Investigation of solid electrolyte interface (SEI) film on LiCoO2 cathode in fluoroethylene carbonate (FEC)-containing electrolyte by 2D correlation X-ray photoelectron spectroscopy (XPS)

Park, Yeonju; Shin, Su Hyun; Hwang, Hyonseok; Lee, Sung Man; Kim, Sung Phil; Choi, Hyun Chul; Jung, Young Mee

doi:10.1016/j.molstruc.2014.01.041

Cited by 62 publications

(28 citation statements)

References 37 publications

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“…These decompositions products have been found on cathode materials for a variety of different cathode chemistries and electrolyte compositions. [33][34][35][36][37][38] Electrolyte ( 5). If all oxidation during the potentiostatic hold was attributed to ethylene carbonate (EC) (∼4 mAh of "oxidation capacity" in the electrolyte), roughly 7% of the EC in the electrolyte would be decomposed during the 60 hour hold, and for ethyl methyl carbonate (EMC) (∼8 mAh of "oxidation capacity" in the electrolyte), about 3%.…”

Section: Resultsmentioning

confidence: 99%

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Tornheim

Trask

Zhang

2016

J. Electrochem. Soc.

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The electrolyte oxidation rate was measured at 4.6 V vs. Li + /Li for a NCM/LTO full cell at temperatures ranging from room temperature to 55 • C. A large (∼2.5) N/P ratio was used in electrode fabrication to enable a stable reference in the Li 4 Ti 5 O 12 electrode for both cycling and the potentiostatic hold regimes. LTO was used to prevent electrolyte reduction from contributing to the signal, as well as providing a stable impedance. For the alkyl carbonate electrolyte used, oxidation rate at room temperature to 45 • C approximately ranged from 1-2 μA, as measured during the terminal 4.2 hours of a 60 hour potentiostatic hold. Many cells aged at 55 • C indicated increasing, unstable currents. Upon the completion of the hold, the cells were cycled to evaluate the effect of the hold and analyzed with AC impedance spectroscopy. Higher temperatures during the potentiostatic hold led to lower capacities during post-aging cycling, as well as higher impedance as measured with EIS.In an effort to increase the energy density of batteries, high-voltage cathodes (V > 4.5 vs. Li/Li + ) are being explored as alternatives to the stable 4-V lithium manganese oxide spinel chemistry, including high voltage spinels, 1-3 nickel-cobalt-manganese layered oxides, 4-6 and olivines. 7,8 As the conventional carbonate electrolytes are traditionally thought to be stable up to 4.5 V vs. Li/Li + , improved electrolytes (either through passivating additives or intrinsically stable electrolytes) will have to be implemented to enable the higher performance of the high-voltage cathodes. 9,10 In the field of electrolyte research, there are many publications that report improved cycling performance with the addition of small amounts of novel molecules designed to 'passivate' the surface and inhibit electrolyte oxidation. 11-16 While these results are promising, the interfacial parameters are poorly constrained in these experiments, making a fundamental understanding of electrolyte anodic stability difficult to characterize. For additives that reportedly passivated the surface, there are additional explanations as to the mechanism of improvement -including HF scavenging and prevention of metal ion dissolution, which would lead to better capacity retention. 17,18 Additionally, there are pursuits of intrinsically stable electrolytes that will experience a lower decomposition rate due to a lower thermodynamic or kinetic driving force for the oxidation reaction. This pursuit has led to a variety of fluorinated solvents that show improved performance in cycling tests. 19,20 In order to enable high voltage battery chemistries, a more stable electrolyte system is necessary, and the comparison of new electrolyte compositions against a baseline anodic stability is critical to improving the high voltage limits of electrolyte systems. In this work, potentiostatic holds are performed on full cells with a lithium titanate (Li 4 Ti 5 O 12 ) anode to shed some light on the reaction rate of the conventional carbonate-based electrolyte at the charged cathode sur...

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Section: Resultsmentioning

confidence: 99%

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Tornheim

Trask

Zhang

2016

J. Electrochem. Soc.

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“…Furthermore, FEC was used as SEI film-formation additive to improve the low-temperature cycle performance of cathode LiFePO 4 [28,29]. FEC exhibited a positive effect on cycling stability of cathode LiCoO 2 when charged to 4.5 V vs. Li/Li + , which was related to the SEI film with abundant polycarbonate components formed on the cathode surface [30]. Although FEC was employed as anti-oxidative co-solvent to improve the stability of the electrolyte in 5 V cathode system [31,32], the effect of FEC on the performance of Li-rich cathode Li 1+x [Ni y Mn 1-y ] 1-x O 2 has still been significantly less reported to our knowledge.…”

Section: Introductionmentioning

confidence: 99%

Fluoroethylene Carbonate as Electrolyte Additive for Improving the electrochemical performances of High-Capacity Li1.16[Mn0.75Ni0.25]0.84O2 Material

Yang

Lian

et al. 2015

Electrochimica Acta

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“…These additives mostly form a thin SEI layer on the cathode to suppress the buildup of decomposition products over cycling and enhance the capacity retention, especially at elevated temperatures. Many of the additives originally developed for the graphite anode have been found to be able to form films on the cathode as well, such as VC [10,36,142], VEC [77], FEC [99], LiBOB [124], and LiDFOB [179]. Other than these additives, the additives [72], dimethylacetamide [154], tris(hexafluoro-iso-propyl)phosphate [121], and tris(trimethylsilyl)phosphate [167].…”

Section: Additives For 4-v Cathode Materialsmentioning

confidence: 99%

Additives for Functional Electrolytes of Li-Ion Batteries

Tornheim

Zhang

et al. 2015

Rechargeable Batteries

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Investigation of solid electrolyte interface (SEI) film on LiCoO2 cathode in fluoroethylene carbonate (FEC)-containing electrolyte by 2D correlation X-ray photoelectron spectroscopy (XPS)

Cited by 62 publications

References 37 publications

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Fluoroethylene Carbonate as Electrolyte Additive for Improving the electrochemical performances of High-Capacity Li1.16[Mn0.75Ni0.25]0.84O2 Material

Additives for Functional Electrolytes of Li-Ion Batteries

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Investigation of solid electrolyte interface (SEI) film on LiCoO2 cathode in fluoroethylene carbonate (FEC)-containing electrolyte by 2D correlation X-ray photoelectron spectroscopy (XPS)

Cited by 62 publications

References 37 publications

Evaluation of Electrolyte Oxidation Stability on Charged LiNi0.5Co0.2Mn0.3O2Cathode Surface through Potentiostatic Holds

Evaluation of Electrolyte Oxidation Stability on Charged LiNi0.5Co0.2Mn0.3O2Cathode Surface through Potentiostatic Holds

Fluoroethylene Carbonate as Electrolyte Additive for Improving the electrochemical performances of High-Capacity Li1.16[Mn0.75Ni0.25]0.84O2 Material

Additives for Functional Electrolytes of Li-Ion Batteries

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Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds