LiCoO2 electrode/electrolyte interface of Li-ion rechargeable batteries investigated by in situ electrochemical impedance spectroscopy

Itagaki, Masayuki; Kobari, Nao; Yotsuda, Sachiko; Watanabe, Kunihiro; Kinoshita, Shinichi; Ue, Makoto

doi:10.1016/j.jpowsour.2005.02.007

Cited by 110 publications

(72 citation statements)

References 23 publications

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“…Numerous recent studies have been published on various aspects of the insertion electrodes used in lithium-ion batteries for the attempt to understand the origin of the observed capacity loss during extended cell cycling or storage [1,30,37,52,66,78,97].…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…Itagaki et al 9 showed that for LiCoO 2 /Li "half" cells, the presence of VC has a slight influence on the charge transfer resistance at room temperature.…”

mentioning

confidence: 99%

The Limited Effect of VC in Graphite/NMC Cells

Deshpande

Ridgway

et al. 2014

J. Electrochem. Soc.

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Degradation at the electrode surfaces is one of the major reasons behind capacity fade in well-constructed batteries. The effect of electrolyte additives, in particular vinylene carbonate (VC), is studied extensively for different lithium-ion chemistries and is shown to improve columbic efficiency of some electrodes. We investigate the effect of VC additive in a graphite/NMC333 (lithiumnickel-manganese-cobalt oxide) cell. The addition of VC improves the rate performance, especially, at moderately high rates. A new three-electrode cell design with Li reference electrode was particularly useful in studying the rate performance of each electrode. The rate of side reactions is found to decrease with the addition of VC. Despite these important performance improvements, no significant improvement in the capacity retention is observed. This suggests that the side reactions in graphite/NCM cells consist of two types, (1) repairing cracked solid electrolyte interphase (SEI) on the negative electrode (results in a net consumption of Li from the positive electrode), (2) reforming SEI components that dissolve from the negative electrode and are oxidized at the positive electrode. The VC appears to reduce the second type but have negligible effect on the first. This indicates that columbic efficiency measurements are not a reliable indicator of cell cycle life. Electrode side reactions are one of the major reasons for the loss of performance of Li-ion batteries. The instability of commonly used electrolytes at typical operating potentials results in side reactions, some of which go to solid electrolyte interphase (SEI) formation at electrode surfaces.1-4 Using electrolyte additives is one effective way to minimize the rate of chemical degradation. Electrolyte additives also may be used to form a thinner, more compact and stable SEI, and thus reduce irreversible capacity loss, reduce parasitic reactions, and improve thermal stability of LiPF 6 salt against the electrolyte solvents. Zhang et al.5 nicely summarize different electrolyte additive studies in the literature classifying them by their SEI stabilization mechanism. In lithium ion batteries, electrolyte additives tend to affect two aspects of cell characteristics, namely, cell impedance and side reactions. In the present work the effect of Vinylene carbonate (VC) on both of these parameters was studied. In the first part of this article, the effect of electrolyte additive on the impedance of the individual electrodes using 3-electrode cell is illustrated. The second part correlates the effect of VC on cell side reactions and coulombic efficiency. This study was useful to demonstrate our hypothesis that coulombic efficiency is not a reliable indicator of cell cycle life.Vinylene carbonate (VC) has been extensively studied as an electrolyte additive and shown to improve battery life in some lithiumion battery chemistries.6 Aurbach et al. 1 observed a reduction of the impedance of synthetic graphite flakes, LiNiO 2 , and LiMn 2 O 4 electrodes against lithium counter electr...

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“…The increase in R ct value of the cathode is in accordance with results from previous studies. 45,49,50 This increase is partly due to the variation of electronic conductivity in the active material, Li x CoO 2.…”

Section: ( ) (D) and (E)mentioning

confidence: 99%

Impedance Analysis with Transmission Line Model for Reaction Distribution in a Pouch Type Lithium-Ion Battery by Using Micro Reference Electrode

Nara

Mukoyama

Yokoshima

et al. 2015

J. Electrochem. Soc.

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Electrochemical impedance spectroscopy (EIS) using an equivalent circuit is a powerful tool in the diagnosis of lithium-ion batteries (LIBs). However, LIBs have been increasingly used in applications requiring power higher than that used for conventional LIBs for portable electric devices. Considering this demand for LIBs, the ionic resistances in the electrodes, which raise a reaction distribution under high-power operation, are important. This consequently means EIS analysis should include ionic resistances in the electrodes in equivalent circuits. Additionally, the impedance response of LIBs are too complicated to be analyzed in detail because the impedance response consists of overlapping elemental processes such as chemical reactions and ion migration. This paper therefore presents an analysis of impedance responses, which are independently obtained by a micro reference electrode, by using a transmission line model (TLM) that possesses the ability to count the ionic resistances in the electrodes. Similar to the conventional Randles equivalent circuit, the equivalent circuit with TLM could fit the impedance responses simulated by the equivalent circuit with measured responses. This paper discusses the potential of EIS using an equivalent circuit coupled with a TLM for diagnosis of LIBs in power applications.

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LiCoO2 electrode/electrolyte interface of Li-ion rechargeable batteries investigated by in situ electrochemical impedance spectroscopy

Cited by 110 publications

References 23 publications

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

The Limited Effect of VC in Graphite/NMC Cells

Impedance Analysis with Transmission Line Model for Reaction Distribution in a Pouch Type Lithium-Ion Battery by Using Micro Reference Electrode

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