Electrochemical performance of a nickel-rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode material for lithium-ion batteries under different cut-off voltages

Abstract

A spherical-like Ni_0.6Co_0.2Mn_0.2(OH)₂ precursor was tuned homogeneously to synthesize LiNi_0.6Co_0.2Mn_0.2O₂ as a cathode material for lithium-ion batteries. The effects of calcination temperature on the crystal structure, morphology, and the electrochemical performance of the as-prepared LiNi_0.6Co_0.2Mn_0.2O₂ were investigated in detail. The as-prepared material was characterized by X-ray diffraction, scanning electron microscopy, laser particle size analysis, charge–discharge tests, and cyclic voltammetry measurements. The results show that the spherical-like LiNi_0.6Co_0.2Mn_0.2O₂ material obtained by calcination at 900°C displayed the most significant layered structure among samples calcined at various temperatures, with a particle size of approximately 10 μm. It delivered an initial discharge capacity of 189.2 mAh•g⁻¹ at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V. The as-prepared cathode material also exhibited good rate performance, with a discharge capacity of 119.6 mAh•g⁻¹ at 5C. Furthermore, within the cut-off voltage ranges from 2.7 to 4.3, 4.4, and 4.5 V, the initial discharge capacities of the calcined samples were 170.7, 180.9, and 192.8 mAh•g⁻¹, respectively, at a rate of 1C. The corresponding retentions were 86.8%, 80.3%, and 74.4% after 200 cycles, respectively.

Keywords

lithium-ion batteries / cathodic materials / calcination / electrochemical properties

References

[1] Gibot P., Casas-Cabanas M., Laffont L., Levasseur S., Carlach P., Hamelet S., Tarascon J.M., Masquelier C. Room-temperature single-phase Li insertion/extraction in nanoscale Li_xFePO₄. Nat. Mater., 2008, 7(9): 741.

[2] Tarascon J.M., Armand M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001, 414(6861): 359.

[3] Yang Z.G., Zhang J.L., Kintner-Meyer M.C.W., Lu X.C., Choi D., Lemmon J.P., Liu J. Electrochemical energy storage for green grid. Chem. Rev., 2011, 111(5): 3577.

[4] Yu L.Y., Qiu W.H., Huang J.Y., Lian F. Synthesis and electrochemical characteristics of xLi₂MnO₃·(1−x)Li-(Ni_1/3Co_1/3Mn_1/3)O₂ compounds. Int. J.^Miner. Metall. Mater, 2009, 16(4): 458.

[5] Yun S.H., Park K.S., Park Y.J. The electrochemical property of ZrF_x-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material. J.^Power Sources, 2010, 195(18): 6108.

[6] Choi J., Manthiram A. Crystal chemistry and electrochemical characterization of layered LiNi_0.5−yCo_0.5−yMn_2yO₂ and LiCo_0.5−yMn_0.5−yNi_2yO₂ (0≤2y≤1) cathodes. J.^Power Sources, 2006, 162(1): 667.

[7] Kim M.H., Shin H.S., Shin D., Sun Y.K. Synthesis and electrochemical properties of Li[Ni_0.8Co_0.1Mn_0.1]O₂ and Li[Ni_0.8Co_0.2]O₂ via co-precipitation. J.^Power Sources, 2006, 159(2): 1328.

[8] Ohzuku T., Makimura Y. Layered lithium insertion material of LiCo_1/3Ni_1/3Mn_1/3O₂ for lithium-ion batteries. Chem. Lett., 2001, 30(7): 642.

[9] Luo W.B., Li X.H., Dahn J.R. Synthesis, characterization, and thermal stability of Li[Ni_1/3Mn_1/3Co_1/3−z(MnMg) _z/2]O₂. Chem. Mater., 2010, 22(17): 5065.

[10] Santhanam R., Rambabu B. High rate cycling performance of Li_1.05Ni_1/3Co_1/3Mn_1/3O₂ materials prepared by sol–gel and co-precipitation methods for lithium-ion batteries. J.^Power Sources, 2010, 195(13): 4313.

[11] Chen Y., Wang G.X., Konstantinov K., Liu H.K., Dou S.X. Synthesis and characterization of LiCo_xMn_yNi_1−x−yO₂ as a cathode material for secondary lithium batteries. J.^Power Sources, 2003, 119-121, 184.

[12] Li J.G., Wang L., Zhang Q., He X.M. Synthesis and characterization of LiNi_0.6Mn0.4−xCoxO₂ as cathode materials for Li-ion batteries. J.^Power Sources, 2009, 189(1): 28.

[13] Liao P.Y., Duh J.G., Sheen S.R. Microstructure and electrochemical performance of LiNi_0.6Co_0.4−xMn_xO₂ cathode materials. J.^Power Sources, 2005, 143(1-2): 212.

[14] Zhang Y., Cao H., Zhang J., Xia B.J. Synthesis of Li-Ni_0.6Co_0.2Mn_0.2O₂ cathode material by a carbonate co-precipitation method and its electrochemical characterization. Solid State Ionics, 2006, 177(37): 3303.

[15] Zhong S.K., Wei L., Zuo Z.G., Tang X., Li Y.H. Synthesis and electrochemical performances of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials. Trans. Nonferrous Met. Soc. China, 2009, 19(6): 1499.

[16] Gan C.L., Hu X.H., Zhan H., Zhou Y.H. Synthesis and characterization of Li_1.2Ni_0.6Co_0.2Mn_0.2O_2+δ as a cathode material for secondary lithium batteries. Solid State Ionics, 2005, 176(7-8): 687.

[17] Saavedra-Arias J.J., Karan N.K., Pradhan D.K., Kumar A., Nieto S., Thomas R., Katiyar R.S. Synthesis and electrochemical properties of Li(Ni_0.8Co_0.1Mn_0.1)O₂ cathode material: ex situ structural analysis by Raman scattering and X-ray diffraction at various stages of charge–discharge process. J.^Power Sources, 2008, 183(2): 761.

[18] Yue P., Wang Z.X., Guo H.J., Wu F.X., He Z.J., Li X.H. Effect of synthesis routes on the electrochemical performance of Li[Ni_0.6Co_0.2Mn_0.2]O₂ for lithium ion batteries. J.^Solid State Electr., 2012, 16(12): 3849.

[19] Yue P., Wang Z.X., Peng W.J., Li L.J., Chen W., Guo H.J., Li X.H. Spray-drying synthesized LiNi_0.6Co_0.2Mn_0.2O₂ and its electrochemical performance as cathode materials for lithium ion batteries. Powder Technol., 2011, 214(3): 279.

[20] Yue P., Wang Z.X., Peng W.J., Li L.J., Guo H.J., Li X.H., Hu Q.Y., Zhang Y.H. Preparation and electrochemical properties of submicron LiNi_0.6Co_0.2Mn_0.2O₂ as cathode material for lithium ion batteries. Scripta Mater., 2011, 65(12): 1077.

[21] Fey G.T.K., Chen J.G., Wang Z.F., Yang H.Z., Kumar T.P. Saturated linear dicarboxylic acids as chelating agents for the sol–gel synthesis of LiNi_0.8Co_0.2O₂. Mater. Chem. Phys., 2004, 87(2-3): 246.

[22] Fey G.T.K., Subramanian V., Lu C.Z. Tartaric acid-assisted sol–gel synthesis of LiNi_0.8Co_0.2O₂ and its electrochemical properties as a cathode material for lithium batteries. Solid State Ionics, 2002, 152, 83.

[23] Lu H.Q., Zhou H.T., Svensson A.M., Fossdal A., Sheridan E., Lu S.G., Vullum-Bruer F. High capacity Li[Ni_0.8Co_0.1Mn_0.1]O₂ synthesized by sol–gel and co-precipitation methods as cathode materials for lithium-ion batteries. Solid State Ionics, 2013, 249, 105.

[24] Cao H., Zhang Y., Zhang J., Xia B.J. Synthesis and electrochemical characteristics of layered LiNi_0.6Co_0.2Mn_0.2O₂ cathode material for lithium ion batteries. Solid State Ionics, 2005, 176(13-14): 1207.

[25] Liang L.W., Du K., Peng Z.D., Cao Y.B., Duan J.G., Jiang J.B., Hu G.R. Co-precipitation synthesis of Ni_0.6Co_0.2Mn_0.2(OH)₂ precursor and characterization of LiNi_0.6Co_0.2Mn_0.2O₂ cathode material for secondary lithium batteries. Electrochim. Acta, 2014, 130, 82.

[26] Abraham D.P., Twesten R.D., Balasubramanian M., Petrov I., McBreen J., Amine K. Surface changes on LiNi_0.8Co_0.2O₂ particles during testing of high-power lithium-ion cells. Electrochem. Commun., 2002, 4(8): 620.

