Fluorinated electrolytes for Li-ion battery: An FEC-based electrolyte for high voltage LiNi0.5Mn1.5O4/graphite couple

Hu, Libo; Zhang, Zhengcheng; Amine, Khalil

doi:10.1016/j.elecom.2013.08.009

Cited by 199 publications

(165 citation statements)

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“…18 , 19 Several novel organic solvents with greater oxidative stability, such as sulfones, 19 nitriles, 20 and fl uorinated solvents, 21 have recently been explored as electrolytes. Unfortunately, these electrolytes may also compromise the anode solid electrolyte interphase-forming reactions required in Li-ion batteries.…”

Section: Rechargeable Li-ion Batteriesmentioning

confidence: 99%

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

2014

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This issue contains assessments of battery performance involving complex, interrelated physical and chemical processes between electrode materials and electrolytes. Transformational changes in battery technologies are critically needed to enable the effective use of renewable energy sources such as solar and wind to allow for the expansion of hybrid electric vehicles (HEVs) to plug-in HEVs and pure-electric vehicles. For these applications, batteries must store more energy per unit volume and weight, and they must be capable of undergoing many thousands of charge-discharge cycles. The articles in this theme issue present details of several growing interest areas, including high-energy cathode and anode materials for rechargeable Li-ion batteries and challenges of Li metal as an anode material for Li batteries. They also address the recent progress in systems beyond Li ion, including Li-S and Li-air batteries, which represent possible next-generation batteries for electrical vehicles. One article reviews the recent understanding and new strategies and materials for rechargeable Mg batteries. The knowledge presented in these articles is anticipated to catalyze the design of new multifunctional materials that can be tailored to provide the optimal performance required for future electrical energy storage applications.

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Section: Rechargeable Li-ion Batteriesmentioning

confidence: 99%

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

2014

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“…Computational and experimental investigations suggest that these effects are due to the comparably high stability of fluorinated carbonates at high potentials 12,33,35 and FEC's specific reductive decomposition properties (reductive CO 2 formation). 15,16,[36][37][38][39] The aim of the study is to present OEMS investigations of O 2 , C 2 H 4 , CO 2 , and POF 3 gas evolution from HE-NCM/SFG6 half-and full-cells during the first two galvanostatic charge/discharge cycles in EC:DEC and FEC:DEC based 1 M LiPF 6 electrolytes.…”

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confidence: 99%

“…Lately, it has been reported in several independent studies that fluoroethylene carbonate (FEC) can have beneficial effects on the cycling behavior of diverse lithium-ion battery anode and cathode 10,[30][31][32][33][34] materials. Computational and experimental investigations suggest that these effects are due to the comparably high stability of fluorinated carbonates at high potentials 12,33,35 and FEC's specific reductive decomposition properties (reductive CO 2 formation).…”

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Online Electrochemical Mass Spectrometry of High Energy Lithium Nickel Cobalt Manganese Oxide/Graphite Half- and Full-Cells with Ethylene Carbonate and Fluoroethylene Carbonate Based Electrolytes

Streich

Guéguen

Méndez

et al. 2016

J. Electrochem. Soc.

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Online electrochemical mass spectrometry (OEMS) was employed to investigate the behavior of ethylene carbonate (EC) and fluoroethylene carbonate (FEC) co-solvents in high voltage lithium-ion batteries based on high energy lithium nickel cobalt manganese oxide (HE-NCM) and SFG6 graphite (SFG6) electrodes. Gas evolution from HE-NCM and SFG6 electrodes was studied during two charge/discharge cycles in half-cell and full-cell configuration using electrolytes composed of 1 M LiPF 6 in either 3:7 (w/w) EC:DEC or 3:7 (w/w) FEC:DEC. The results suggest that some CO 2 formation is caused by reactive oxygen species originating from Li 2 MnO 3 domain activation. The electrolyte composition has no effect on O 2 evolution during Li 2 MnO 3 domain activation and oxidative CO 2 evolution in HE-NCM/Li half-cells. In contrast, decomposition of PF 6 − is significantly enhanced in electrolyte containing FEC and found to be strongly facilitated by the SuperC65 conductive carbon additive employed in the HE-NCM electrodes. EC and FEC clearly follow different reductive decomposition pathways. This leads to major differences in solid electrolyte interphase (SEI) formation and affects follow-up reactions involving CO 2 and possibly other processes relevant for the stability and endurance of high voltage lithium-ion batteries.

