Safer and Sustainable Co-precipitation Synthesis of NCA (LiNi0.80Co0.15Al0.05O2) Cathodes: Eliminating Ammonia in Favor of NaOH for pH Control
Abstract
Developing safer and more sustainable synthesis routes for lithium ion battery cathodes is important for both environmental practice and laboratory education. This study reports an ammonia free oxalate coprecipitation route to synthesize LiNi0.80Co0.15Al0.05O2 (NCA), in which ammonia as the usual pH controller was fully replaced by sodium hydroxide (NaOH). NaOH dosage was varied at 20 g, 40 g, 60 g, and 80 g to control precipitation, precursor quality, and the properties of the final cathode after calcination and sintering. X ray diffraction confirmed formation of a layered α NaFeO2 type structure with R3m symmetry for all samples without detectable secondary phases. The 40 g NaOH condition showed the best structural ordering, reflected by a relatively high I(003)/I(104) intensity ratio associated with reduced cation mixing. Fourier transform infrared spectra verified oxalate ligand decomposition during thermal treatment and the appearance of metal oxygen lattice vibrations consistent with NCA formation. Scanning electron microscopy revealed that the 40 g NaOH sample produced more uniform particles with a narrower size distribution than other variants. Based on these results, the 40 g NaOH sample was selected for electrochemical evaluation and delivered an initial discharge capacity of about 110 mAh g−1 at 0.1 C in a full cell configuration. Overall, NaOH is demonstrated as an effective and safer substitute for ammonia in oxalate coprecipitation, enabling greener NCA synthesis protocols for research and teaching.
Keywords
References
[1] D. A. Elalfy, E. Gouda, M. F. Kotb, V. Bureš, and B. E. Sedhom, “Comprehensive review of energy storage systems technologies, objectives, challenges, and future trends,” Energy Strateg. Rev., vol. 54, no. June, 2024, doi: 10.1016/j.esr.2024.101482.
[2] T. A. Manfo and M. E. Şahin, “Intercalation reaction in lithium-ion battery: effect on cell characteristics,” Int. J. Mater. Eng. Technol., vol. 6, no. 2, pp. 70–78, 2023, [Online]. Available: http://dergipark.gov.tr/tijmet
[3] S. A. Arote, “Fundamentals and perspectives of lithium-ion batteries,” Lithium-ion Lithium–Sulfur Batter., pp. 1-1-1–26, 2022, doi: 10.1088/978-0-7503-4881-2ch1.
[4] A. K. Koech, G. Mwandila, F. Mulolani, and P. Mwaanga, “Lithium-ion battery fundamentals and exploration of cathode materials: A review,” South African J. Chem. Eng., vol. 50, no. June, pp. 321–339, 2024, doi: 10.1016/j.sajce.2024.09.008.
[5] B. Cui, Z. Xiao, S. Cui, S. Liu, X. Gao, and G. Li, Safety Issues and Improvement Measures of Ni-Rich Layered Oxide Cathode Materials for Li-Ion Batteries, vol. 7, no. 1. Springer Nature Singapore, 2024. doi: 10.1007/s41918-024-00211-2.
[6] B. Fu, M. Moździerz, A. Kulka, and K. Świerczek, “Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells,” Int. J. Miner. Metall. Mater., vol. 31, no. 11, pp. 2345–2367, 2024, doi: 10.1007/s12613-024-2948-y.
[7] C. S. Yudha, L. M. Hasanah, S. U. Muzayanha, H. Widiyandari, and A. Purwanto, “Synthesis and Characterization of Material LiNi0.8Co0.15Al0.05O2 Using One-Step Co-Precipitation Method for Li-Ion Batteries,” JKPK (Jurnal Kim. dan Pendidik. Kim., vol. 4, no. 3, p. 134, 2019, doi: 10.20961/jkpk.v4i3.29850.
[8] A. Purwanto, C. S. Yudha, U. Ubaidillah, H. Widiyandari, T. Ogi, and H. Haerudin, “NCA cathode material: Synthesis methods and performance enhancement efforts,” Mater. Res. Express, vol. 5, no. 12, 2018, doi: 10.1088/2053-1591/aae167.
