Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Lewandowski, Andrzej; Kurc, Beata; Stępniak, Izabela; Swiderska‐Mocek, Agnieszka

doi:10.1016/j.electacta.2011.04.105

Cited by 32 publications

(16 citation statements)

References 33 publications

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“…Despite these interesting properties and studies focusing on cathodes performance [30,31], only few reports deal with carbon-based electrodes [32] and even less [33] with EC-free electrolytes able to operate a full Li-ion cell including graphite. Recently, Dahn's group reported on full Li-ion using VC and other additives in SL-based electrolytes [34] and we reported that, by use of carboxymethyl cellulose (CMC)/styrene-butadiene rubber (SBR)-based graphite anodes, efficient cycling of graphite is possible in a 1 M LiPF6 SL:DMC (1:1, wt.)…”

Section: Introductionmentioning

confidence: 99%

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Zhang

Porcher

Paillard

2018

Journal of Power Sources

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Abstract:Sulfolane (tetramethylene sulfone, SL) is known for leading to Li-ion electrolytes with high anodic stability. However, the operation of graphite electrodes in alternative electrolytes is usually challenging, especially when ethylene carbonate (EC) is not used as co-solvent. Thus, we study here the influence of the lithium salt on the physico-chemical and electrochemical properties of EC-free SL-based electrolytes and on the performance of graphite electrodes based on carboxymethyl cellulose (CMC). SL mixed with dimethyl carbonate (DMC) leads to electrolytes as conductive as state-of-theart alkyl carbonate-based electrolytes with wide electrochemical stability windows. The compatibility with graphite electrodes depends on the Li salt used and, even though cycling is possible with most salts, lithium difluoro-oxalato borate (LiDFOB) is especially interesting for graphite operation.LiDFOB electrolytes are conductive at room temperature (ca. 6 mS cm -1 ) with an anodic stability slightly below 5 V vs. Li/Li + on particulate carbon black electrodes. In addition, it allows cycling graphite electrodes with steady capacity and high coulombic efficiency without any additive. The testing of graphite electrodes in half-cells is, however, problematic with SL:DMC mixtures and, by switching the Li metal counter electrode for LiFePO4, the graphite electrode achieves better practical performance in terms of rate capability.

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Section: Introductionmentioning

confidence: 99%

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Zhang

Porcher

Paillard

2018

Journal of Power Sources

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“…Co-solvents and/or additives have been introduced either to decrease the viscosity and melting point or to help form a protective solid electrolyte interface (SEI) film. 5,6,14,15 For example, Xu and Angell et al 5 found that Li/graphite and Li/Li 1-x Mn 2 O 4 half cells with 3,3,3-trifluoropropylmethyl sulfone/ethyl-methyl carbonate (EMC) (1:1 or 1:2 wt% ratio) could cycle 20 times with CEs close to unity. In another publication, 14 they found that the introduction of 1% VC to the methoxyethyl methyl sulfone system could provide similar cycling performance to 1.0 M LiPF 6 /EC:DMC (1:1 by volume) in LiCoO 2 /graphite full cells cycled between 3.0 to 4.2 V. Abouimrane et al 6 demonstrated that tetramethylsulfone can be used with EMC as a co-solvent and LiPF 6 Recently, our group has begun studying the effect of electrolyte additives and different solvents in Li[Ni 0.42 Mn 0.42 Co 0.…”

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confidence: 99%

Sulfolane-Based Electrolyte for High Voltage Li(Ni_0.42Mn_0.42Co_0.16)O₂(NMC442)/Graphite Pouch Cells

