Conductivity and Viscosity of PC-DEC and PC-EC Solutions of LiBOB

Ding, Michael S.; Xu, Ke; Jow, T. Richard

doi:10.1149/1.1833611

Cited by 62 publications

(81 citation statements)

References 27 publications

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“…Propylene carbonate is a popular choice of solvent both as a single solvent [40] and as part of a multiple solvent system [41,14,15,42] with various, usually lithium based salts.…”

Section: Conductivitymentioning

confidence: 99%

“…The ionic conductivity of an electrolyte is of scientific interest due to the primary application of these solutions as electrochemical devices; which require high conductivities to adequately perform. Detailed research into liquid electrolytes containing LiBF 4 have been measured elsewhere with carbonated solvents such as propylene carbonate and their mixtures [12,13,14,15]. In these papers many salt concentrations and temperatures have been probed and have a main emphasis on covering a large range of solvent mixtures.…”

Section: Introductionmentioning

confidence: 99%

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Pulsed-Field Gradient NMR Self Diffusion and Ionic Conductivity Measurements for Liquid Electrolytes Containing LiBF4 and Propylene Carbonate

Richardson

Voice

Ward

2014

Electrochimica Acta

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This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Page 1 of 42A c c e p t e d M a n u s c r i p t 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 AbstractLiquid electrolytes have been prepared using lithium tetrafluoroborate (LiBF 4 ) and propylene carbonate (PC). Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) measurements were taken for the cation, anion and solvent molecules using lithium ( 7 Li), fluorine ( 19 F) and hydrogen ( 1 H) nuclei, respectively. It was found that lithium diffusion was slow compared to the much larger fluorinated BF 4 anion likely resulting from a large solvation shell of the lithium. Ionic conductivity and viscosity have also been measured for a range of salt concentrations and temperatures. By comparing the measured conductivity with a ideal predicted conductivity derived from the Nernst-Einstein equation and self diffusion coefficients the degree of ionic association of the anion and cation was determined and was observed to increase with salt concentration and temperature. Using the measured viscosity and self diffusion coefficients the effective radius of each of the species was determined for various salt concentrations.

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“…Propylene carbonate is a popular choice of solvent both as a single solvent [40] and as part of a multiple solvent system [41,14,15,42] with various, usually lithium based salts.…”

Section: Conductivitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Pulsed-Field Gradient NMR Self Diffusion and Ionic Conductivity Measurements for Liquid Electrolytes Containing LiBF4 and Propylene Carbonate

Richardson

Voice

Ward

2014

Electrochimica Acta

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“…25-27 LiPF 6 , LiClO 4 and KPF 6 in PC; 28 LiBOB in PC 29 and the conductivity of three Na systems but at 25…”

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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“…Our group focused on the kinetics of charge ͑lithium ion͒-transfer reactions at a graphite/electrolyte interface 14,15 and other interfaces. [16][17][18][19] The activation energies of the charge-transfer reactions were around 50 kJ mol −1 or more, which were higher compared to those of lithium-ion transport in solid [20][21][22][23] or liquid [24][25][26] electrolytes. This is because the desolvation of lithium ion from solvents occurs during the charge transfer at the interfaces, and the energy for the desolvation is large.…”

mentioning

confidence: 99%

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Yamada

Iriyama

Abe

et al. 2010

J. Electrochem. Soc.

135

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The kinetics of the electrochemical insertion and extraction of lithium ion at silicon monoxide ͑SiO͒ were investigated by ac impedance spectroscopy. The resultant Nyquist plots showed two semicircles at high and middle frequency regions. These two semicircles were attributed to lithium-ion transport resistance in a surface film and alloying reaction resistance ͑charge-transfer resistance͒, respectively. We evaluated the activation energies of the charge-transfer reaction from the temperature dependences of the interfacial conductivities. When an ethylene-carbonate-based electrolyte was used, the activation energy of the charge transfer was 32 kJ mol −1 . This activation energy was much smaller than those at graphite electrode or positive electrode materials ͑around 50 kJ mol −1 or more͒. Based on these results, the charge transfer at SiO is exceptionally fast compared to those at other insertion materials. Furthermore, the activation energies of the charge transfer at SiO remained unchanged in various electrolytes. These results suggest that the charge-transfer kinetics at SiO is not influenced by the desolvation of lithium ion from solvent molecules. Lithium-ion batteries have recently attracted much attention as a power source for electric vehicles ͑EVs͒ and plug-in hybrid EVs. These applications of lithium-ion batteries give severe requirements to electrode materials. One such requirement is a significant improvement in the energy density of electrode materials. Therefore, an alternative electrode material has been explored for a much higher energy density. Among the candidates for a new negative electrode are alloying materials such as Si and Sn.1,2 These materials electrochemically react with lithium to form a lithium alloy that has an extremely high energy density compared to graphite. However, the alloying reaction shows a large volume change in the materials, 3 which leads to capacity fade during charge-discharge cycles. 4 To overcome the problem, silicon monoxide ͑SiO͒ has recently attracted much attention as a next generation negative electrode. 5-13SiO shows a small volume change because it contains a relatively small amount of Si element that is active for the alloying reaction. The discharge capacity of SiO electrodes was reported to be over 600 mAh g −1 in several papers, 9-12 which is much higher than that of a graphite electrode ͑372 mAh g −1 ͒. To commercialize the SiO electrode, we need to consider the rate performance in addition to the energy density. However, there are few reports on the kinetic aspect of alloying materials. Our group focused on the kinetics of charge ͑lithium ion͒-transfer reactions at a graphite/electrolyte interface 14,15 and other interfaces. [16][17][18][19] The activation energies of the charge-transfer reactions were around 50 kJ mol −1 or more, which were higher compared to those of lithium-ion transport in solid [20][21][22][23] or liquid [24][25][26] electrolytes. This is because the desolvation of lithium ion from solvents occurs during the charge transfer at the...

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Conductivity and Viscosity of PC-DEC and PC-EC Solutions of LiBOB

Cited by 62 publications

References 27 publications

Pulsed-Field Gradient NMR Self Diffusion and Ionic Conductivity Measurements for Liquid Electrolytes Containing LiBF4 and Propylene Carbonate

Pulsed-Field Gradient NMR Self Diffusion and Ionic Conductivity Measurements for Liquid Electrolytes Containing LiBF4 and Propylene Carbonate

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

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

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