Lithium-ion transfer on a LixCoO2 thin film electrode prepared by pulsed laser deposition—Effect of orientation-

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

doi:10.1016/j.jpowsour.2007.05.072

Cited by 72 publications

(72 citation statements)

References 11 publications

(10 reference statements)

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“…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: LIsupporting

confidence: 58%

“…+ 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%

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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

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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Section: LIsupporting

confidence: 58%

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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“…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%

(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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“…Our group focused on the kinetics of charge ͑lithium ion͒-transfer reactions at a graphite/electrolyte interface 14,15 and other interfaces. [16][17][18][19] The activation energies of the charge-transfer reactions were around 50 kJ mol −1 or more, which were higher compared to those of lithium-ion transport in solid [20][21][22][23] or liquid [24][25][26] electrolytes. This is because the desolvation of lithium ion from solvents occurs during the charge transfer at the interfaces, and the energy for the desolvation is large.…”

mentioning

confidence: 99%

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Yamada

Iriyama

Abe

et al. 2010

J. Electrochem. Soc.

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135

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The kinetics of the electrochemical insertion and extraction of lithium ion at silicon monoxide ͑SiO͒ were investigated by ac impedance spectroscopy. The resultant Nyquist plots showed two semicircles at high and middle frequency regions. These two semicircles were attributed to lithium-ion transport resistance in a surface film and alloying reaction resistance ͑charge-transfer resistance͒, respectively. We evaluated the activation energies of the charge-transfer reaction from the temperature dependences of the interfacial conductivities. When an ethylene-carbonate-based electrolyte was used, the activation energy of the charge transfer was 32 kJ mol −1 . This activation energy was much smaller than those at graphite electrode or positive electrode materials ͑around 50 kJ mol −1 or more͒. Based on these results, the charge transfer at SiO is exceptionally fast compared to those at other insertion materials. Furthermore, the activation energies of the charge transfer at SiO remained unchanged in various electrolytes. These results suggest that the charge-transfer kinetics at SiO is not influenced by the desolvation of lithium ion from solvent molecules. Lithium-ion batteries have recently attracted much attention as a power source for electric vehicles ͑EVs͒ and plug-in hybrid EVs. These applications of lithium-ion batteries give severe requirements to electrode materials. One such requirement is a significant improvement in the energy density of electrode materials. Therefore, an alternative electrode material has been explored for a much higher energy density. Among the candidates for a new negative electrode are alloying materials such as Si and Sn.1,2 These materials electrochemically react with lithium to form a lithium alloy that has an extremely high energy density compared to graphite. However, the alloying reaction shows a large volume change in the materials, 3 which leads to capacity fade during charge-discharge cycles. 4 To overcome the problem, silicon monoxide ͑SiO͒ has recently attracted much attention as a next generation negative electrode. 5-13SiO shows a small volume change because it contains a relatively small amount of Si element that is active for the alloying reaction. The discharge capacity of SiO electrodes was reported to be over 600 mAh g −1 in several papers, 9-12 which is much higher than that of a graphite electrode ͑372 mAh g −1 ͒. To commercialize the SiO electrode, we need to consider the rate performance in addition to the energy density. However, there are few reports on the kinetic aspect of alloying materials. Our group focused on the kinetics of charge ͑lithium ion͒-transfer reactions at a graphite/electrolyte interface 14,15 and other interfaces. [16][17][18][19] The activation energies of the charge-transfer reactions were around 50 kJ mol −1 or more, which were higher compared to those of lithium-ion transport in solid [20][21][22][23] or liquid [24][25][26] electrolytes. This is because the desolvation of lithium ion from solvents occurs during the charge transfer at the...

show abstract

Lithium-ion transfer on a LixCoO2 thin film electrode prepared by pulsed laser deposition—Effect of orientation-

Cited by 72 publications

References 11 publications

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

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

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

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

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Lithium-ion transfer on a LixCoO2 thin film electrode prepared by pulsed laser deposition—Effect of orientation-

Cited by 72 publications

References 11 publications

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

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

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

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

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Product

Resources

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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

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