[27] Cho Y., Oh P., Cho J. A new type of protective surface layer for high-capacity Ni-based cathode materials: nanoscaled surface pillaring layer. Nano Lett., 2013, 13(3): 1145.

[28] Thackeray M.M., Johnson C.S., Vaughey J.T., Li N., Hackney S.A. Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries. J.^Mater. Chem., 2005, 15(23): 2257.

[29] Aurbach D. Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. J.^Power Sources, 2000, 89(2): 206.

[30] Lee M.H., Kang Y.J., Myung S.T., Sun Y.K. Synthetic optimization of Li[Ni_1/3Co_1/3Mn_1/3]O₂ via co-precipitation. Electrochim. Acta, 2004, 50(4): 939.

[31] Ying J.R., Wan C.R., Jiang C.Y., Li Y.X. Preparation and characterization of high-density spherical LiNi_0.8Co_0.2O₂ cathode material for lithium secondary batteries. J.^Power Sources, 2001, 99(1-2): 78.

[32] Kong J.Z., Zhai H.F., Ren C., Tai G.A., Yang X.Y., Zhou F., Li H., Li J.X., Tang Z. High-capacity Li(Ni_0.5Co_0.2Mn_0.3)O₂ lithium-ion battery cathode synthesized using a green chelating agent. J.^Solid State Electrochem., 2013, 18(1): 181.

[33] Mohanty D., Gabrisch H. Microstructural investigation of Li_xNi_1/3Mn_1/3Co_1/3O₂ (x≤1) and its aged products via magnetic and diffraction study. J.^Power Sources, 2012, 220, 405.

[34] Ryu W.H., Lim S.J., Kim W.K., Kwon H.S. 3-D dumbbell-like LiNi_1/3Mn_1/3Co_1/3O₂ cathode materials assembled with nano-building blocks for lithium-ion batteries. J.^Power Sources, 2014, 257, 186.

[35] Li D., Lian F., Hou X.M., Chou K.C. Reaction mechanisms for 0.5Li₂MnO₃·0.5LiMn_0.5Ni_0.5O₂ precursor prepared by low-heating solid state reaction. Int. J.^Miner. Metall. Mater., 2012, 19(9): 856.

[36] Shaju K.M., Rao G.V.S., Chowdari B.V.R. Performance of layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ as cathode for Li-ion batteries. Electrochim. Acta, 2002, 48(2): 145.

[37] Liang L.W., Du K., Peng Z.D., Cao Y.B., Hu G.R. Synthesis and electrochemical performance of Li-Ni_0.6Co_0.2Mn_0.2O₂ as a concentration-gradient cathode material for lithium batteries. Chin. Chem. Lett., 2014, 25(6): 883.

[38] Reimers J.N., Rossen E., Jones C.D., Dahn J.R. Structure and electrochemistry of Li_xFe_yNi_1−yO₂. Solid State Ionics, 1993, 61(4): 335.

[39] Eom J., Kim M.G., Cho J. Storage characteristics of Li-Ni_0.8Co_0.1+xMn_0.1−xO₂ (x = 0, 0.03, and 0.06) cathode materials for lithium batteries. J.^Electrochem. Soc., 2008, 155(3): 239.

[40] Jung S.K., Gwon H., Hong J., Park K.Y., Seo D.H., Kim H., Hyun J., Yang W., Kang K. Understanding the degradation mechanisms of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material in lithium ion batteries. Adv. Energy Mater., 2014

[41] Lin F., Markus I.M., Nordlund D., Weng T.C., Asta M.D., Xin H.L., Doeff M.M. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat. Commun., 2014

[42] Lin F., Nordlund D., Li Y.Y., Quan M.K., Cheng L., Weng T.C., Liu Y.J., Xin H.L., Doeff M.M. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries. Nat. Energy, 2016

[43] Lee Y.S., Ahn D., Cho Y.H., Hong T.E., Cho J. Improved rate capability and thermal stability of Li-Ni_0.5Co_0.2Mn_0.3O₂ cathode materials via nanoscale SiP₂O₇ coating. J.^Electrochem. Soc., 2011, 158(12): 1354.

[44] Yue P., Wang Z.X., Li X.H., Xiong X., Wang J.X., Wu X.W., Guo H.J. The enhanced electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by low temperature fluorine substitution. Electrochim. Acta, 2013, 95, 112.