Phase Diagram and Conductivity of Zn(TFSI)<sub>2</sub>–H<sub>2</sub>O Electrolytes

Ding, Michael S.; Ma, Lin; Schroeder, Marshall A.; Xu, Kang

doi:10.1021/acs.jpcc.0c07937

Cited by 13 publications

(17 citation statements)

References 15 publications

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“…LiTFSI material was purchased from Gotion and used as is, EC was purchased from Ferro and dried before use, and H 2 O was doubly distilled before use. The series of LiTFSI + EC samples was obtained by successively diluting a starting solution of 0.239 mole fraction of salt with the EC solvent . The LiTFSI + H 2 O samples of different compositions were prepared separately.…”

Section: Methodsmentioning

confidence: 99%

“…A functional representation of the conductivities of the LiTFSI + EC samples of different compositions and temperatures was obtained by fitting the experimentally determined data with a parameterized Vogel–Fulcher–Tammann (VFT) function using Wolfram Mathematica to be used for later calculation and data presentation …”

Section: Methodsmentioning

confidence: 99%

“…The series of LiTFSI + EC samples was obtained by successively diluting a starting solution of 0.239 mole fraction of salt with the EC solvent. 4 The LiTFSI + H 2 O samples of different compositions were prepared separately.…”

Section: ■ Methodsmentioning

confidence: 99%

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A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

Ding

2021

J. Phys. Chem. C

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As aqueous electrolytes have been gaining renewed interest in battery research, understanding how the properties of these electrolytes change at icing and other phase transitions becomes imperative for both monitoring such occurrences in extreme environments and identifying the service temperature limits for the battery devices containing such electrolytes. In this study, we devised a coupled thermoconductometric measurement system in which the impedance and temperature of an electrolyte sample, along with the temperature of a reference, were concurrently, continuously, and speedily measured while the sample was subjected to an external temperature ramp across its phase transitions. The synchronized curves of conductivity and temperature differential thus obtained were used effectively to study and understand the different processes in the phase transitions and their impact on the apparent conductivity of the electrolytes. The solutions of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in water and in ethylene carbonate (EC) were chosen as the representative aqueous and nonaqueous electrolytes, respectively. Results showed that while the differential temperature signal at a phase transition was always pronounced, a change in apparent conductivity could be deceptively unremarkable and easily escape notice, which may lead to erroneous estimation for the temperature limits of the electrolytes. It was also revealed that the nature of the solvent, the degree of supercooling, and the electrolyte composition were factors in determining the magnitude of the apparent conductivity drop at a phase transition. Furthermore, the apparent conductivity curves of a precipitated hypoeutectic LiTFSI + EC electrolyte were accurately calculated from the properties and proportion of its remaining liquid, using several functional relationships made available by an experimentally mapped phase diagram and a measurement-based conductivity function plus a form of mixing rule with an adjustable factor to account for the spatial configuration of the precipitates. Such in-depth understanding of ion-transport behavior at phase transition sets the foundation for quantitative prediction of electrolyte properties at extreme temperatures.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

Ding

2021

J. Phys. Chem. C

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“…New axis was added for a better resolution, Reproduced with permission. [ 47 ] Copyright 2020, American Chemical Society. c) Ionic conductivity and viscosity of Zn(OTF) 2 aqueous electrolyte versus the concentration, Reproduced with permission.…”

Section: Fundamentals Of Azibsmentioning

confidence: 99%

“…[ 45,46 ] The ionic conductivity is also influenced by the concentration and viscosity. [ 47,48 ] Generally, as the concentration increases, the ionic conductivity climbs before reaching a peak value (Figure 2b) and then fades due to a detrimental viscosity increasement (Figure 2c). [ 45,49 ] The anions also influences the stability of the electrolyte and the pH value (Table 1), [ 50–58 ] for instance, unstable ClO 4 − and NO 3 − anions may first be decomposed and generate dense layer on Zn.…”

Section: Fundamentals Of Azibsmentioning

confidence: 99%

Insight on Organic Molecules in Aqueous Zn‐Ion Batteries with an Emphasis on the Zn Anode Regulation

Wang

Zhao

et al. 2022

Advanced Energy Materials

269

177

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Rechargeable aqueous zinc ion batteries (AZIBs), as a rising star in aqueous ion batteries, are restricted by the narrow voltage window and the unsatisfactory reversibility, which are dominated by the high activity of H2O molecules, side reaction, Zn dendrites, and structural degeneration of the cathode. Electrolyte manipulation has seen a great deal of research recently, particularly various kinds of organic molecules have been shown to achieve outstanding effects on stabilizing the Zn anode, yet the exploration of the mechanism behind the high performance has not been thorough. In an attempt to find such underlying principles, the basic reactions and the corresponding progress on the anode side of AZIBs are first assessed. Then, the roles of organic molecules in recent studies are researched, followed by a deep insight into the role of organic molecules. Finally, several designed strategies are proposed for the further exploration of high performance aqueous rechargeable ZIBs through incorporating appropriate organic molecules in the electrolytes.

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Design Strategies for Anti‐Freeze Electrolytes in Aqueous Energy Storage Devices at Low Temperatures

You,

Fan,

Xiong

et al. 2024

Adv Funct Materials

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With the continuous development of electrochemical energy storage technology, especially in the current pursuit of environmental sustainability and safety, aqueous energy storage devices, due to their high safety, environmental friendliness, and cost‐effectiveness, are becoming an important direction of development in the field of energy storage. Diverse application scenarios require that energy storage systems be capable of continuous power supply under low temperature conditions. However, conventional aqueous electrolytes freeze at extremely low temperatures, causing limited ion transport and slow reaction kinetics, degrading the performance of the energy storage system. The design of low‐temperature anti‐freeze aqueous electrolytes has become an effective way to address this issue. In this review, the deep connection between hydrogen bonds (HBs) interactions in aqueous electrolytes and the liquid‐to‐solid conversion process, and the fundamental principles of the anti‐freeze mechanism is first explored. Subsequently, a systematic categorization and discussion of the design strategies for low‐temperature anti‐freeze aqueous electrolytes are conducted. Finally, potential directions are proposed. This review aims to provide comprehensive scientific guidance and technical reference for the development of anti‐freeze aqueous electrolytes with excellent low‐temperature performance, thereby promoting the application and innovation of aqueous energy storage devices in low‐temperature environments.

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Phase Diagram and Conductivity of Zn(TFSI)₂–H₂O Electrolytes

Cited by 13 publications

References 15 publications

A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

Insight on Organic Molecules in Aqueous Zn‐Ion Batteries with an Emphasis on the Zn Anode Regulation

Design Strategies for Anti‐Freeze Electrolytes in Aqueous Energy Storage Devices at Low Temperatures

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Phase Diagram and Conductivity of Zn(TFSI)2–H2O Electrolytes

Cited by 13 publications

References 15 publications

A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

A Thermoconductometric Study of Transient Behavior of Liquid Electrolytes at Phase Transition

Insight on Organic Molecules in Aqueous Zn‐Ion Batteries with an Emphasis on the Zn Anode Regulation

Design Strategies for Anti‐Freeze Electrolytes in Aqueous Energy Storage Devices at Low Temperatures

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Phase Diagram and Conductivity of Zn(TFSI)₂–H₂O Electrolytes