Complete characterization of a lithium battery electrolyte using a combination of electrophoretic NMR and electrochemical methods

Hickson, Darby; Halat, David M.; Ho, Alec S.; Reimer, Jeffrey A.; Balsara, Nitash P.

doi:10.1039/d2cp02622h

Cited by 6 publications

(13 citation statements)

References 47 publications

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“…This suggests that lithium transference decreases only slightly as c + increases from 0.53 to 0.73 mol L −1 . The fact that this value is significantly higher than values obtained with univalent lithium salts, which range between 0.3 and 0.4, 8,29,51,53,54 suggests that lithium transference has generally improved due to the presence of the bulky POSS-PSTFSI 20− . The transference number measured using the PFG-NMR ( t +,PFG ) method is 0.15 in the c + ≤ 0.40 mol L −1 regime and increases sharply to overlap with ρ + at c + = 0.73 mol L −1 .…”

Section: Resultsmentioning

confidence: 77%

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Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR

Chakraborty¹,

Halat²,

Im³

et al. 2023

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 77%

“…These data are consistent with the extensive literature of monovalent salts dissolved in solvents. 20,51,52 We can also calculate k using the eNMR data in Fig. 5 and eqn (16).…”

Section: Resultsmentioning

confidence: 99%

Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR

Chakraborty¹,

Halat²,

Im³

et al. 2023

Phys. Chem. Chem. Phys.

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“…1 The ionic conductivity κ is also readily measured, e.g., from ac impedance measurements using blocking electrodes. We have previously reported thermodynamic and ionic transport data in LiTFSI/tetraglyme electrolytes as a function of c. 31,42 All measurements are reported at 30 °C.…”

Section: Resultsmentioning

confidence: 99%

“…[26][27][28] A commonly used method for determining the transference number was proposed by Ma et al, 29 wherein t 0 + is determined using four separate electrochemical experiments. 18,26,[29][30][31] Large error bars result from the need for combining results from different experiments, and from the intrinsic coupling between transport and thermodynamic parameters in the expressions used to analyze the data. On the other hand, electrophoretic NMR (eNMR) 32,33 provides a more direct approach for determining t 0 + from a single type of experiment.…”

Section: List Of Symbols Cmentioning

confidence: 99%

Transference Number of Electrolytes from the Velocity of a Single Species Measured by Electrophoretic NMR

Halat

Mistry²,

Hickson³

et al. 2023

J. Electrochem. Soc.

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Accurate measurement of the cation transference number is critical for designing batteries with a given electrolyte. A promising approach for measuring this parameter is electrophoretic nuclear magnetic resonance (eNMR). In the standard approach, the average cation, anion, and solvent velocities under an applied electric field are used to estimate the cation transference number with respect to the solvent velocity, t + 0. In this study, we show that t + 0 can be determined from measurements of the electric-field-induced velocities of individual species. The t + 0 values obtained from eNMR experiments on a model electrolyte (LiTFSI/tetraglyme) based on single species velocities are consistent with the standard approach. An important parameter that enters into the analysis is the velocity of the electrode–electrolyte interface which must be finite in an eNMR experiment. Agreement is only obtained after accounting for this velocity. The single-species approach is particularly valuable when one or more components of the electrolytic mixture are not easily accessible by NMR, for example zinc and magnesium cations.

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“…Conventional electrochemical characterization of t + 0 that is based on concentrated solution theory involves four separate experiments to determine quantities that are, in some cases, indirectly related to the transport parameters. ,, This causes large uncertainties . Electrophoretic-NMR can determine the average velocities of all three species of interest, thereby enabling measurement of t + 0 (eq ) with greater precision. ,− Notwithstanding these challenges, values of t + 0 have been reported by numerous researchers. ,− A common nontrivial observation centers on negative t + 0 in some of electrolytes at high salt concentrations. ,,− It has been widely postulated that negative t + 0 originates from the migration of negatively charged ion clusters toward positive electrode as illustrated in Figure . , …”

Section: Introductionmentioning

confidence: 99%

Elucidating the Molecular Origins of the Transference Number in Battery Electrolytes Using Computer Simulations

Fang

Mistry

Srinivasan

et al. 2023

JACS Au

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The rate at which rechargeable batteries can be charged and discharged is governed by the selective transport of the working ions through the electrolyte. Conductivity, the parameter commonly used to characterize ion transport in electrolytes, reflects the mobility of both cations and anions. The transference number, a parameter introduced over a century ago, sheds light on the relative rates of cation and anion transport. This parameter is, not surprisingly, affected by cation–cation, anion–anion, and cation–anion correlations. In addition, it is affected by correlations between the ions and neutral solvent molecules. Computer simulations have the potential to provide insights into the nature of these correlations. We review the dominant theoretical approaches used to predict the transference number from simulations by using a model univalent lithium electrolyte. In electrolytes of low concentration, one can obtain a quantitative model by assuming that the solution is made up of discrete ion-containing clusters–neutral ion pairs, negatively and positively charged triplets, neutral quadruplets, and so on. These clusters can be identified in simulations using simple algorithms, provided their lifetimes are sufficiently long. In concentrated electrolytes, more clusters are short-lived and more rigorous approaches that account for all correlations are necessary to quantify transference. Elucidating the molecular origin of the transference number in this limit remains an unmet challenge.

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Complete characterization of a lithium battery electrolyte using a combination of electrophoretic NMR and electrochemical methods

Abstract: Improving transport properties of the electrolyte is important for developing lithium-ion batteries for future energy storage applications. In Newman’s concentrated solution theory, electrolytes are characterized by three transport parameters, conductivity,...

Cited by 6 publications

References 47 publications

Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR

Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR

Transference Number of Electrolytes from the Velocity of a Single Species Measured by Electrophoretic NMR

Elucidating the Molecular Origins of the Transference Number in Battery Electrolytes Using Computer Simulations

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