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“…However, using X-ray photoelectron and Fourier-transform infrared (FT-IR) spectroscopy measurements, Yang et al 10 showed that constant polarization of LNMO at 4.5 V vs Li + /Li results in the oxidation and polymerization of EC, forming poly(ethylenecarbonate) (PEC) species. EC oxidation has been rationalized on the basis of a high highest occupied molecular 11,12 Despite these advances, an accurate understanding of the chemical composition and thickness of the EEI in LNMO remains elusive. Raman, EIS and FT-IR measurements are not specifically sensitive to the surface chemistry of parasitic species formed during electrochemical conditioning, and conventional, lab-based XPS probes only ∼ 2 nm of product, whereas EEI thicknesses are typically larger.…”

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Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

Mansour

Kwabi

Quinlan

et al. 2016

J. Electrochem. Soc.

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X-ray photoelectron spectroscopy (XPS) was used to investigate the surface chemistry of high voltage spinel, LiNi 0.5 Mn 1.5 O 4 (LNMO) positive electrodes cycled 5 and 10 times in Li-cells with 1 M LiPF 6 in (3:7) EC:DMC. The XPS spectra were collected using conventional Mg X-rays with energy of 1253.6 eV as well as synchrotron X-rays with energies of 2493.6 and 3498.4 eV in order to examine the depth distribution of various surface chemical species induced during cycling. The XPS spectra revealed a 5 -10 nm surface layer of organic and Li x PF y O z -type species formed as result of electrolyte decomposition, and a comparatively thinner layer composed of transition metal fluorides and LiF. These results suggest that electrolyte decomposition is a major contributor to parasitic reactions in LNMO battery electrochemistry. Limiting electrolyte decomposition with the use of solvents with wide electrochemical stability windows thus comprises a promising strategy for ensuring the practical feasibility of high voltage spinel materials in future Li-ion systems. Rechargeable lithium-ion batteries (LIBs) are among the widest used energy sources for portable electronic devices, but are currently being considered for more energy-dense applications such as electric vehicles and short-term grid support. In order to realize these possibilities, gravimetric energy densities of typical LIBs, which currently provide 400-550 Wh/kg need to be improved. LiNi 0.5 Mn 1.5 O 4 (LNMO) is a particularly promising positive electrode material in this regard, as it operates at an exceptionally high voltage of 4.8 V vs Li + /Li, 1 resulting in an energy density of ∼706 Wh/kg based on a theoretical capacity of 147 mAh/g for 1e − transfer. 2 Such a high voltage is however above the potential at which most LIB electrodes, cell components and electrolytes decompose (>4.2 V vs Li + /Li), and results in the formation of highly resistive parasitic species that hamper battery reversibility and cycle life.In order to design LIBs that are chemically stable enough for practical application, a strong fundamental understanding of electrolyte decomposition and side product formation mechanisms is required. In positive LIB electrodes, battery cycling typically results in an electrode-electrolyte interface (EEI), the study of which can yield mechanistic insights into particularly critical parasitic reaction pathways responsible for poor electrochemical performance.3 Thus, understanding the structure and composition of the surface EEI in LNMObased positive electrodes is key to their commercial realization.Previous studies exploring LNMO performance degradation during cycling have explored the influence of stoichiometry, 4 cation ordering, 4,5 doping 6 and particle morphology. 5,7,8 There have been relatively fewer studies exploring EEI formation in detail, likely owing to the difficulty of characterizing thin layers (typically < 20 nm) of product. Using Raman and Electrochemical Impedance Spectroscopy (EIS) measurements, Aurbach et al. 9 suggested that LNMO...

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Fluorinated electrolytes for Li-ion battery: An FEC-based electrolyte for high voltage LiNi0.5Mn1.5O4/graphite couple

Cited by 199 publications

References 20 publications

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

Online Electrochemical Mass Spectrometry of High Energy Lithium Nickel Cobalt Manganese Oxide/Graphite Half- and Full-Cells with Ethylene Carbonate and Fluoroethylene Carbonate Based Electrolytes

Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays

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Fluorinated electrolytes for Li-ion battery: An FEC-based electrolyte for high voltage LiNi0.5Mn1.5O4/graphite couple

Cited by 199 publications

References 20 publications

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

Rechargeable lithium batteries and beyond: Progress, challenges, and future directions

Online Electrochemical Mass Spectrometry of High Energy Lithium Nickel Cobalt Manganese Oxide/Graphite Half- and Full-Cells with Ethylene Carbonate and Fluoroethylene Carbonate Based Electrolytes

Probing the Electrode-Electrolyte Interface in Cycled LiNi0.5Mn1.5O4by XPS Using Mg and Synchrotron X-rays

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Probing the Electrode-Electrolyte Interface in Cycled LiNi_0.5Mn_1.5O₄by XPS Using Mg and Synchrotron X-rays