[9] B. Huang et al., “Layered Cathode Materials: Precursors, Synthesis, Microstructure, Electrochemical Properties, and Battery Performance,” Small, vol. 18, no. 20, pp. 1–18, 2022, doi: 10.1002/smll.202107697.
[10] S. Mallick et al., “Low-cobalt active cathode materials for high-performance lithium-ion batteries: synthesis and performance enhancement methods,” J. Mater. Chem. A, vol. 11, no. 8, pp. 3789–3821, 2023, doi: 10.1039/d2ta08251a.
[11] W. Li, S. Lee, and A. Manthiram, “High-Nickel NMA: A Cobalt-Free Alternative to NMC and NCA Cathodes for Lithium-Ion Batteries,” Adv. Mater., vol. 32, no. 33, pp. 1–6, 2020, doi: 10.1002/adma.202002718.
[12] D. A. Khudhur, T. A. Tuan Abdullah, and N. Norazahar, “A Review of Safety Issues and Risk Assessment of Industrial Ammonia Refrigeration System,” ACS Chem. Heal. Saf., vol. 29, no. 5, pp. 394–404, 2022, doi: 10.1021/acs.chas.2c00041.
[13] S. C. D’Angelo et al., “Planetary Boundaries Analysis of Low-Carbon Ammonia Production Routes,” ACS Sustain. Chem. Eng., vol. 9, no. 29, pp. 9740–9749, 2021, doi: 10.1021/acssuschemeng.1c01915.
[14] C. S. Yudha et al., “Production of nickel-rich LiNi0.89Co0.08Al0.03O2cathode material for high capacity NCA/graphite secondary battery fabrication,” Open Eng., vol. 12, no. 1, pp. 501–510, 2022, doi: 10.1515/eng-2022-0051.
[15] A. Jumari, C. S. Yudha, M. Nizam, E. R. Dyartanti, Suranto, and A. Purwanto, “An environmentally friendly hydrometallurgy process for the recovery and reuse of metals from spent lithium-ion batteries, using organic acid,” Open Eng., vol. 12, no. 1, pp. 485–494, 2022, doi: 10.1515/eng-2022-0050.
[16] Z. Zhu et al., “Multichannel pathway-enriched mesoporous NiO nanocuboids for the highly sensitive and selective detection of 3-hydroxy-2-butanone biomarkers,” J. Mater. Chem. A, vol. 7, no. 17, pp. 10456–10463, 2019, doi: 10.1039/c9ta01013k.
[17] H. J. Oh et al., “Nickel oxalate dihydrate nanorods attached to reduced graphene oxide sheets as a high-capacity anode for rechargeable lithium batteries,” NPG Asia Mater., vol. 8, no. 5, 2016, doi: 10.1038/am.2016.59.
[18] Q. Ma et al., “Induction and Maintenance of Local Structural Durability for High-Energy Nickel-Rich Layered Oxides,” Small Methods, vol. 6, no. 6, pp. 1–11, 2022, doi: 10.1002/smtd.202200255.
[19] J. Meng et al., “Modulating Crystal and Interfacial Properties by W-Gradient Doping for Highly Stable and Long Life Li-Rich Layered Cathodes,” Adv. Funct. Mater., vol. 32, no. 19, pp. 1–11, 2022, doi: 10.1002/adfm.202113013.
[20] S. M. Kim et al., “Cs desorption behavior during hydrothermal treatment of illite with oxalic acid,” Environ. Sci. Pollut. Res., vol. 27, no. 28, pp. 35580–35590, 2020, doi: 10.1007/s11356-020-09675-3.
[21] Z. Zhang et al., “Hierarchical Structure Design of ZIF-Derived CoNiFe LDH Nanocages Grown on Ag Nanowires as High-Performance Cathode for Zn-Air Batteries,” Small, vol. 21, no. 23, pp. 1–11, 2025, doi: 10.1002/smll.202502344.
[22] C. Lv, Z. Li, X. Ren, K. Li, J. Ma, and X. Duan, “Revealing the degradation mechanism of Ni-rich cathode materials after ambient storage and related regeneration method,” J. Mater. Chem. A, vol. 9, no. 7, pp. 3995–4006, 2021, doi: 10.1039/d0ta10378kRefbacks
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