Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions

Sloop, Steven E; Pugh, James K.; Wang, S.; Kerr, John B.; Kinoshita, K.

doi:10.1149/1.1353158

Cited by 539 publications

(427 citation statements)

References 7 publications

Supporting

Mentioning

418

Contrasting

Order By: Relevance

“…[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 mechanism of HF formation in LiPF6 based organic carbonate electrolytes

Lux

Lucas

Elam

et al. 2012

Electrochemistry Communications

439

350

View full text Add to dashboard Cite

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.

show abstract

Section: (2)mentioning

confidence: 99%

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes

Lux

Lucas

Elam

et al. 2012

Electrochemistry Communications

439

350

View full text Add to dashboard Cite

show abstract

“…Often the electrolytes used in LIBs contain the lithium hexafluorophosphate (LiPF 6 ) salt dissolved in different volatile organic solvents which altogether restrict battery usage to temperatures <60 • C [4,5]. As a result, the LIB in hybrid or fully electric vehicles (xEVs) has its own cooling system, keeping it at a safe but slightly elevated operating temperature-often ca.…”

Section: Introductionmentioning

confidence: 99%

Pyrrolidinium FSI and TFSI-Based Polymerized Ionic Liquids as Electrolytes for High-Temperature Lithium-Ion Batteries

Kerner

Johansson

2018

Batteries

View full text Add to dashboard Cite

Promising electrochemical and dynamical properties, as well as high thermal stability, have been the driving forces behind application of ionic liquids (ILs) and polymerized ionic liquids (PILs) as electrolytes for high-temperature lithium-ion batteries (HT-LIBs). Here, several ternary lithium-salt/IL/PIL electrolytes (PIL el ) have been investigated for synergies of having both FSI and TFSI anions present, primarily in terms of physico-chemical properties, for unique application in HT-LIBs operating at 80 • C. All of the electrolytes tested have low T g and are thermally stable ≥100 • C, and with TFSI as the exclusive anion the electrolytes (set A) have higher thermal stabilities ≥125 • C. Ionic conductivities are in the range of 1 mS/cm at 100 • C and slightly higher for set A PIL el , which, however, have lower oxidation stabilities than set B PIL el with both FSI and TFSI anions present: 3.4-3.7 V vs. 4.2 V. The evolution of the interfacial resistance increases for all PIL el during the first 40 h, but are much lower for set B PIL el and generally decrease with increasing Li-salt content. The higher interfacial resistances only influence the cycling performance at high C-rates (1 C), where set B PIL el with high Li-salt content performs better, while the discharge capacities at the 0.1 C rate are comparable. Long-term cycling at 0.5 C, however, shows stable discharge capacities for 100 cycles, with the exception of the set B PIL el with high Li-salt content. Altogether, the presence of both FSI and TFSI anions in the PIL el results in lower ionic conductivities and decreased thermal stabilities, but also higher oxidation stabilities and reduced interfacial resistances and, in total, result in an improved rate capability, but compromised long-term capacity retention. Overall, these electrolytes open for novel designs of HT-LIBs.

show abstract

“…However, LiPF 6 is known to be extremely sensitive to moisture and thermally decompose at about 60°C. Its decomposition components consist of high toxic and corrosive HF, PF 5 and POF 3 , where HF can dissolve cathode active materials, PF 5 can react with electrolyte solvents and consequently bring about thermal runaway [22][23][24]. In the last few years, a kind of lithium borate salts, for example, lithium bis(oxalato) borate (LiBOB) has attracted great interest to researchers because of superior thermal stability, considerable ionic conductivity and fair dissociation constant [25][26][27].…”

Section: Introductionmentioning

confidence: 99%

A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance

et al. 2014

View full text Add to dashboard Cite

A single-ion gel polymer electrolyte of PLTB@PVDF-HFP (polymeric lithium tartaric acid borate@poly(vinylidene fluoride-co-hexafluoropropene)) was prepared and its ionic conductivity was optimized via solvent composition tailoring. It was manifested that the ethylene carbonate/dimethyl carbonate (EC/DMC) swollen PLTB@PVDF-HFP exhibited a superior lithium ionic conductivity at room temperature to that of the traditional liquid electrolyte system (1 M LiPF 6 /EC/DMC). The Li 4 Ti 5 O 12 /LiFePO 4 cells using the EC/DMC swollen PLTB@PVDF-HFP as polymer electrolyte showed stable charge/discharge voltage profiles with small voltage hysteresis, preferable rate capability and excellent cycle performance at room temperature. These superior performances of EC/DMC swollen PLTB@ PVDF-HFP could endow this class of gel polymer electrolyte a very promising alternative to state of the art liquid electrolyte system.

show abstract

Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions

Cited by 539 publications

References 7 publications

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes

Pyrrolidinium FSI and TFSI-Based Polymerized Ionic Liquids as Electrolytes for High-Temperature Lithium-Ion Batteries

A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance

Contact Info

Product

Resources

About