Comparative study of EC/DMC LiTFSI and LiPF6 electrolytes for electrochemical storage

Dahbi, Mouad; Ghamouss, Fouad; Tran‐Van, François; Lemordant, Daniel; Anouti, Mérièm

doi:10.1016/j.jpowsour.2011.07.071

Cited by 298 publications

(223 citation statements)

References 25 publications

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“…On the other hand, the LiTFSI containing electrolyte shows an exponential growth from the start, which can be correlated to strong aluminum dissolution and is well-known in literature. 69,70 As the structures of the two investigated salts are so similar and a dissolution behavior has been reported for the LiTFSM, the same may be expected for the LiPFSM. 61 Both salts indeed show a similar increase in electric charge over the time of the experiment, indicating anodic dissolution.…”

supporting

confidence: 72%

Electrochemical Performance and Thermal Stability Studies of Two Lithium Sulfonyl Methide Salts in Lithium-Ion Battery Electrolytes

Murmann

Schmitz

Nowak

et al. 2015

J. Electrochem. Soc.

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Electrolyte solutions, containing the lithium sulfonyl methide salts lithium-tris(trifluoromethanesulfonyl)methide (LiTFSM) and lithium-[bis(trifluoromethylsulfonyl)-pentafluoroethylsulfonyl]methide (LiPFSM) dissolved in organic carbonate solvents, were electrochemically investigated in Li/graphite, Li/LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) half-cells and compared to the LiPF 6 based electrolyte with regard to their ionic conductivity, electrochemical stability, thermal stability at 60 • C and the anodic dissolution behavior vs. Al. While the investigated salts show almost the same performance in Li/graphite half-cells compared to the LiPF 6 containing electrolyte, the methide salts show very promising results in Li/NCM half-cells, which depict superior capacity retention as well as higher Coulombic efficiencies compared to the LiPF 6 containing electrolyte. Taking the limited anodic stability as well as the occurring anodic dissolution into account, both salts but especially LiTFSM indicate the applicability in lithium ion battery electrolytes for cells with a cutoff potential up to 4. In the last 25 years the demand for lithium-ion batteries has grown tremendously. As a consequence, fundamental research has been carried out regarding the improvement and understanding of technological and safety related aspects. [1][2][3][4][5][6][7][8] Individual applications demand specifically tailored batteries in order to maximize the performance of the device which depicts a great challenge and opportunity for the scientific community to diversify the spectrum of compounds that can be utilized and to adapt the setup in a fast and efficient manner. 9,10 In this respect, the electrolyte, as a multifunctional battery component, can consist of a wide array of compounds such as different solvents, conductive salts and numerous additives. The combination of various electrolyte compounds opens up the possibility to tailor the electrolyte and thus, to a significant extent, the battery cell performance. 11-14The current state-of-the-art electrolyte composition is comprised of the conductive salt lithium hexafluorophosphate (LiPF 6 ) dissolved in a mixture of cyclic (e.g. ethylene carbonate and propylene carbonate [15][16][17][18][19] ) and linear carbonates (e.g. dimethyl-, diethyl-and ethyl-methyl carbonate). 11,[19][20][21][22][23][24][25] However, with increasing demands on the electrolyte regarding thermal and/or electrochemical stability, the limitations of such electrolyte mixtures are unraveled. 11,26,27 Alternative electrolyte compositions that depict certain improvements compared to the state-of-the-art electrolyte are still required to fulfil the following properties: a sufficient ionic conductivity to transport the lithium ions, the ability to form an effective solid electrolyte interphase (SEI) on the graphitic anode 28-37 which enables stable cycling in the low potential range as well as inertness toward aluminum to avoid anodic dissolution of the current collector on the cathode side. 38,39 In addition to performance, more...

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supporting

confidence: 72%

Electrochemical Performance and Thermal Stability Studies of Two Lithium Sulfonyl Methide Salts in Lithium-Ion Battery Electrolytes

Murmann

Schmitz

Nowak

et al. 2015

J. Electrochem. Soc.

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“…However, LiPF 6 is thermally unstable and moisture sensitive. It can trigger detrimental side reactions with residual trace water in organic solvent and generate HF that is detrimental to cell performance [9].…”

Section: Introductionmentioning

confidence: 99%

Anticorrosive flexible pyrolytic polyimide graphite film as a cathode current collector in lithium bis(trifluoromethane sulfonyl) imide electrolyte

Han

Zhang

Huang

et al. 2014

Electrochemistry Communications

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a b s t r a c t a r t i c l e i n f oFlexible pyrolytic polyimide graphite film (PGF) is explored as a cathode current collector in lithium ion batteries using lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) based electrolyte. It is demonstrated that no obvious anodic current is observed up to 4.5 V versus Li + /Li for PGF, while significant corrosion current is found from 3.6 V for aluminum, indicative of better electrochemical stability of PGF than that of aluminum in LiTFSI based electrolyte. LiMn 2 O 4 on aluminum and PGF has been used as model electrode for testing. There is hardly any capacity retained after 10 cycles at room temperature for the LiMn 2 O 4 /aluminum electrode. With regard to the LiMn 2 O 4 /PGF electrode, the capacity retention ratio remained 89% after 1000 cycles. Moreover, at an elevated temperature of 55°C, the capacity retention ratio kept at 81% after 300 cycles. Since LiTFSI-based electrolyte shows advantages in safety, stability and conductivity but could not be used due to Al-corrosion, the application of the PGF current collector could overcome this barrier.

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“…In general, the electrolyte resistance is the only parameter here, which can be compared to literature values as very precise conductivity meters exist and the conductivities have been tabulated. [25][26][27][28][29] However, the main feature is the muting factor H and the exchange current density j 0,H of the SEI resistance. For all seven Li systems a jump of both H and j 0,H is observed with a change of each parameter of one to two orders of magnitude.…”

mentioning

confidence: 99%

Temperature-Dependence of the Solid-Electrolyte Interphase Overpotential: Part I. Two Parallel Mechanisms, One Phase Transition

Heß¹

2018

J. Electrochem. Soc.

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It has been shown recently that the overpotential originating from ionic conduction of alkali-ions through the inner dense solidelectrolyte interphase (SEI) is strongly non-linear. An empirical equation was proposed to merge the measured resistances from both galvanostatic cycling (GS) and electrochemical impedance spectroscopy (EIS) at 25 • C. Here, this analysis is extended to the full temperature range of batteries from −40 • C to +80 • C for Li, Na, K and Rb-metal electrodes in carbonate electrolytes. Two different transport mechanisms are found. The first one conducts alkali-ions at all measured temperatures. The second transport mechanism conducts ions for all seven measured Li-ion electrolytes and one out of four Na-ion electrolytes; however, only above a certain critical temperature T C . At T C a phase transition is observed switching-off the more efficient transport mechanism and leaving only the general ion conduction mechanism. The associated overpotentials increase rapidly below T C depending on alkali-ion, salt and solvent and become a limiting factor during galvanostatic operation of all Li-ion electrolytes at low temperature. In general, the current analysis merges the SEI resistances measured by EIS ranging from 26 cm 2 for the best Li up to 292 M cm 2 for Rb electrodes to its galvanostatic response over seven orders of magnitude. The determined critical temperatures are between 0-25 • C for the tested Li and above 50 • C for Na electrolytes. Extensive research over the last thirty years on Li-ion batteries (LIB) has advanced the field so that LIBs do not only power electronic gadgets anymore as in the 1990's but are also starting to drive new transportation systems like electric bikes, cars and buses. However, in transportation performance at different temperatures is far more relevant especially during recharge.Recently, it was shown that the overpotential originating from the solid-electrolyte interphase (SEI) is strongly non-linear.1,2 At ambient temperature, this overpotential is negligible for Li-metal in alkylcarbonate solvents, however, severe for Na and K-metal electrodes. The resistances from both, electrochemical impedance spectroscopy (EIS) and short galvanostatic charge and discharges (GS) could be fit with the same parameter set by introducing an empirical equation.

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Comparative study of EC/DMC LiTFSI and LiPF6 electrolytes for electrochemical storage

Cited by 298 publications

References 25 publications

Electrochemical Performance and Thermal Stability Studies of Two Lithium Sulfonyl Methide Salts in Lithium-Ion Battery Electrolytes

Electrochemical Performance and Thermal Stability Studies of Two Lithium Sulfonyl Methide Salts in Lithium-Ion Battery Electrolytes

Anticorrosive flexible pyrolytic polyimide graphite film as a cathode current collector in lithium bis(trifluoromethane sulfonyl) imide electrolyte

Temperature-Dependence of the Solid-Electrolyte Interphase Overpotential: Part I. Two Parallel Mechanisms, One Phase Transition

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