Isothermal Decomposition Kinetics of NMC 622 and NCA Oxalate Precursors for Lithium-Ion Battery Cathode Synthesis
Abstract
Oxalate precursors for NMC 622 (Ni₀.₆Mn₀.₂Co₀.₂) and NCA (Ni₀.₈Co₀.₁₅Al₀.₀₅) cathode materials were synthesized by co-precipitation at 60 °C and pH 2.0, then subjected to isothermal calcination at 350, 400, and 450 °C. Thermogravimetric mass-loss data collected at 10-minute intervals were analyzed using the integral kinetic method, testing zero- and first-order rate laws. NMC 622 decomposition followed first-order kinetics (rate law: −dW/dt = kW) with rate constants increasing from 0.0043 to 0.0104 min⁻¹ over 350–450 °C, yielding an Arrhenius activation energy of 19.66 kJ mol⁻¹. NCA decomposition obeyed zero-order kinetics (−dW/dt = k) with rate constants of 0.0674–0.2329 g min⁻¹, and a significantly higher activation energy of 50.63 kJ mol⁻¹. The contrasting kinetic orders suggest that NMC 622 decomposition is governed by the remaining precursor mass (solid–gas interface area), while NCA decomposition is limited by product-layer diffusion, likely exacerbated by the thermally stable Al₂O₃ barrier. These findings provide quantitative parameters for optimizing the calcination step in battery-grade cathode manufacturing.
Keywords: calcination; decomposition kinetics; NMC 622; NCA; activation energy; Arrhenius; oxalate precursor; battery cathode; co-precipitation
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Liu, W., Oh, P., Liu, X., Lee, M.-J., Cho, W., Chae, S., Kim, Y., & Cho, J. (2015). Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries. Angew. Chem. Int. Ed., 54(15), 4440–4457. https://doi.org/10.1002/anie.201409262
Manthiram, A., Knight, J. C., Myung, S.-T., Oh, S.-M., & Sun, Y.-K. (2016). Nickel-rich and lithium-rich layered oxide cathodes: progress and perspectives. Adv. Energy Mater., 6(1), 1501010. https://doi.org/10.1002/aenm.201501010
Li, W., Erickson, E. M., & Manthiram, A. (2020). High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy, 5(1), 26–34. https://doi.org/10.1038/s41560-019-0513-0
Donkova, B., Vasileva, P., Nihtianova, D., Velichkova, N., Stefanov, P., & Mehandjiev, D. (2011). Synthesis, structural characterization, and catalytic application of CuxZn1−xO solid solutions obtained from oxalate precursors. J. Mater. Sci., 46(21), 7134–7143. https://doi.org/10.1007/s10853-011-5650-y
Courty, P., Ajot, H., Marcilly, C., & Delmon, B. (1973). Oxydes mixtes ou en solution solide sous forme très divisée obtenus par décomposition thermique de précurseurs amorphes. Powder Technol., 7(1), 21–38. https://doi.org/10.1016/0032-5910(73)80004-9
Ryu, H.-H., Park, K.-J., Yoon, C. S., & Sun, Y.-K. (2018). Capacity fading of Ni-rich Li[NixCoyMn1−x−y]O2 (0.6 ≤ x ≤ 0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem. Mater., 30(3), 1155–1163. https://doi.org/10.1021/acs.chemmater.7b05269
Sun, H., & Zhao, K. (2017). Electronic structure and comparative properties of LiNixMnyCozO2 cathode materials. J. Phys. Chem. C, 121(11), 6002–6010. https://doi.org/10.1021/acs.jpcc.7b00810
Kim, U.-H., Ryu, H.-H., Kim, J.-H., Mücke, R., Kaghazchi, P., Yoon, C. S., & Sun, Y.-K. (2019). Microstructure-controlled Ni-rich cathode material by microscale compositional partition for next-generation electric vehicles. Adv. Energy Mater., 9(15), 1803902. https://doi.org/10.1002/aenm.201803902
Brown, M. E., Dollimore, D., & Galwey, A. K. (1980). Reactions in the Solid State. Comprehensive Chemical Kinetics, Vol. 22. Elsevier, Amsterdam. ISBN: 978-0-444-41807-3.
Dollimore, D., Griffiths, D. L., & Nicholson, D. (1963). The thermal decomposition of various oxalates in air and in nitrogen. J. Chem. Soc., 2617–2623. https://doi.org/10.1039/JR9630002617
Dollimore, D. (1987). The thermal decomposition of oxalates: a review. Thermochim. Acta, 117, 331–363. https://doi.org/10.1016/0040-6031(87)88023-1
Baes, C. F., & Mesmer, R. E. (1976). The Hydrolysis of Cations. Wiley-Interscience, New York. ISBN: 978-0-471-03985-7.
Yue, P., Wang, Z., Li, X., Xiong, X., Wang, J., Wu, X., & Guo, H. (2013). The enhanced electrochemical performance of Li[Ni0.6Co0.2Mn0.2]O2 cathode material by a low temperature Co-precipitation method. Electrochim. Acta, 95, 112–118. https://doi.org/10.1016/j.electacta.2013.02.029
Maciejewski, M., Ingier-Stocka, E., Emmerich, W. D., & Baiker, A. (2000). Monitoring of the gas phase composition: a prerequisite for unravelling the mechanism of decomposition of solids. Thermal decomposition of cobalt oxalate dihydrate. J. Therm. Anal. Calorim., 60, 735–758. https://doi.org/10.1023/A:1010135003141
Martell, A. E., & Smith, R. M. (2004). NIST Standard Reference Database 46: Critically Selected Stability Constants of Metal Complexes, Version 8.0. National Institute of Standards and Technology, Gaithersburg, MD. https://www.nist.gov/srd/nist46
Varga, T., Kumar, A., Vlahos, E., Denev, S., Park, M., Hong, S., Sanehira, T., Wang, J., Fennie, C. J., Streiffer, S. K., Ke, X., Schiffer, P., Gopalan, V., & Mitchell, J. F. (2009). Coexistence of weak ferromagnetism and ferroelectricity in the high pressure LiNbO3-type phase of FeTiO3. Phys. Rev. Lett., 103, 047601. [Note: Ref. 16 in manuscript text refers to IR characterisation of mixed oxalates; replace with a dedicated IR spectroscopy study of NMC/NCA oxalate precursors when available.]
Galwey, A. K., & Brown, M. E. (1999). Thermal Decomposition of Ionic Solids: Chemical Properties and Reactivities of Ionic Crystalline Phases. Studies in Physical and Theoretical Chemistry, Vol. 86. Elsevier, Amsterdam. ISBN: 978-0-444-82437-5.
Abd El-Salaam, K. M., & Hassan, E. A. (1982). Kinetics of the thermal decomposition of nickel oxalate. Surf. Technol., 16(3), 179–188. https://doi.org/10.1016/0376-4583(82)90023-7
Khawam, A., & Flanagan, D. R. (2006). Solid-state kinetic models: basics and mathematical fundamentals. J. Phys. Chem. B, 110(35), 17315–17328. https://doi.org/10.1021/jp062746a
Levenspiel, O. (1999). Chemical Reaction Engineering (3rd ed.). John Wiley & Sons, New York, pp. 376–392. ISBN: 978-0-471-25424-9.
Chromčíková, M., Liška, M., & Plško, A. (2013). Kinetics of crystallization of cordierite glass. J. Therm. Anal. Calorim., 114, 947–954. https://doi.org/10.1007/s10973-013-3154-8 [Placeholder — replace with a diffusion-controlled alumina formation reference, e.g., Wefers & Misra, Alcoa Technical Paper No. 19, 1987.]
Muraleedharan, K., Kannan, M. P., & Gangadevi, T. (1994). The thermal decomposition of cobalt oxalate dihydrate in flowing atmospheres of different gases. Thermochim. Acta, 232(2), 187–197. https://doi.org/10.1016/0040-6031(94)80059-6
Shannon, R. D. (1976). Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A, 32(5), 751–767. https://doi.org/10.1107/S0567739476001551
Atkinson, A. (1985). Transport processes during the growth of oxide films at elevated temperature. Rev. Mod. Phys., 57(2), 437–470. https://doi.org/10.1103/RevModPhys.57.437
Liu, T., Yu, L., Liu, J., Lu, J., Bi, X., Dai, A., Li, M., Li, M., Hu, Z., Ma, L., Luo, D., Zhong, J., Zhou, T., Yu, X., Li, H., Ren, Y., & Amine, K. (2019). Understanding Co roles towards developing Co-free Ni-rich cathodes for Li-ion batteries. Nat. Energy, 6, 277–286. https://doi.org/10.1038/s41560-021-00776-y [Placeholder for ref. 25 on NMC thermal decomposition kinetics; replace with Dong et al. (2021) J. Alloys Compd. 856, 158099 when DOI confirmed.]
Qian, G., Li, T., Zhao, P., & Liang, J. (2020). Thermal stability and decomposition kinetics of NCA cathode hydroxide precursors. J. Therm. Anal. Calorim., 139(2), 1313–1321. https://doi.org/10.1007/s10973-019-08547-0
DOI: https://doi.org/10.20961/esta.v4i2.117683
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