Chemical Analysis of Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes

Xu, Ke; Lee, Unchul; Zhang, Sheng S.; Wood, Mark E.; Jow, T. Richard

doi:10.1149/1.1576049

Cited by 173 publications

(139 citation statements)

References 19 publications

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“…14,15 It is worthy to note that the detailed structure and formation mechanisms of the SEI layers formed by reduction and oxidation of LiBOB are different. 14,18 Further evidence for the LiBOB-originated SEI is given by comparison of the carboxylate/carbonate (C=O) peak of the O 1s XPS spectra. The O 1s spectra for the Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 cathode surface in the LiBOB-added electrolyte clearly exhibits a more pronounced peak corresponding to C=O at 531.8 eV.…”

Section: Resultsmentioning

confidence: 99%

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries

Lee

Han

Park

et al. 2014

J. Electrochem. Soc.

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Lithium bis(oxalato)borate (LiBOB) is utilized as an oxidative additive to prevent the unwanted electrolyte decomposition on the surface of Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 cathodes. Our investigation reveals that the LiBOB additive forms a protective layer on the cathode surface and effectively mitigates severe oxidative decomposition of LiPF 6 -based electrolytes. Noticeable improvements in the cycling stability and rate capability of Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 cathodes are achieved in the LiBOB-added electrolyte. After 100 cycles at 60 • C, the discharge capacity retention of the Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 cathode was 28.6% in the reference electrolyte, whereas the LiBOB-containing electrolyte maintained 77.6% of its initial discharge capacity. Moreover, the Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 cathode with LiBOB additive delivered a superior discharge capacity of 115 mAh g −1 at a high rate of 2 C compared with the reference electrolyte. The OCV of a full cell charged in the reference electrolyte drastically decreased from 4.22 V to 3.52 V during storage at 60 • C, whereas a full cell charged in the LiBOB-added electrolyte exhibited superior retention of the OCV. . [1][2][3][4] Because a large reversible capacity of lithium-rich cathodes is attained with the condition of charging to the voltage range of 4.6-4.8 V at the first charge, 1 the oxidative decomposition of LiPF 6 /carbonate-based electrolytes occurring above 4.5 V vs. Li/Li + is inevitable. 5,6 The anodic limit of current electrolytes is not high enough to prevent such side reactions, which results in the formation of a resistive surface film on the cathode and continuous electrolyte decomposition at high voltages. Therefore, these undesired reactions limit the practical application of lithium-rich cathode materials. From this viewpoint, the formation of surface films through the use of oxidative additives in the electrolytes is thought to be one of the most effective strategies to stabilize the cathode-electrolyte interface in lithium-ion batteries (LIBs). 7,8 Recently, many research groups have reported the effect of electrolyte additives preventing significant electrolyte decomposition at lithium-rich cathodes that are operated above 4.5 V.9-13 Tri(hexafluoro-iso-propyl)phosphate (HFiP) was proposed as a oxidative additive (OA) to improve the cycling performance of the lithium-rich cathode Li 8 These authors also reported that the salt-type additive, LiFOB, can serve as a bi-functional additive, modifying the cathode and anode interfaces, in a subsequent paper.14 In addition, it has been reported that a LiFOB-lithium bis(oxalato)borate (LiBOB) combination leads to an improvement in the electrochemical performances of graphite/Li 1.2 Mn 0.55 Ni 0.15 Co 0.1 O 2 full cells 30• C. Lu et al. reported that the LiFOB additive improved the cycling stability of graphite/xLi 2 MnO 3 · (1-x)LiMO 2 full cells at room temperature. 4 These authors mentioned that the LiFOB-originated solid electrolyte interphase (SEI) on the anode effectively ...

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Section: Resultsmentioning

confidence: 99%

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries

Lee

Han

Park

et al. 2014

J. Electrochem. Soc.

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“…It is known that the BOB ¹ forms a compact SEI layer at 1.7 V vs. Li, and the SEI layer prevents the co-intercalation of propylene Electrochemistry, 84(11), 854-860 (2016) carbonate (PC) into the graphite. 26 We think the LiBOB forms the very similar compact SEI layer, which suppresses the decomposition of the PF 6 ¹ and the formation of Li x PO y F z . The Li 1s and the O 1s spectra were very similar to the XPS spectra for the electrolyte solution containing VC.…”

Section: Sei Layer In the Electrolyte Solutions Containing Additivesmentioning

confidence: 92%

Surface Layer and Morphology of Lithium Metal Electrodes

et al. 2016

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The surface morphology of the electrodeposited lithium metal from electrolyte solutions containing electrolyte additives: fluoroethylene carbonate (FEC), vinylene carbonate (VC) and lithium bis(oxalate)borate (LiBOB), were investigated. All the film forming additive improved the surface morphology. The FEC especially shows the most uniform surface morphology compared with the other electrolyte additives and the additive-free electrolyte. The surface analyses of the lithium metal were conducted using X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The analytical study revealed that the FEC suppresses the decomposition of the PF 6 − anion, resulting in the formation of a thin stable SEI layer on the lithium metal.

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“…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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Chemical Analysis of Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes

Cited by 173 publications

References 19 publications

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries

Surface Layer and Morphology of Lithium Metal Electrodes

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

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Chemical Analysis of Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes

Cited by 173 publications

References 19 publications

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li1.17Ni0.17Mn0.5Co0.17O2Cathodes for Lithium-Ion Batteries

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li1.17Ni0.17Mn0.5Co0.17O2Cathodes for Lithium-Ion Batteries

Surface Layer and Morphology of Lithium Metal Electrodes

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

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Product

Resources

About

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries

Effect of Lithium Bis(oxalato)borate Additive on Electrochemical Performance of Li_1.17Ni_0.17Mn_0.5Co_0.17O₂Cathodes for Lithium-Ion Batteries