Intrinsic Interfacial Property between High-Voltage LiNi_0.5Mn_1.5O₄ Cathode and Electrolyte

Authors

Li LI, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215125, China;University of science and technology of China, Nanoscience and Technology Institute, Suzhou, Jiangsu 215125, China;
Jing-jing XU, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215125, China;
Shao-jie HAN, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215125, China;
Wei LU, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215125, China;
Li-wei Chen, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215125, China;Follow

Corresponding Author

Li-wei Chen(lwchen2008@sinano.ac.cn)

Abstract

To obtain high energy density, developing high-voltage cathode materials is an effective approach. The cathode/electrolyte interface stability is the key factor for the cycle performance and safety performance of high-voltage lithium ion batteries. It is, therefore, of significant importance to study the stability of cathode/electrolyte interface. However, many reports have shown that at the cathode/electrolyte interface the cathodes were prepared by coating the mixture of active materials with a conductive additive and a binder on an Al current collector. The introduction of additives will interfere the surface morphology and component analyses, resulting in difficulty to acquire the intrinsic information at the cathode/electrolyte interface. In this paper, the LiNi_0.5Mn_1.5O₄ (LNMO) film electrodes were prepared via sol-gel method without using conductive additive and binder. The surface morphology and the intrinsic property of LNMO electrode/electrolyte interface during the charge/discharge process were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Electrochemical impedance spectroscopy (EIS). The results demonstrated that both solvents and LiPF₆ salt degraded during the charge/discharge process. The degradation of LiPF₆ mainly happened at the high-voltage charge process and the intermediate POF₃ was unstable which continued to be reacted during the discharge process. The degraded residues deposit on the surface of LNMO cathode to form a surface film and the compositions of the surface film varied with voltages during the electrochemical process.

Graphical Abstract

Keywords

high-voltage LiNi0.5Mn1.5O4 cathode material, cathode/electrolyte interface, intrinsic property, solid electrolyte interphase, oxidized decomposition of electrolyte, surface film

DOI Link

https://doi.org/10.13208/j.electrochem.160564

Publication Date

2016-12-28

Online Available Date

2016-07-29

Revised Date

2016-07-27

Received Date

2016-06-16

Recommended Citation

Li LI, Jing-jing XU, Shao-jie HAN, Wei LU, Li-wei Chen. Intrinsic Interfacial Property between High-Voltage LiNi_0.5Mn_1.5O₄ Cathode and Electrolyte[J]. Journal of Electrochemistry, 2016 , 22(6): 582-589.
DOI: 10.13208/j.electrochem.160564
Available at: https://jelectrochem.xmu.edu.cn/journal/vol22/iss6/6

References

[1] Okubo M, Hosono E, Kim J, et al. Nanosize effect on high-rate Li-ion intercalation in LiCoO₂ electrode[J]. Journal of the American Chemical Society, 2007, 129(23): 7444-7452.

[2] Zhu JP, Xu QB, Junjie-Zhao, et al. Synthesis and Electrochemical Properties of Modification LiNi_1/3Co_1/3Mn_1/3O₂ Cathode Materials for Li-ion Battery[J]. Journal of Nanoscience and Nanotechnology, 2012, 12(3): 2534-2538.

[3] Okubo M, Mizuno Y, Yamada H, et al. Fast Li-Ion Insertion into Nanosized LiMn₂O₄ without Domain Boundaries[J]. ACS Nano, 2010, 4(2): 741-752.

[4] Li QY, Zheng FH, Huang YG, et al. Surfactants assisted synthesis of nano-LiFePO₄/C composite as cathode materials for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(5): 2025-2035.

[5] Liu J, Manthiram A. Understanding the Improved Electrochemical Performances of Fe-Substituted 5 V Spinel Cathode LiMn_1.5Ni_0.5O₄[J]. Journal of Physical Chemistry C, 2009, 113(33): 15073-15079.

[6] Kim K, Kim Y, Oh ES, et al. The role of fluoride in protecting LiNi_0.5Mn_1.5O₄ electrodes against high temperature degradation[J]. Electrochimica Acta, 2013, 114: 387-393.

[7] Konishi H, Suzuki K, Taminato S, et al. Effect of surface Li₃PO₄ coating on LiNi_0.5Mn_1.5O₄ epitaxial thin film electrodes synthesized by pulsed laser deposition[J]. Journal of Power Sources, 2014, 269(4): 293-298.

[8] Manthiram A, Chemelewski K, Lee ES. A perspective on the high-voltage LiMn_1.5Ni_0.5O₄ spinel cathode for lithium-ion batteries[J]. Energy & Environmental Science, 2014, 7(4): 1339-1350.

[9] Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. Chemical Reviews, 2004, 104(10): 4303-4417.

[10] Zhang SS. A review on electrolyte additives for lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 1379-1394.

[11] Liu J, Manthiram A. Kinetics Study of the 5 V Spinel Cathode LiMn_1.5Ni_0.5O₄ Before and After Surface Modifications[J]. Journal of Electrochemical Society, 2009, 156(12): A833-A838.

