Document Type : Original Reaearch Article

Authors

1 Department of advanced materials and new energy, Iranian Research Organization for Science and Technology, Tehran, Iran.

2 Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran.

Abstract

In this study, the effect of excess lithium content on lithiated cathode in lithium ion battery and non-stoichiometric state has been investigated. For this purpose, the precursor was compounded with co-precipitation synthesized Ni0.3Mn0.5Co0.2 and subsequently lithiated with different amounts of LiOH to investigate the effect of excess lithium content on the Lix (Ni0.3Mn0.5Co0.2) O2 cathode. The results of ICP, XRD and SEM analysis showed that the samples were well synthesized and the compositions were layered and the particle size in the samples was less than 10 microns. The results of battery charge-discharge tests for all three samples at 0.5-5C showed that the sample of Li1.5 (Ni0.3Mn0.5Co0.2) O2 had the best electrochemical performance; such that at 1C discharge rate its capacity 200mAh/g and after 30 cycles, its capacity reached 138mAh/g at 5C discharge rate. The impedance analysis (EIS) revealed that the sample of Li1.5 (Ni0.3Mn0.5Co0.2) O2 had the lowest internal resistance. Finally, it can be concluded that increasing the amount of excess lithium has the optimum value for improving the battery performance, so that in non-stoichiometric mode, the increase of lithium up to Li1.5 is associated with improved performance and above this level will result in reduced battery performance.

Keywords

1.      Delmas, C., et al., Lithium batteries: a new tool in solid state chemistry. International Journal of Inorganic Materials, 1999. 1(1) 11-19. (https://doi.org/10.1016/S1463-0176(99)00003-4)
2.      Ammundsen, B. and J. Paulsen,Novel Lithium-Ion Cathode Materials Based on Layered Manganese Oxides. Advanced Materials, 2001. 13(12‐13)  943-956. (https://doi.org/10.1002/1521-4095(200107)13:12/13%3C943::AID-ADMA943%3E3.0.CO;2-J)
3.      Whittingham, M.S., Electrical energy storage and intercalation chemistry. Science, 1976. 192(4244) 1126-1127(https://doi.org/DOI: 10.1126/science.192.4244.1126)
4.      Needham, S.A., et al., Synthesis and electrochemical performance of doped LiCoO2 materialsJournal of Power Sources, 2007. 174(2) 828-831(https://doi.org/10.1016/j.jpowsour.2007.06.228)
5.      Yan, S., et al., Charge and discharge curves: a unique reliable evidence for the electrochemical properties of LiCoO2. Journal of University of Science and Technology Beijing, Mineral, Metallurgy, Material, 2007. 14(5) 473-476(https://doi.org/10.1016/S1005-8850(07)60093-0)
6.      Li, A., et al., Cathode interfacial engineering to enhance cycling stability of rechargeable lithium-ion batteries. Journal of Solid State Chemistry, 2019. 277, 531-537. (https://doi.org/10.1016/j.jssc.2019.06.031)
7.      Ko, Y., et al., Redox Mediators: A Solution for Advanced Lithium–Oxygen Batteries. Trends in Chemistry, 2019. 1(3) 349-360(https://doi.org/10.1016/j.trechm.2019.03.016)
8.      Zhou, L., et al., Much improved capacity and cycling performance of LiVMoO6 cathode for lithium ion batteries. Journal of Alloys and Compounds, 2008. 457(1) 389-3. (http://dx.doi.org/10.1016/j.jallcom.2007.02.126)
9.      Zhu, X.J., et al., Synthesis and performance of lithium vanadium phosphate as cathode materials for lithium ion batteries by a sol–gel method. Journal of Power Sources, 2008. 184(2) 578-582(https://doi.org/10.1016/j.jpowsour.2008.01.007)
10.    Cho, J., Y.J. Kim, and B. Park, Novel LiCoO2 cathode material with Al2O3 coating for a Li ion cell. Chemistry of Materials, 2000. 12(12) 3788-3791(https://doi.org/10.1021/cm000511k)
11.    Nitta, N., et al., Li-ion battery materials: present and future. Materials Today, 2015. 18(5) 252-264(https://doi.org/10.1016/j.mattod.2014.10.040)
12.    Tu, J., et al., Enhanced cycling stability of LiMn 2 O 4 by surface modification with melting impregnation method. Electrochimica Acta, 2006. 51(28) 6456-6462(https://doi.org/10.1016/j.electacta.2006.04.031)
13.    Sobkowiak, A., et al., Understanding and controlling the surface chemistry of LiFeSO4F for an enhanced cathode functionalityChemistry of Materials, 2013. 25(15) 3020-3029(https://doi.org/10.1021/cm401063s)
14.    Yoncheva, M., et al., Carbon-coated nano-sized LiFe1− x Mn x PO4 solid solutions (0≤ x≤ 1) obtained from phosphate–formate precursors. Journal of materials science, 2011. 46(22) 7082-7089(https://doi.org/10.1007/s10853-011-5555-z)
15.    Liu, N., et al., A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature nanotechnology, 2014. 9(3) 187-192(https://doi.org/10.1038/nnano.2014.6)
16.    Lee, W.J., et al., Nitrogen-doped carbon nanotubes and graphene composite structures for energy andcatalytic applications. Chemical Communications, 2014. 50(52) 6818-6830(https://doi.org/10.1039/C4CC00146J)
17.    Fergus, J.W., Recent developments in cathode materials for lithium ion batteries. Journal of Power Sources, 2010. 195(4) 939-954(https://doi.org/10.1016/j.jpowsour.2009.08.089)
18.    Xu, B., et al., Recent progress incathode materials research for advanced lithium ion batteries. Materials Science and Engineering, R: Reports, 2012. 73(5) 51-65(https://doi.org/10.1016/j.mser.2012.05.003)
19.    Ohzuku, T. and Y. Makimura, Layered Lithium Insertion Material of LiCo1/3Ni1/3Mn1/3O2 for Lithium-Ion Batteries. Chemistry Letters, 2001(7) 642-643. (https://doi.org/10.1246/cl.2001.642)
20.    Ohzuku, T. and Y. Makimura, Layered Lithium Insertion Material of LiNi1/2Mn1/2O2: A Possible Alternative to LiCoO2 for Advanced Lithium-Ion Batteries. Chemistry Letters, 2001(8) 744-745(https://doi.org/10.1246/cl.2001.744)
21.    Gu, Y.-J., et al., Reduction of the lithium and nickel site substitution in Li1+xNi0.5Co0.2Mn0.3O2 with Li excess as a cathode electrode material for Li-ion batteries. Journal of Alloys and Compounds, 2015. 630, 316-322(https://doi.org/10.1016/j.jallcom.2014.12.235)
22.    Zhao, W., et al., Synthesis of Li-excess layeredcathode material with enhanced reversible capacity for Lithium ion batteries through the optimization of precursor synthesis method. Electrochimica Acta, 2014. 143, 347-356(https://doi.org/10.1016/j.electacta.2014.08.006)
23.    Ko, M., et al., Considering Critical Factors of Li-rich Cathode and Si Anode Materials for Practical Li-ion Cell Applications. Small (Weinheim an der Bergstrasse, Germany), 2015. 11(https://doi.org/10.1002/smll.201500474)
24.    Tolouei, A., A. Kaflou, and S. K Sadrnezhaad, Effects of lithium excess and Ni content on the electrochemical performance of Li1 + x (Ni0.45-x Mn0.4Co0.15) O2 lithium-ion cathode materials in stoichiometric state. Materials Research Express, 2019. 6(https://doi.org/10.1088/2053-1591/ab2019)
25.    Jiang, M., et al., Electrochemical and Structural Study of the Layered, "Li-Excess" Lithium-Ion Battery Electrode Material Li[Li 1/9Ni 1/3MnO 2. Chemistry of Materials, 2009. 21, 2733-2745(https://doi.org/10.1021/cm900279u)
26.    Dolotko, O., et al., Understanding structural changes in NMC Li-ion cells by in situ neutron diffraction. Journal of Power Sources, 2014. 255, 197-203(https://doi.org/10.1016/j.jpowsour.2014.01.010)
27.    Samarasingha, P.B., et al., Development of cathode materials for lithium ion rechargeable batteries based on the system Li(Ni1/3Mn1/3Co(1/3-x)Mx)O2, (M=Mg, Fe, Al and x=0.00 to 0.33). Solid State Ionics, 2014. 268, 226-230(https://doi.org/10.1016/j.ssi.2014.07.012)
28.    Kim, J.W., et al., Unexpected high power performance of atomic layer deposition coated Li[Ni1/3Mn1/3Co1/3]O2 cathodes. Journal of Power Sources, 2014. 254, 190-197(https://doi.org/0.1016/j.jpowsour.2013.12.119)
29.    Yin, K., et al., The effects of precipitant agent on structure and performance of LiNi1/3Co1/3Mn1/3O2 cathode material via a carbonate co-precipitation method. Electrochimica Acta, 2012. 85, 99-103(https://doi.org/10.1016/j.electacta.2012.06.064)
30.    Kong, J.-Z., et al., Effects of Li source and calcination temperature on the electrochemical properties of LiNi0.5Co0.2Mn0.3O2 lithium-ion cathode materials. Journal of Alloys and Compounds, 2013, 554,  221-226(https://doi.org/10.1016/j.jallcom.2012.11.090)
31.    Xu, Z., et al., Effects of precursor, synthesis time and synthesis temperature on the physical and electrochemical properties of Li(Ni1−x−yCoxMny)O2 cathode materials. Journal of Power Sources, 2014. 248, 180-189(https://doi.org/10.1016/j.jpowsour.2013.09.064)
32.    ShajuK.M., G.V. Subba Rao, and B.V.R. Chowdari, Performance of layered Li(Ni1/3Co1/3Mn1/3)O2 as cathode for Li-ion batteries. Electrochimica Acta, 2002. 48(2), 145-151(https://doi.org/10.1016/S0013-4686(02)00593-5)
33.    Mohanty, D., et al., Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0O2 cathode during high voltage cycling resolved by in situ X-ray diffraction. Journal of Power Sources, 2013. 229, 239-248(https://doi.org/10.1016/j.jpowsour.2012.11.144)
34.    Xu, B., et al., Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study. Energy & Environmental Science, 2011. 4(6), 2223-2233(https://pubs.rsc.org/en/content/articlelanding/2011/ee/c1ee01131f#!divAbstract)
35.    Li, J., et al., Uniform LiNi1/3Co1/3Mn1/3O2 hollow microspheres: Designed synthesis, topotactical structural transformation and their enhanced electrochemical performance. Nano Energy, 2013. 2(6),1249-1260(https://doi.org/10.1016/j.nanoen.2013.06.003)
36.    Xiang, X. and W. Li, Self-directed chemical synthesis of lithium-rich layered oxide Li[Li0.2Ni0.2Mn0.6]O2 with tightly interconnected particles as cathode of lithium ion batteries with improved rate capability. Electrochimica Acta, 2014. 127, 259-265(http://dx.doi.org/10.1016/j.electacta.2014.02.037)
37.    Yang, Z., et al., K-doped layered LiNi0.5Co0.2Mn0.3O2 cathode material: Towards the superior rate capability and cycling performance. Journal of Alloys and Compounds, 2017, 699,  358-365(http://dx.doi.org/10.1016/j.jallcom.2016.11.245)
38.    Lin, C., et al., Hydrogen peroxide assisted synthesis of LiNi1/3Co1/3Mn1/3O2 as high-performance cathode for lithium-ion batteries. Journal of Power Sources, 2015. 280, 263-271(https://doi.org/10.1016/j.jpowsour.2015.01.084)