A holistic review on the synthesis techniques of spinel structured lithium cobalt manganese tetroxide
Keywords:LiCoMnO4 cathode, solid-state, sol-gel, flux, hydrothermal
Spinel structured lithium cobalt manganese tetroxide (LiCoMnO4) which exhibit unrivalled reduction potential of 5.3V (vs. Li0 | Li+) was identified to be one of the potential cathode candidates for next generation lithium-ion batteries offering high voltage output and energy density. The focal point of this article is to holistically review relevant techniques established for the synthesis of LiCoMnO4 compound, particularly solid-state reaction, sol-gel synthesis, flux method and hydrothermal technology. Electrochemical performances of lithium cobalt manganese tetroxide (LiCoMnO4) synthesised via the four distinctive approaches as well as the critical process parameters will be compared and scrutinised. Adversities associated with deoxygenation in the course of synthesis process at high temperature and proposed countermeasure via fluorine-substitution will also be discussed.
H. Orru, K. L. Ebi, and B. Forsberg, "The Interplay of Climate Change and Air Pollution on Health," Current Environmental Health Reports, vol. 4, no. 4, pp. 504-513, December 01 2017.
E. E. van der Wall, "Air pollution: 6.6 million premature deaths in 2050!," Netherlands Heart Journal, journal article vol. 23, no. 12, pp. 557-558, December 01 2015.
C. K. Gately, L. R. Hutyra, S. Peterson, and I. Sue Wing, "Urban emissions hotspots: Quantifying vehicle congestion and air pollution using mobile phone GPS data," Environ Pollut, vol. 229, pp. 496-504, Oct 2017.
P. Arévalo-Cid, P. Dias, A. Mendes, and J. Azevedo, "Redox flow batteries: a new frontier on energy storage," Sustainable Energy & Fuels, vol. 5, no. 21, pp. 5366-5419, 2021.
N. F. Attia and K. E. Geckeler, "Polyaniline as a material for hydrogen storage applications," Macromolecular Rapid Communication, vol. 34, no. 13, pp. 1043-55, Jul 12 2013.
N. F. Attia, M. Jung, J. Park, S.-Y. Cho, and H. Oh, "Facile synthesis of hybrid porous composites and its porous carbon for enhanced H2 and CH4 storage," International Journal of Hydrogen Energy, vol. 45, no. 57, pp. 32797-32807, 2020.
N. F. Attia, M. Jung, J. Park, H. Jang, K. Lee, and H. Oh, "Flexible nanoporous activated carbon cloth for achieving high H2, CH4, and CO2 storage capacities and selective CO2/CH4 separation," Chemical Engineering Journal, vol. 379, 2020.
Y. Deng, C. Eames, B. Fleutot, R. David, J-N. Chotard, E. Suard, C. Masquelier, and M. S. Islam, "Enhancing the Lithium Ion Conductivity in Lithium Superionic Conductor (LISICON) Solid Electrolytes through a Mixed Polyanion Effect," ACS Applied Materials & Interfaces, vol. 9, no. 8, pp. 7050-7058, Mar 1 2017.
W. G. El-Sayed, N. F. Attia, I. Ismail, M. El-Khayat, M. Nogami, and M. S. A. Abdel-Mottaleb, "Innovative and cost-effective nanodiamond based molten salt nanocomposite as efficient heat transfer fluid and thermal energy storage media," Renewable Energy, vol. 177, pp. 596-602, 2021.
M. Jung, J. Park, K. Lee, N. F. Attia, and H. Oh, "Effective synthesis route of renewable nanoporous carbon adsorbent for high energy gas storage and CO2/N2 selectivity," Renewable Energy, vol. 161, pp. 30-42, 2020.
H. Lee, V. S. Kumbhar, J. Lee, Y. Choi, and K. Lee, "Highly reversible crystal transformation of anodized porous V2O5 nanostructures for wide potential window high-performance supercapacitors," Electrochimica Acta, vol. 334, 2020.
J. Park, S. Y. Cho, M. Jung, K. Lee, Y-C. Nah, N. F. Attia, and H. Oh, "Efficient synthetic approach for nanoporous adsorbents capable of pre- and post-combustion CO2 capture and selective gas separation," Journal of CO2 Utilization, vol. 45, 2021.
J. Park, M. Jung, H. Jang, K. Lee, N. F. Attia, and H. Oh, "A facile synthesis tool of nanoporous carbon for promising H2, CO2, and CH4 sorption capacity and selective gas separation," Journal of Materials Chemistry A, vol. 6, no. 45, pp. 23087-23100, 2018.
B. Singh, B. Singh, Z. Wang, S. Park, G. S. Gautam, J-N. Chotard, L. Croguennec, D. Carlier, A. K. Cheetham, C. Masquelier, and P. Canepa, "A chemical map of NaSICON electrode materials for sodium-ion batteries," Journal of Materials Chemistry A, vol. 9, no. 1, pp. 281-292, 2021.
V. Etacheri, R. Marom, R. Elazari, G. Salitra, and D. Aurbach, "Challenges in the development of advanced Li-ion batteries: a review," Energy & Environmental Science, vol. 4, no. 9, 2011.
Y. Yang, Z. Tan, and Y. Ren, "Research on factors that influence the fast charging behavior of private battery electric vehicles," Sustainability, vol. 12, no. 8, 2020.
C. M. Hayner, X. Zhao, and H. H. Kung, "Materials for rechargeable lithium-ion batteries," Annual Review of Chemical and Biomolecular Engineering, vol. 3, pp. 445-471, 2012.
M. Root, The TAB Battery Book: An In-Depth Guide to Construction, Design, and Use. McGraw-Hill Education, 2010.
R. Schmuch, R. Wagner, G. Hörpel, T. Placke, and M. Winter, "Performance and cost of materials for lithium-based recharge-able automotive batteries," Nature Energy, vol. 3, no. 4, pp. 267-278, 2018.
J. Gao, S.-Q. Shi, and H. Li, "Brief overview of electro-chemical potential in lithium ion batteries," Chinese Physics B, vol. 25, no. 1, 2016.
P. Krivik and P. Bac, "Electrochemical Energy Storage," in Energy Storage - Technologies and Applications, 2013.
C. Liu, Z. G. Neale, and G. Cao, "Understanding electrochemical potentials of cathode materials in rechargeable batteries," Materials Today, vol. 19, no. 2, pp. 109-123, 2016.
C. Julien, A. Mauger, K. Zaghib, and H. Groult, "Optimization of Layered Cathode Materials for Lithium-Ion Batteries," Materials, vol. 9, no. 7, Jul 19 2016.
R. Tatara, P. Karayaylali, Y. Yu, Y. Zhang, L. Giordano, F. Maglia, R. Jung, J. P. Schmidt, I. Lund, and Y. Shao-Horn, "The Effect of Electrode-Electrolyte Interface on the Electrochemical Impedance Spectra for Positive Electrode in Li-Ion Battery," Journal of The Electrochemical Society, vol. 166, no. 3, pp. A5090-A5098, 2018.
M. Osiak, H. Geaney, E. Armstrong, and C. O' Dwyer, "Structuring materials for lithium-ion batteries: advancements in nanomaterial structure, composition, and defined assembly on cell performance," Journal of Materials Chemistry A, vol. 2, no. 25, 2014.
C. Julien, A. Mauger, A. Vijh, and K. Zaghib, Lithium Batteries: Science and Technology. Springer International Publishing, 2015, p. 51.
K. N. Wood, E. Kazyak, A. F. Chadwick, K-H. Chen, J-G. Zhang, K. Thornton, and N. P. Dasgupta, "Dendrites and pits: Untangling the complex behavior of lithium metal anodes through operando video microscopy," ACS Central Science, vol. 2, no. 11, pp. 790-801, Nov 23 2016.
R. Zhu, J. Feng, and Z. Guo, "In situ observation of dendrite behavior of electrode in half and full cells," Journal of The Electrochemical Society, vol. 166, no. 6, pp. A1107-A1113, 2019.
J. B. Quinn, T. Waldmann, K. Richter, M. Kasper, and M. Wohlfahrt-Mehrens, "Energy density of cylindrical li-ion cells: A comparison of commercial 18650 to the 21700 cells," Journal of The Electrochemical Society, vol. 165, no. 14, pp. A3284-A3291, 2018.
C. Sun, "Batteries & Fuel Cells" Advanced Battery Materials. Wiley, 2019.
X. Hu, Y. Zheng, D. A. Howey, H. Perez, A. Foley, and M. Pecht, "Battery warm-up methodologies at subzero temperatures for automotive applications: Recent advances and perspectives," Progress in Energy and Combustion Science, vol. 77, 2020.
A. Tomaszewska, Z. Chu, X. Feng, S. O'Kane, X. Liu, J. Chen C. Ji, E. Endler, R. Li, L. Liu, Y. Li, S. Zheng, S. Vetterlein, M. Gao, J. Du, M. Parkes, M. Ouyang, M. Marinescu, and B. Wu, "Lithium-ion battery fast charging: A review," eTransportation, vol. 1, 2019.
S. Chauque, F. Y. Oliva, A. Visintin, D. Barraco, E. P. M. Leiva, and O. R. Cámara, "Lithium titanate as anode material for lithium ion batteries: Synthesis, post-treatment and its electrochemical response," Journal of Electroanalytical Chemistry, vol. 799, pp. 142-155, 2017.
J. Christensen, V. Srinivasan, and J. Newman, "Optimization of lithium titanate electrodes for high-power cells," Journal of The Electrochemical Society, vol. 153, no. 3, 2006.
R. Fu, X. Zhou, H. Fan, D. Blaisdell, A. Jagadale, X. Zhang, and R. Xiong, "Comparison of lithium-ion anode materials using an experimentally verified physics-based electrochemical model," Energies, vol. 10, no. 12, 2017.
H. Zhao, "Lithium titanate-based anode materials," in Recharge-able Batteries(Green Energy and Technology, 2015, pp. 157-187.
M. S. Whittingham, "Lithium batteries and cathode materials," Chemical Reviews, vol. 104, no. 10, pp. 4271-4302, 2004.
N. Van Hiep, and K. Young Ho, "Recent advances in cathode and anode materials for lithium ion batteries," Applied Chemistry for Engineering, vol. 29, no. 6, pp. 635-644, 2018.
E. A. Suslov, O. V. Bushkova, E. A. Sherstobitova, O. G. Reznitskikh, and A. N. Titov, "Lithium intercalation into TiS2 cathode material: phase equilibria in a Li–TiS2 system," Ionics, vol. 22, no. 4, pp. 503-514, 2015.
S. Fang, D. Bresser, and S. Passerini, "Transition metal oxide anodes for electrochemical energy storage in lithium‐ and sodium‐ion batteries," Advanced Energy Materials, vol. 10, no. 1, 2019.
M. A. Kebede, and F. I. Ezema, Electrochemical Devices for Energy Storage Applications. CRC Press, 2019.
H. R. Shaari and V. Sethuprakhash, "Review of Electrochemical performance of LiNiO2 and their derivatives as cathode material for lithium-ion batteries," Jurnal Teknologi, vol. 70, no. 1, 2014.
P. Kalyani, and N. Kalaiselvi, "Various aspects of LiNiO2 chemistry: A review," Science and Technology of Advanced Materials, vol. 6, no. 6, pp. 689-703, 2005.
Y. C. Lyu, J. Huang, and H. Li, "Layered and spinel structural cathodes," in Rechargeable Batteries, 2015, pp. 67-92.
Z. Liu, A. Yu, and J. Y. Lee, "Synthesis and characterization of LiNi1-x-yCoxMnyO2 as the cathode materials of secondary lithium batteries," Journal of Power Sources, vol. 81-82, pp. 416-419, 1999.
F. Schipper, E. M. Erickson, C. Erk, J.-Y. Shin, F. F. Chesneau, and D. Aurbach, "Review—recent advances and remaining challenges for lithium ion battery cathodes," Journal of The Electrochemical Society, vol. 164, no. 1, pp. A6220-A6228, 2016.
Q. Zhen, S. Bashir, and J. L. Liu, Nanostructured Materials for Next-Generation Energy Storage and Conversion: Advanced Battery and Supercapacitors. Springer Berlin Heidelberg, 2019.
X. Sun, Z. Li, X. Wang, and C. Li, "Technology development of electric vehicles: A review," Energies, vol. 13, no. 1, 2019.
F. Zhou, M. Cococcioni, K. Kang, and G. Ceder, "The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni," Electrochemistry Communications, vol. 6, no. 11, pp. 1144-1148, 2004.
N. Reeves-McLaren, M. Hong, H. Alqurashi, L. Xue, J. Sharp, A. J. Rennie, and R. Boston "The Spinel LiCoMnO4: 5V cathode and conversion anode," Energy Procedia, vol. 151, pp. 158-162, 2018.
X. Huang, M. Lin, Q. Tong, X. Li, Y. Ruan, and Y. Yang, "Synthesis of LiCoMnO4 via a sol–gel method and its application in high power LiCoMnO4/Li4Ti5O12 lithium-ion batteries," Journal of Power Sources, vol. 202, pp. 352-356, 2012.
A. Windmüller, C-L. Tsai, S. Moller, M. Baski, Y. J. Sohn, S. Uhlenbruck, and O. Guillon, "Enhancing the performance of high-voltage LiCoMnO4 spinel electrodes by fluorination," Journal of Power Sources, vol. 341, pp. 122-129, 2017.
K. Ariyoshi, H. Yamamoto, and Y. Yamada, "High dimensional stability of LiCoMnO4 as positive electrodes operating at high voltage for lithium-ion batteries with a long cycle life," Electrochimica Acta, vol. 260, pp. 498-503, 2018.
