Microelectrode Studies of the Li/Li+ Couple in SOCl2 / LiAlCl4

Hedges, W. M.; Pletcher, Derek; Gosden, C.

doi:10.1149/1.2100669

Cited by 16 publications

(8 citation statements)

References 8 publications

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“…The Gibbs activation energies were found to be around 29 kJ mol -1 even with PEGDME1000 added into the electrolytic solutions. Such activation energy for the exchange current density of the Li + /Li couple in ether and/or ester based electrolytes was reported by some research groups as a range of 25−69 kJ mol -1 , ,,− which depends on the solvents and salts. As explained in the Raman spectroscopic studies, the solvation state of lithium ions in the PEGDME500 and PEGDME1000 should be similar, since lithium ions are incorporated into the helix structures of EO chains. , Therefore, the activation energy is independent of the amounts of PEGDME1000.…”

Section: Resultsmentioning

confidence: 81%

Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

et al. 2004

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The exchange current densities of the Li + /Li couple reaction in polyether based electrolytes, 0.5 M LiCF 3 -SO 3 /poly(ethylene glycol) dimethyl ether whose molecular weight is 500 (PEGDME500), were investigated for the studies about charge-transfer reaction rate at the electrode/electrolyte interfaces. It was found that the exchange current densities in the PEGDME500 based electrolytes decreased with increasing amounts of PEGDME1000 (molecular weight: 1000). Raman spectroscopic studies indicated that the activity of lithium ions, which is a factor for the exchange current densities, was found to be the almost constant even with the addition of PEGDME1000 in to the electrolytes. The Gibbs activation energies for the interfacial reaction were also the almost constant. Meanwhile, inversely proportional relationships between the exchange current densities and viscosities of the electrolytes were observed. Our studies elucidated that viscosity of the electrolytes was the only important factor for the charge-transfer reaction rate at polyether based electrolyte/electrode interfaces.

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Section: Resultsmentioning

confidence: 81%

Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

et al. 2004

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“…V = Vinsertlo n electrode --VLith .... lectrode ----U + in ~ + A(I) [8] where U is the open-circuit (equilibrium) potential, a function of the state of charge, but a constant for our transportcontrolled analysis. The potential drop across the electrolyte is given by A~P.…”

Section: ~_ C(l)mentioning

confidence: 99%

Microelectrode Study of the Lithium/Propylene Carbonate Interface: Temperature and Concentration Dependence of Physicochemical Parameters

Verbrugge

Koch

1994

J. Electrochem. Soc.

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Selected physicochemical parameters useful for characterizing the metallic lithium electrode exposed to a lithium perehlorate salt in a propylene carbonate solvent are reported as functions of temperature and salt composition. The advantages of using microelectrodes for the measurements are elucidated. Transport parameters governing the electrolytephase limiting current density are found to be independent of salt composition over a concentration range of interest for lithium batteries. The Li-Li + reaction is shown to correspond to classic electron-transfer theory, with a symmetry factor of one-half, as would be expected for a strongly solvated ionic reactant. Simplified equations are derived that allow one to focus on specific aspects of a lithium thin-film battery, demonstrating the utility of the measured parameters for engineering design studies.For the optimal design of lithium batteries, it is necessary to know the transport properties of the nonaqueous electrolyte and the reaction-rate parameters characterizing the electrolyte-electrode interfaces. Using these physicochemical parameters, one can determine which resistance dominates the electrolyte/lithium-electrode portion of the battery, expediting the design of an efficient system.A number of publications ~-~ review early studies concerning the behavior of the lithium electrode in nonaqueous solvents. Microelectrodes are used in this work to investigate kinetic and transport phenomena. Recent studies ~-n have elucidated the virtues of mieroelectrodes for the study of the Li-Li + system. This utility of microelectrodes can be understood by considering the overall behavior of the electrode-electrolyte interface to be represented by Electrochemical reaction: Li + + e-~ Li Chemical reaction: Li + Solvent -> Degradation product If the electrochemical reaction is accelerated relative to the chemical degradation reaction, then the effect of the parallel chemical degradation reaction is reduced. Mieroelectrodes provide a means for studying electrodeposition processes in the ampere/em 2 current-density range, thereby reducing greatly the exposure of deposited lithium to solvent.In addition to providing a tool for investigating the Li-Lt + reaction, the microelectrode is useful for extracting transport parameters from well-defined limiting current plateaus (cf. Fig. 2). However, because very high current densities can be obtained using microeleetrodes, the microelectrode current-potential relation does not represent achievable performance from actual lithium batteries. The lithium electrode in such batteries is usually covered with a resistive surface film, and the overall cell resistance is much larger than that observed in this mieroeleetrode study. During high-rate lithium deposition required for rapid recharge of secondary batteries, metallic lithium does exist on the electrode surface, often in the form of microscopic lithium nodules, and each isolated nodule may be viewed as a mieroelectrode.This communication is organized in the following manner. After a sh...

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“…Understanding the electron transfer kinetics has historically been challenging, because measurements are typically convoluted by Li-ion transport through the SEI. Earlier studies showed that fast scan cyclic voltammetry (CV) minimizes the effects of SEI, but insufficiently fast scan rates placed the measurements under Nernstianor mass transportcontrol, as opposed to kineticor electron transfercontrol. ,,− These studies led to two common assumptions in lithium electrochemistry: (1) the electron transfer is described well by the Butler–Volmer model of electrode kinetics, and (2) the electron transfer resistance is negligible in electrochemical impedance spectra . However, the Nernstian conditions of previous measurements merit a reevaluation of the electron transfer kinetics and these common assumptions.…”

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confidence: 99%

Transient Voltammetry with Ultramicroelectrodes Reveals the Electron Transfer Kinetics of Lithium Metal Anodes

et al. 2020

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Fully understanding the mechanism of lithium metal deposition is critical for the development of rechargeable lithium battery anodes. The heterogeneous electron transfer kinetics are an important aspect of lithium electrodeposition, but they have been difficult to measure and understand. Here, we use transient voltammetry with ultramicroelectrodes to explicitly investigate the electron transfer kinetics of lithium electrodeposition. The results deviate from the Butler−Volmer model of electrode kinetics; instead, a Marcus model accurately describes the electron transfer. Measuring the kinetics in a series of electrolytes shows the mechanism of lithium deposition under electron transfer control is consistent with the general framework of Marcus theory. Comparison of the transient voltammetry results to electrochemical impedance spectra provides a strategy for understanding how the interplay of the electron transfer and mass transport resistances affect the morphology of lithium.

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Microelectrode Studies of the Li/Li+ Couple in SOCl2 / LiAlCl4

Cited by 16 publications

References 8 publications

Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

Microelectrode Study of the Lithium/Propylene Carbonate Interface: Temperature and Concentration Dependence of Physicochemical Parameters

Transient Voltammetry with Ultramicroelectrodes Reveals the Electron Transfer Kinetics of Lithium Metal Anodes

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Microelectrode Studies of the Li/Li+ Couple in SOCl2 / LiAlCl4

Cited by 16 publications

References 8 publications

Charge-Transfer Reaction Rate of Li+/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

Charge-Transfer Reaction Rate of Li+/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

Microelectrode Study of the Lithium/Propylene Carbonate Interface: Temperature and Concentration Dependence of Physicochemical Parameters

Transient Voltammetry with Ultramicroelectrodes Reveals the Electron Transfer Kinetics of Lithium Metal Anodes

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Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes

Charge-Transfer Reaction Rate of Li⁺/Li Couple in Poly(ethylene glycol) Dimethyl Ether Based Electrolytes