Enabling LiTFSI‐based Electrolytes for Safer Lithium‐Ion Batteries by Using Linear Fluorinated Carbonates as (Co)Solvent

Kalhoff, Julian; Bresser, Dominic; Bolloli, Marco; Alloin, Fannie; Sanchez, Jean‐Yves; Passerini, Stefano

doi:10.1002/cssc.201402502

Cited by 86 publications

(73 citation statements)

References 42 publications

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“…[33,[46][47][48][49] Thisi nability may be explained by two differentr easons. One mayb et hat LiTFSI is too stable to provide fluoride anions fort he formation of the protectivea luminum (oxy-)fluorides urface layer.…”

Section: Imide-based Lithium Saltsmentioning

confidence: 97%

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

et al. 2015

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Lithium-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mechanical, thermal, or electrical abuse conditions. These safety issues are intrinsically related to their superior energy density, combined with the (present) utilization of highly volatile and flammable organic-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of organic carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather "facile" electrolyte modifications by (partially) replacing the organic solvent or lithium salt and/or the addition of functional electrolyte additives, conceptually new electrolyte systems, including ionic liquids, solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mechanical, thermal, physicochemical, and electrochemical performance.

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Section: Imide-based Lithium Saltsmentioning

confidence: 97%

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

et al. 2015

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“…The cyclic voltammetry test of LiTFSI in cyclic fluorinated carbonate F 2 EC (Fig. 8c) shows a continuous increase of the anodic current flowing comparable to F 1 EC, although the current density and the pitting corrosion is, indeed, reduced relatively to F 1 EC [10]. Indeed, only 10 cycles permit a large corrosion of aluminum, whereas 100 cycles are necessary with F 2 EC to observe pitting corrosion.…”

Section: Anodic Aluminum Dissolutionmentioning

confidence: 90%

“…Very recently, we reported that the utilization of a solvent mixture of mono-fluorinated ethylene carbonate and mono-fluorinated diethyl carbonate (1:1 by weight), containing 1 M LiTFSI, provides a solution to overcome the detrimental anodic aluminum current collector dissolution by forming a protective aluminum fluoride film on the aluminum surface [10]. Moreover, the investigation of this electrolyte composition in lithium-ion cells, comprising commercially available graphite as negative electrode and Li [Ni 1/3 Mn 1/3 Co 1/3 ]O 2 as positive material, revealed very stable cycling performance and good rate capability [10]. Nevertheless, so far only few studies were reported on the correlation between the fluorination and the physico-chemical and electrochemical properties of the fluorinated solvents.…”

Section: Introductionmentioning

confidence: 99%

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Effect of carbonates fluorination on the properties of LiTFSI-based electrolytes for Li-ion batteries

Bolloli

Alloin

Kalhoff³

et al. 2015

Electrochimica Acta

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“…Nevertheless, electron conduction between the active material particles as well as between the LTO particles and the aluminum current collector certainly represent a major contribution to these interfacial phenomena. 57 The latter is frequently affected by the presence of a native oxide layer on the aluminum current collector surface, 58 potentially resulting in a reduced adhesion of the electrode coating. Basically, R int is very similar for all the three electrodes after ten cycles (Figures 8d to 8f), though slightly higher for PVdF-based ones (Figure 8d).…”

Section: 21mentioning

confidence: 99%

Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Birrozzi

Copley

Zamory

et al. 2015

J. Electrochem. Soc.

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Herein, we present the upscaled synthesis of nanoparticulate Li 4 Ti 5 O 12 (LTO) by means of flame spray pyrolysis (FSP), yielding high phase purity and appropriate morphology for application as high-power lithium-ion anode material. Electrodes based on this optimized LTO nanopowder, carboxymethyl cellulose (CMC) as binder, and copper as current collector revealed excellent rate performance, providing specific capacities of 133, 131, 129, 127, 124, and 115 mAh g −1 when applying C rates of 1C, 2C, 5C, 10C, 20C, and 50C, respectively. Targeting the commercial application of thus synthesized nanoparticles, we optimized also the electrode composition, comparing three different binding agents (CMC, PVdF, and poly(acrylic acid), PAA) and substituting the copper current collector by aluminum. The results of this comparative analysis show, that the combination of nanoparticulate LTO, CMC, and an aluminum current collector appears most suitable toward the realization of environmentally friendly and cost-efficient lithium-ion anodes, presenting very stable cycling performance for more than 1000 cycles at 10C without substantial capacity decay. While lithium-ion batteries are already the energy storage device of choice for portable electronic devices, they are recently gaining importance for large-scale applications like (hybrid) electric vehicles and stationary energy storage.1-5 However, beside advances regarding the energy density, such applications still require an improved safety, long-term cycling stability, as well as enhanced power densities with respect to state-of-the-art lithium-ion cells, commonly employing graphite as anode material.1-5 Spinel-structured Li 4 Ti 5 O 12 (LTO), reported for the first time by Colbow et al. in 1989, 6 is presently considered as one of the most promising alternative anode materials for realizing safer, long-lasting, high power lithium-ion batteries 7-13 and is, for such reasons, already utilized in commercial cells.2 While the enhanced safety and advanced long-term cycling stability, resulting from the relatively higher lithium (de-)insertion potential and the negligible volume variation upon (de-)lithiation, 14-17 respectively, are, to a great extent intrinsic to LTO, the high power performance, i.e., the rate capability, of the material is highly dependent on the utilized synthesis method and the resulting particle size and morphology. 9,13,[18][19][20][21] Indeed, downsizing the particle size to the nanometer-scale resulted in excellent power performance, 21-25 allowing (dis-)charging LTObased electrodes in as little as a few seconds. However, one of the major challenges toward the commercialization of nano-sized LTO is the development of easily scalable synthesis methods, providing large batches of active material at competitive prices.13 A highly attractive method for the large-scale preparation of metal oxide nanoparticles appears to be flame spray pyrolysis (FSP). 26,27 We have recently reported the electrochemical characterization of the first generation of FSP-synthesi...

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Enabling LiTFSI‐based Electrolytes for Safer Lithium‐Ion Batteries by Using Linear Fluorinated Carbonates as (Co)Solvent

Cited by 86 publications

References 42 publications

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Effect of carbonates fluorination on the properties of LiTFSI-based electrolytes for Li-ion batteries

Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

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Enabling LiTFSI‐based Electrolytes for Safer Lithium‐Ion Batteries by Using Linear Fluorinated Carbonates as (Co)Solvent

Cited by 86 publications

References 42 publications

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Effect of carbonates fluorination on the properties of LiTFSI-based electrolytes for Li-ion batteries

Scaling up “Nano” Li4Ti5O12for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

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Product

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Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis