Study on the AC Impedance Spectroscopy for the Li Insertion Reaction of LixLa1/3NbO3 at the Electrode−Electrolyte Interface

Nakayama, Masanobu; Ikuta, Hiromasa; Uchimoto, Yoshiharu; Wakihara, Masataka

doi:10.1021/jp036059k

Cited by 79 publications

(63 citation statements)

References 17 publications

(23 reference statements)

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“…In general, metal deposition in liquid electrolytes contains electron transfer from an electrode to metal ion and the following desolvation or solvent reorganization. Abe et al 16 and Uchimoto et al 17 suggested that Li/Li + couple reactions at the electrode/electrolyte interface in various organic electrolyte soutions had high activation barrier which was strongly influenced by the solvation and desolvation of Li ions. These strongly suggest that for the Li deposition in the present liquid electrolyte the desolvation step after electron transfer from the electrode to Li + ion is rate-determining.…”

Section: Resultsmentioning

confidence: 99%

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

et al. 2012

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Charge transfer kinetics at the Li metal electrode/electrolyte interface for three inorganic solid electrolytes and an organic liquid electrolyte were elucidated with two parameters, exchange current density (i 0 ) for Li/Li + couple reactions and ionic conductivity in electrolyte. The former was evaluated by potential step method with a microelectrode, while the latter was done by electrochemical impedance spectroscopy. Both i 0 and ionic conductivity showed Arrhenius type dependence, and activation energies (E a ) for the charge transfer reactions and ionic conduction were evaluated. In the case of the organic liquid electrolyte, E a for the Li/Li + couple reactions was higher than that for ionic conduction because of the solvation/desolvation of Li + ion. However, for the Li 2 S-P 2 S 5 solid solid electrolytes, the E a for the Li/Li + couple reactions was quite close to that for ionic conduction due to the lack of the solvation/desolvation.

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Section: Resultsmentioning

confidence: 99%

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

et al. 2012

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“…This result confirms that semicircle A is attributable to the desolvation process according to the adatom model. 7,8 In contrast, the activation energy for semicircle B does not depend on whether EC + DEC or GBL is used as the solvent and does depend on the voltage; that is, the chemical potential of Li + , where the activation energy increases as the voltage is increased. Therefore, semicircle B does not originate from the properties of these electrolytes, but from the surface properties of the electrode material.…”

Section: Experimentmentioning

confidence: 99%

“…We thus conclude that semicircle B corresponds to the lattice incorporation process on the basis of the adatom model. 7,8 ■ DISCUSSION In the adatom model, two factorsdesolvation (semicircle A) and lattice incorporation (semicircle B)affect the Li + exchange at the electrode/electrolyte interface. Although the physicochemical interpretation is clear with respect to the desolvation process, there are ambiguities with respect to lattice incorporation.…”

Section: Experimentmentioning

confidence: 99%

“…We previously confirmed this twostep mechanism by using electrochemical impedance spectroscopy (EIS) for Li + insertion into perovskite-type La 1/3 NbO 3 . 8 Abe and colleagues have carried out particularly in depth experimental and computational studies on the adatom process for various materials, showing that solvation/desolvation of Li + is one of the key factors affecting the overall reaction kinetics in LIBs (e.g., refs 9−13). A clear atomic-level understanding of the mechanism for incorporating the Li + into the electrode lattice, however, remains elusive, which prevents rational design of the surface of electrode materials.…”

Section: ■ Introductionmentioning

confidence: 99%

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Combined Computational and Experimental Study of Li Exchange Reaction at the Surface of Spinel LiMn₂O₄ as a Rechargeable Li-Ion Battery Cathode