[12] Wu HM, Belharouak I, Abouimrane A, et al. Surface modification of LiNi_0.5Mn_1.5O₄ by ZrP₂O₇ and ZrO₂ for lithium-ion batteries[J]. Journal of Power Sources, 2010, 195(5): 2909-2913.

[13] Xu JJ, Hu YY, Liu T, et al. Improvement of cycle stability for high-voltage lithium-ion batteries by in-situ growth of SEI film on cathode[J]. Nano Energy, 2014, 5(4): 67-73.

[14] Choi NS, Han JG, Ha SY, et al. Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries[J]. RSC Advances, 2015, 5(4): 2732-48.

[15] Bae SY, Shin WK, Kim DW. Protective organic additives for high voltage LiNi_0.5Mn_1.5O₄ cathode materials[J]. Electrochimica Acta, 2014, 125(12): 497-502.

[16] Li B, Wang YQ, Tu WQ, et al. Improving cyclic stability of lithium nickel manganese oxide cathode for high voltage lithium ion battery by modifying electrode/electrolyte interface with electrolyte additive[J]. Electrochimica Acta, 2014, 147: 636-642.

[17] Wang Y, Peng Q, Yang G, et al. High-stability 5 V spinel LiNi_0.5Mn_1.5O₄ sputtered thin film electrodes by modifying with aluminium oxide[J]. Electrochimica Acta, 2014, 136(8): 450-456.

[18] Xu JJ, Xia QB, Chen FY, et al. Facilely solving cathode/electrolyte interfacial issue for high-voltage lithium ion batteries by constructing an effective solid electrolyte interface film[J]. Electrochimica Acta, 2016, 191: 687-694.

[19] Han JG, Lee SJ, Lee J,et al. Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries. ACS Applied Materials & Interfaces, 2015, 7(15): 8319-8329.

[20] Gellert M, Gries KI, Zakel J, et al. LiNi_0.5Mn_1.5O₄ Thin-Film Cathodes on Gold-Coated Stainless Steel Substrates: Formation of Interlayers and Electrochemical Properties[J]. Electrochimica Acta, 2014, 133: 146-152.

[21] Talyosef Y, Markovsky B, Salitra G, et al. The study of LiNi_0.5Mn_1.5O₄ 5-V cathodes for Li-ion batteries[J]. Journal of Power Sources, 2005, 146(1): 664-669.

[22] Chong J, Xun SD, Zhang JP, et al. Li₃PO₄-Coated LiNi_0.5Mn_1.5O₄: A Stable High-Voltage Cathode Material for Lithium-Ion Batteries[J]. Chemistry-European Journal, 2014, 20(24): 7479-7485.

[23] Tan S, Ji YJ, Zhang ZR, et al. Recent Progress in Research on High-Voltage Electrolytes for Lithium-Ion Batteries[J]. Chemphyschem, 2014, 15(10): 1956-1969.

[24] Aurbach D, Levi MD, Levi E, et al. Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides[J]. Journal of Electrochemical Society, 1998, 145(9): 3024-3034.

[25] Duncan H, Duguay D, Abu-Lebdeh Y, et al. Study of the LiMn_1.5Ni_0.5O₄∕Electrolyte Interface at Room Temperature and 60°C[J]. Journal of Electrochemical Society, 2011, 158(5): A537-A545.

[26] Duncan H, Abu-Lebdeh Y, Davidson IJ. Study of the Cathode€“Electrolyte Interface of LiMn_1.5Ni_0.5O₄ Synthesized by a Sol€“Gel Method for Li-Ion Batteries[J]. Journal of Electrochemical Society, 2010, 157(4): A528-A535.

[27] Yang L, Ravdel B, Lucht BL. Electrolyte Reactions with the Surface of High Voltage LiNi_0.5Mn_1.5O₄ Cathodes for Lithium-Ion Batteries[J]. Electrochemical and Solid-State Letters, 2010, 13(8): A95-A97.

[28] Kim JW, Kim DH, Oh DY, et al. Surface chemistry of LiNi_0.5Mn_1.5O₄ particles coated by Al₂O₃ using atomic layer deposition for lithium-ion batteries[J]. Journal of Power Sources, 2015, 274: 1254-1262.

[29] Haik O, Leifer N, Samuk-Fromovich Z, et al. On the Surface Chemistry of LiMO₂ Cathode Materials (M=[MnNi] and [MnNiCo]): Electrochemical, Spectroscopic, and Calorimetric Studies[J]. Journal of Electrochemical Society, 2010, 157(10): A1099-A1107.

[30] Wu C, Bai Y, Wu F. Fourier-transform infrared spectroscopic studies on the solid electrolyte interphase formed on Li-doped spinel Li_1.05Mn_1.96O₄ cathode[J]. Journal of Power Sources, 2009, 189(1): 89-94.