Lithium-ion transfer at LiMn2O4 thin film electrode prepared by pulsed laser deposition

Yamada, Izumi; Abe, Takeshi; Iriyama, Yasutoshi; Ogumi, Zempachi

doi:10.1016/s1388-2481(03)00113-9

Cited by 146 publications

(105 citation statements)

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“…The values of the activation energy obtained for Li + charge transfer across the interfaces at the Li 4/3 Ti 5/3 O 4 , LiMn 2 O 4 , and LiCoO 2 electrodes are about 44-48, 50 and 46 kJ/mol [13][14][15] , respectively. The values of the activation energy are even slightly lower for Li + charge transfer across the interface at these electrodes than that at the HOPG electrode suggesting that the Li + charge transfer kinetics are electrode dependent.…”

Section: + Charge Transfer Kinetics Studiesmentioning

confidence: 88%

“…Li + charge transfer kinetics at the interface between the thin film lithium transition metal oxide electrodes such as Li 4 13 and Yamada et al [14][15] . The values of the activation energy obtained for Li + charge transfer across the interfaces at the Li 4/3 Ti 5/3 O 4 , LiMn 2 O 4 , and LiCoO 2 electrodes are about 44-48, 50 and 46 kJ/mol [13][14][15] , respectively.…”

Section: + Charge Transfer Kinetics Studiesmentioning

confidence: 99%

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(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

et al. 2010

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Charge discharge kinetics of Li-ion batteries is dominated by the lithium ion (Li + ) charge transfer kinetics, which involves the process of transporting the solvated Li + in the electrolyte to the insertion of Li + and the accepting of an electron at the same time in the electrode active materials. The importance of electrolytes and recent studies of Li + charge transfer kinetics were briefly reviewed. Using 3-electrode cells and a DC Pulse Current Impedance method, we examined the charge discharge kinetics of the anode and the cathode in the same electrolyte at the same time. We observed a slower kinetics at the graphitic carbon anode as indicated by higher activation energy than that at the lithium nickel cobalt aluminum mixed oxide (LiNi 0.80 Co 0.15 Al 0.05 O 2 ) cathode. While desolvation is a dominating step as concluded in recent studies on the Li + charge transfer kinetics, this study suggests that the nature of SEIs and electrode materials play crucial roles on Li + charge discharge kinetics.

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Section: + Charge Transfer Kinetics Studiesmentioning

confidence: 88%

Section: + Charge Transfer Kinetics Studiesmentioning

confidence: 99%

(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

et al. 2010

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“…+ charge transfer kinetics across various electrode/electrolyte interfaces was extensively studied by the group led by Ogumi and Abe (1)(2)(3)(4)(5)(6)(7) [5][6][7] , respectively, which are also large and appear only to be slightly lower than that for Li + charge transfer across that at the HOPG/electrolyte interface. The similar E a for both electrodes seem to suggest that the Li + charge transfer kinetics at both the transition metal oxides cathode and the graphite anode are limited by the same charge transfer step, which is the de-solvation step as identified by Ogumi and Abe et al (1)(2)(3)(4)(5)(6)(7).…”

Section: LImentioning

confidence: 99%

Distinguishing Li⁺ Charge Transfer Kinetics at 1. NCA/Electrolyte and Graphite/Electrolyte Interfaces and 2. NCA/Electrolyte and LFP/Electrolyte Interfaces in Li-ion Cells

2011

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In examining the Li + charge transfer kinetics at the graphite anode and the lithium nickel cobalt aluminum oxide, LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA), cathode in a complete cell, we found that the activation energy, E a , for the charge transfer at the graphite/electrolyte interface is about 68 kJ/mol, which is consistent with the recently reported values. However, the E a for the charge transfer at the NCA/electrolyte interface is about 50 kJ/mol, which is lower than that at the graphite anode. With desolvation as the predominate step for limiting the kinetics and both of the electrodes were subject to the same electrolyte, the difference in E a suggests that the E a is influenced greatly with respect to the nature of electrode materials and their associated SEIs. This is further confirmed by the examination of the LiFePO 4 (LFP)/electrolyte and the graphite/electrolyte interfaces using a LFP/graphite complete cell.

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“…This result agreed well with a previous paper. 21 Effects of chain structure in the substituent on the interfacial resistance at the LiMn 2 O 4 thin-film electrodes/liquid electrolytes with boroxine compounds.- Figure 4a summarizes the CVs of LiMn 2 O 4 thin-film electrodes at 3.5-4.5 V in different kinds of liquid electrolytes. Two couples of redox peaks assigned to the lithium insertion/extraction reaction into LiMn 2 O 4 were clearly observed in every case.…”

Section: Resultsmentioning

confidence: 99%

High Voltage Stability of Interfacial Reaction at the LiMn[sub 2]O[sub 4] Thin-Film Electrodes/Liquid Electrolytes with Boroxine Compounds

Horino¹,

Tamada²,

Kishimoto³

et al. 2010

J. Electrochem. Soc.

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Liquid electrolytes with boroxine compounds were prepared, and interfacial reactions at the liquid electrolytes/LiMn 2 O 4 thin-film electrodes were investigated. Boroxine compounds, B 3 O 3 ͑OR͒ 3 , with different kinds of substituents ͓R = CH 3 , CH 2 CH 3 , ͑CH 2 ͒ 2 CH 3 , and CH͑CH 3 ͒ 2 ͔ were dissolved in 1 mol kg −1 LiCF 3 SO 3 /ethylene carbonate + EMC ͑1:1 by volume͒. Both cyclic voltammetry and electrical impedance spectroscopy measurements revealed that interfacial resistance depended on the chain length in the substituent of the boroxine compounds, and the resistance decreased with the increase in the chain length. Moreover, the anodic stability of the electrolytes was improved up to 5.0 V ͑vs Li/Li + ͒ on the film electrodes by the addition of tri-isopropoxy boroxine ͓R = CH͑CH 3 ͒ 2 ͔ with a steric structure ͑branched chain substituent͒. These results indicate that mixing boroxine compounds with both appropriate chain length and steric structure can be an effective way to develop advanced liquid electrolytes for high voltage rechargeable lithium ion batteries. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3374638͔ All rights reserved. Rechargeable lithium ion batteries have been expected as power sources for hybrid and electric vehicles, and some of them have been commercialized. However, further improvements in the current battery system are strongly demanded at the social end, and one of the most expected properties is the enhancement of energy density to prolong the cruising distance of electric vehicles. In this prospect, increase in battery operating voltage must be a possible way because there are several kinds of 5 V class positive electrode materials such as LiNi 0.5 Mn 1.5 O 4 , 1 LiCoPO 4 , 2 and LiCoMnO 4 . 3One of the drawbacks to realize 5 V class rechargeable lithium ion batteries is to develop advanced electrolytes with a wide potential window, high ionic conductivity, sufficient safety, low cost, etc. Although new kinds of electrolytes, typically ionic liquids 4 and solid electrolytes, 5 have been proposed, several problems such as cost, power density, and large resistance at the interface still remained to put them in practical use.In addition to the developments of the above electrolytes, various boron-based compounds have been studied as a new class of electrolytes. Zhang and Angell discovered the electrolytes with boronbased cosolvent. They showed that the electrolyte obtains an approximately 5 V stability on platinum electrodes and that the electrolyte can work well in both Li/LiMnO 2 and carbon/LiMnO 2 cells at 2.0-4.4 V.6 Barthel et al. proposed new lithium salts with a cherate-type anion of boron. 7,8 Sasaki et al. prepared their derivatives and applied them to a practical lithium ion battery system. 9,10Although the anodic stability of these lithium salts was ca. 4.2 V vs Li/Li + , Xu and Angell discovered lithium bis͑oxalate͒ borate ͑Li-BOB͒, which obtained superior anodic stability up to 4.5 V vs Li/Li + on platinum electrode. 11 The LiBOB obtained other interactiv...

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Lithium-ion transfer at LiMn2O4 thin film electrode prepared by pulsed laser deposition

Cited by 146 publications

References 11 publications

(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

Distinguishing Li⁺ Charge Transfer Kinetics at 1. NCA/Electrolyte and Graphite/Electrolyte Interfaces and 2. NCA/Electrolyte and LFP/Electrolyte Interfaces in Li-ion Cells

High Voltage Stability of Interfacial Reaction at the LiMn[sub 2]O[sub 4] Thin-Film Electrodes/Liquid Electrolytes with Boroxine Compounds

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Lithium-ion transfer at LiMn2O4 thin film electrode prepared by pulsed laser deposition

Cited by 146 publications

References 11 publications

(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

(Invited) Electrolytes, SEI and Charge Discharge Kinetics in Li-Ion Batteries

Distinguishing Li+ Charge Transfer Kinetics at 1. NCA/Electrolyte and Graphite/Electrolyte Interfaces and 2. NCA/Electrolyte and LFP/Electrolyte Interfaces in Li-ion Cells

High Voltage Stability of Interfacial Reaction at the LiMn[sub 2]O[sub 4] Thin-Film Electrodes/Liquid Electrolytes with Boroxine Compounds

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Distinguishing Li⁺ Charge Transfer Kinetics at 1. NCA/Electrolyte and Graphite/Electrolyte Interfaces and 2. NCA/Electrolyte and LFP/Electrolyte Interfaces in Li-ion Cells