Nakayama

Taki

Nakamura³

et al. 2014

J. Phys. Chem. C

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Lithium manganese oxide (LiMn 2 O 4 ) is regarded as an attractive positive electrode for rechargeable Li-ion batteries, in particular for the power source of electric vehicles, and there is thus an urgent need to improve its charge−discharge kinetics. In the current paper, the kinetics of a Li-ion exchange reaction at the interface between a LiMn 2 O 4 cathode and nonaqueous liquid electrolytes is studied using experimental and computational techniques. Electrochemical ac impedance measurements showed two semicircles corresponding to the interfacial Li-ion exchange, and they are ascribed to the desolvation and lattice incorporation processes according to the adatom model [Bruce, P. G.; Saidi, M. Y. J. Electroanal. Chem. 1992, 322, 93]. To gain deeper insight into the latter process, delithiation from the electrode surface was simulated using density functional theory (DFT), and the DFT results were compared to the dependence of the ac impedance behavior on potential. We conclude that the chemical potential gradient is formed at the surface of positive electrodes, and the difference of the potential between the surface and the bulk corresponds to the activation energy of lattice incorporation. ■ INTRODUCTIONElectrochemical lithium intercalation is a reaction with particular significance to high-energy-density electrode materials used in Li-ion batteries (LIBs). 1−5 Thus, materials that possess lithium intercalation sites have attracted considerable attention owing to both the range of practical battery applications and the fundamental interest in the electrochemical electron/ion exchange reaction in the bulk of the electrode and at the interface of the electrode and electrolyte. This reaction involves a relatively simple mechanism: (1) the host crystal structure of the electrode remains almost unchanged from before to after the electrochemical reaction, and (2) the free energy of the reaction, the molar amount of reacted species, and kinetic parameters can be obtained easily by measuring cell voltage and electric current.There have been numerous reports on the bulk properties of the crystalline phases of LIB electrodes, such as their phase stability, crystal and electronic structures, and ion-diffusion properties. However, our understanding of the acquired knowledge on kinetic properties at the electrode/electrolyte interface, (i.e., the kinetics of fundamental electron/ion exchange reactions) is still limited at the atomic and electronic levels. In general, the kinetics of electron transfer in soluble redox systems, such as the ferrocene/ferrocenium redox couple, have been well established, according to the theory underlying the Butler−Volmer-type charge-transfer reaction. 6 In these reactions, electron transfer is assumed to occur at the electric double layer formed at the part of the liquid electrolyte adjacent to the surface of the electron-conductive solid-state electrode. The electron transfer reaction, however, takes place inside the solid-state electrode materials of LIB (oxidizing Co 3+ to Co 4+ for the ...

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“…It was first used to depict the lithium ions insertion/desertion process of LiTiS 2 by Bruce [19,20] in the lithium-ion battery field, and then was developed by Kobayashi as well as many others [40,71,76,114]. In this model, the intercalation reaction proceeds in several steps, as shown in Figure 2-1: a solvated cation in solution adjacent to the electrode loses part of its solvation sheath and becomes adsorbed, thus forming an adion, on the electrode surface, accompaning by the injection of an electron into the conduction band of the solid host.…”

Section: Kinetic Models For Lithium Ions Insertion Into the Intercalamentioning

confidence: 99%

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

Zhuang¹,

Qiu²,

Xu³

et al. 2012

Lithium Ion Batteries - New Developments

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Study on the AC Impedance Spectroscopy for the Li Insertion Reaction of Li_xLa_1/3NbO₃ at the Electrode−Electrolyte Interface

Cited by 79 publications

References 17 publications

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

Combined Computational and Experimental Study of Li Exchange Reaction at the Surface of Spinel LiMn₂O₄ as a Rechargeable Li-Ion Battery Cathode

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

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Study on the AC Impedance Spectroscopy for the Li Insertion Reaction of LixLa1/3NbO3 at the Electrode−Electrolyte Interface

Cited by 79 publications

References 17 publications

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

Microelectrode Studies on Kinetics of Charge Transfer at an Interface of Li Metal and Li2S-P2S5 Solid Electrolytes

Combined Computational and Experimental Study of Li Exchange Reaction at the Surface of Spinel LiMn2O4 as a Rechargeable Li-Ion Battery Cathode

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

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Study on the AC Impedance Spectroscopy for the Li Insertion Reaction of Li_xLa_1/3NbO₃ at the Electrode−Electrolyte Interface

Combined Computational and Experimental Study of Li Exchange Reaction at the Surface of Spinel LiMn₂O₄ as a Rechargeable Li-Ion Battery Cathode