thermal oxide layer. Here, the LiPF 6 -6-decomposition starts, the salt is further dissociated and the PF 5 is reacting with the solvent and water traces to initialize polymerization of the organic carbonates [8] and further decompose to HF. Later, a second phase, namely the "formation phase" begins, in which the first Si-O-Si bond is broken, is observable.…”

Section: Methodsmentioning

confidence: 99%

“…[8,11] Furthermore, quantum chemical calculations demonstrate the influence of the highly positive lithium ion on the solvent coordination sphere of the complex anion. [7] As a consequence, a lowered stability of LiPF 6 in organic carbonate electrolyte is observed, when compared with other alkali metals hexafluorophosphates.…”

Section: (2)mentioning

confidence: 99%

“…The decomposition is not only catalyzed by the elevated temperature nor by the presence of moisture , it is also activated by the release of protons upon formation of LiF either within the Solid electrolyte interphase (SEI) at the negative electrode or within the passivation layer at the positive electrode. [8] (3)…”

Section: (2)mentioning

confidence: 99%

“…However, the protons released can react further with LiPF 6 molecules to produce additional HF. [8] (4) (5) HF formed by this different possible reactions, can significantly influence the calendar and cycle life time of the cell. [10,12] A special case of this degradation problem occurs when a LiPF 6 based electrolyte is combined with an electrochemical system containing SiO 2 or SiOH.…”

Section: (2)mentioning

confidence: 99%

“…[1][2][3][4][5] However, despite the relatively high thermal stability in dry inert atmosphere up to 107°C where only solid lithium fluoride and PF 5 are formed [6], this salt suffers from degradation upon exposure to traces of water, moisture or alcohols [7]. In literature it is proposed that the reaction starts with the decomposition of LiPF 6 [7][8][9][10]: (1) to form phosphorous pentafluoride which can react with water to form HF and POF 3 .…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes

Lux

Lucas

Elam

et al. 2012

Electrochemistry Communications

429

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Spectroscopic ellipsometry was used to study the time-dependent formation of HF upon the thermal degradation of LiPF 6 at 50°C in a lithium ion battery electrolyte containing ethylene carbonate and diethyl carbonate. The generated HF was monitored by following the etching rate of a 300 nm thick SiO 2 layer, grown on both sides of a silicon wafer substrate, as a function of the immersion time in the electrolyte at 50°C. It was found that the formation of HF starts after 70 hours of exposure time and occurs following several different phases. The amount of generated HF was calculated using an empirical formula correlating the etching rate to the temperature. Combining the results of the HF formation with literature data, a simplified mechanism for the formation of the HF involving LiPF 6 degradation, and a simplified catalytical reaction pathway of the formed HF and silicon dioxide is proposed to describe the kinetics of HF formation.

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Section: Methodsmentioning

confidence: 99%