X. Fan, X. Ji, L. Chen, J. Chen, T. Deng, F. Han, J. Yue, N. Piao, R. Wang, X. Zhou, X. Xiao, L. Chen, and C. Wang, "All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents," Nature Energy, vol. 4, no. 10, pp. 882-890, 2019.
T.-F. Yi, S.-Y. Yang, and Y. Xie, "Recent advances of Li4Ti5O12 as a promising next generation anode material for high power lithium-ion batteries," Journal of Materials Chemistry A, vol. 3, no. 11, pp. 5750-5777, 2015.
H. Kawai, M. Nagata, H. Kageyama, H. Tukamoto, and A. R. West, "5 V lithium cathodes based on spinel solid solutions Li2Co1+XMn3−XO8: -1≤X≤1," Electrochimica Acta, vol. 45, no. 1, pp. 315-327, 1999.
H. Kawai, M. Nagata, H. Tukamoto, and A. R. West, "A new lithium cathode LiCoMnO: Toward practical 5 V lithium batteries," Electrochemical and Solid-State Letters, vol. 1, no. 5, 1999.
N. Kuwata, S. Kudo, Y. Matsuda, and J. Kawamura, "Fabrication of thin-film lithium batteries with 5-V-class LiCoMnO4 cathodes," Solid State Ionics, vol. 262, pp. 165-169, 2014.
Y. Hamada, N. Hamao, K. Kataoka, N. Ishida, Y. Idemoto, and J. Akimoto, "Single crystal synthesis, crystal structure and electrochemical property of spinel-type LiCoMnO4 as 5 V positive electrode materials," Journal of the Ceramic Society of Japan, vol. 124, no. 6, pp. 706-709, 2016.
C. M. Julien and A. Mauger, "Review of 5-V electrodes for Li-ion batteries: status and trends," Ionics, vol. 19, no. 7, pp. 951-988, 2013.
M. You, X. Huang, M. Lin, Q. Tong, X. Li, Y. Ruan, and Y. Yang, "Preparation of LiCoMnO4 assisted by hydrothermal approach and its electrochemical performance," American Journal of Engineering and Applied Sciences, vol. 9, no. 2, pp. 396-405, 2016.
E. McCalla, Consequences of Combinatorial Studies of Positive Electrodes for Li-ion Batteries. Springer International Publishing, 2014.
D. Pasero, S. de Souza, N. Reeves, and A. R. West, "Oxygen content and electrochemical activity of LiCoMnO4–δ," Journal of Materials Chemistry, vol. 15, no. 41, 2005.
K. Ariyoshi, H. Yamamoto, and Y. Yamada, "Synthesis optimization of electrochemically active LiCoMnO4 for high-voltage lithium-ion batteries," Energy & Fuels, vol. 35, no. 16, pp. 13449-13456, 2021.
M. Hu, Y. Tian, J. Wei, D. Wang, and Z. Zhou, "Porous hollow LiCoMnO4 microspheres as cathode materials for 5 V lithium ion batteries," Journal of Power Sources, vol. 247, pp. 794-798, 2014.
A. Windmüller, "Synthesis and analysis of spinel cathode materials for high voltage solid-state lithium batteries," PhD, Institut für Energie- und Klimaforschung, RWTH Aachen University, 2018.
S. Liu, H. He, and C. Chang, "Understanding the improvement of fluorination in 5.3 V LiCoMnO4 spinel," Journal of Alloys and Compounds, vol. 860, 2021.
A. Windmüller, C. A. Bridges, C-L. Tsai, S. Lobe, C. Dellen, G. M. Veith, M. Finsterbusch, S. Uhlenbruck, and O. Guillon, "Impact of fluorination on phase stability, crystal chemistry, and capacity of LiCoMnO4 high voltage spinels," ACS Applied Energy Materials, vol. 1, no. 2, pp. 715-724, 2018.
A. Windmüller, C. Dellen, S. Lobe, C-L. Tsai, S. Moller, Y. J. Sohn, N. Wettengl, M. Finsterbusch, S. Uhlenbruck, and O. Guillon, "Thermal stability of 5 V LiCoMnO4 spinels with LiF additive," Solid State Ionics, vol. 320, pp. 378-386, 2018.
C. Zhang, "High-voltage electrolytes," Nature Energy, vol. 4, no. 5, pp. 350-350, 2019.
L. Chen, X. Fan, E. Hu, X. Ji, j. Chen, S. Hou, T. Deng, J. Li, D. Su, X. Yang, and C. Wang "Achieving high energy density through increasing the output voltage: A highly reversible 5.3 V Battery," Chem, vol. 5, no. 4, pp. 896-912, 2019.
How to Cite
Copyright (c) 2022 Journal of Metals, Materials and Minerals
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Authors who publish in this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgment of the work's authorship and initial publication in this journal.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgment of its initial publication in this journal.