Xia

Self

et al. 2015

J. Electrochem. Soc.

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Ethylene carbonate (EC)-free electrolyte composed of sulfolane (SL), ethylmethyl carbonate (EMC) and vinylene carbonate (VC) was studied in Li(Ni 0.42 Mn 0.42 Co 0.16 )O 2 (NMC442)/graphite pouch cells using in situ measurements of gas evolution, ultra high precision coulometry (UHPC), automated storage experiments, long-term cycling and electrochemical impedance spectroscopy (EIS). Although cells using 1 M LiPF 6 in SL:EMC 3:7 (w:w) do not function at all, the addition of only 1% VC allows the cells to operate normally. In situ gas measurements show that NMC442/Graphite pouch cells containing SL:EMC:VC electrolyte produce less gas during formation than cells containing control (1 M LiPF 6 EC:EMC 3:7 (w:w)) electrolyte or 2% VC in control electrolyte. Cycling and storage experiments show that cells containing SL:EMC:VC electrolytes can provide better performance than control electrolyte without additives and similar performance to state-of-the-art electrolyte with the ternary additive blend 2% prop-1-ene-1,3-sultone (PES) +1% methylene methanedisulfonate (MMDS) +1% tris(trimethylsilyl) phosphite (TTSPi) ("PES-211") in EC:EMC 3:7 (w:w). The SL:EMC:VC system needs to be further explored with additional additives and from a safety perspective. The development of high voltage Li-ion batteries is one of the best ways to increase their energy density. However, this simple approach has proven to be difficult since electrolyte solvents and additives are unstable at high potentials and the parasitic degradation of these components results in gas evolution, severe impedance growth, low coulombic efficiency (CE) and poor capacity retention.1-4 Therefore, the development of high voltage electrolyte systems is one of the major bottlenecks in the path of Li-ion cells with high energy density.There have been many efforts to develop high voltage electrolyte systems. Some examples include: sulfone-based electrolytes; 5,6 room temperature ionic liquid-based electrolytes; 7 fluorinated electrolytes; 8 nitrile-based electrolytes; 9 as well as electrolyte additives that can properly passivate the positive electrode surface.10 Sulfone-based solvents were first reported in rechargeable lithium batteries by Matsuda et al in 1985. 11 The oxidation potentials of sulfones are generally higher than 5.0 V vs. Li/Li + , independent of the sulfone structure. 12The oxidation potentials of sulfones can be further increased when they are functionalized with strong electron-withdrawing groups. (442)/graphite cells with highly concentrated lithium bis(fluorosulfonyl)imide (LiFSI) in ethyl acetate electrolyte (no EC present) could be cycled to 4.2 V and 4.4 V at 40• C for at least several weeks without dramatic capacity loss. Thus, electrolyte additives, concentrated salts and atypical solvents all can play a part in the successful implementation of high voltage Li-ion cells.Here, the sulfolane (SL) -ethylmethyl carbonate (EMC) -vinylene carbonate (VC) system is shown to be viable in NMC442/graphite pouch cells that can be cycled to 4.5 V for s...

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“…The formation of nanoparticles can reduce the Li-ion diffusion path as well as provide a large contact area between the nanoparticles. Doping by other metal cations and adding carbon or metal powder into the Li 4 [30][31][32]. Another approach is to test low vapour pressure molecular solvents, e.g., tetramethylene sulfone (sulfolane, TMS, T b = 280°C) [33] or gamma-butyrolactone (GBL, T b = 205°C) [34].…”

Section: -10mentioning

confidence: 99%

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

Kurc

Swiderska‐Mocek

2013

J Appl Electrochem

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Two non-flammable electrolytes 1 M LiPF 6 in sulfolane (TMS) ? 5 wt% VC and 0.7 M lithium bis(trifluoromethanesulphonyl)imide (LiNTf 2 ) in N-methyl-Npropylpyrrolidinium bis(trifluoromethanesulphonyl)imide (MePrPyrNTf 2 ) ? 10 wt% gamma-butyrolactone (GBL) were tested with Li 4 Ti 5 O 12 (LTO) as highly promising anode material for application in lithium-ion batteries. The results were compared for the titanium anode in the classic electrolyte: 1 M LiPF 6 in propylene carbonate ? dimethyl carbonate (PC ? DMC, 1:1). The performances of LTO/ electrolyte/Li cell were tested using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge and scanning electron microscopy (SEM). SEM images of electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of solid-state interface formation. Good charge/discharge capacities and low capacity loss at medium C rates preliminary cycling was obtained for the Li 4 Ti 5 O 12 anode. For LTO/1 M LiPF 6 in PC ? DMC/Li system, the best capacity was obtained at C/10 and C/3 (145 and 154 mAh g -1 , respectively). In the case of a system working on the basis of a TMS solution (1 M LiPF 6 in TMS ? 5 wt% VC) the best value was obtained at a C/5 current and an average of more than 150 mAh g -1 (86 % of theoretical capacity). For the 0.7 M LiNTf 2 in MePrPyrNTf 2 ? 10 wt% GBL electrolyte, the highest capacitance value (at C/20 current) of about 150 mAh g -1 was observed. The 1 M LiPF 6 in TMS ? 5 wt% VC and 0.7 M LiNTf 2 in MePrPyrNTf 2 ? 10 wt% GBL electrolytes had a relatively broad thermal stability range and no decomposition peak was observed below 150°C.

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Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Cited by 32 publications

References 33 publications

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Sulfolane-Based Electrolyte for High Voltage Li(Ni_0.42Mn_0.42Co_0.16)O₂(NMC442)/Graphite Pouch Cells

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

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Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Cited by 32 publications

References 33 publications

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Sulfolane-Based Electrolyte for High Voltage Li(Ni0.42Mn0.42Co0.16)O2(NMC442)/Graphite Pouch Cells

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

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Sulfolane-Based Electrolyte for High Voltage Li(Ni_0.42Mn_0.42Co_0.16)O₂(NMC442)/Graphite Pouch Cells