Electrochemical performance of Na2MnPO4F/C cathode synthesized through a solid-state method with variation of carbon concentration between citric acid and coconut shell charcoal
DOI:
https://doi.org/10.61511/jimese.v4i1.2026.2692Keywords:
carbon, citric acid, diffusion, electrochemistry, solid-stateAbstract
Background: The increasing demand for sustainable and low-cost energy storage systems has encouraged the development of sodium-ion batteries as an alternative to lithium-ion batteries. However, the low electronic conductivity and slow Na⁺ diffusion kinetics of Na₂MnPO₄F remain major limitations for its cathode performance. Methods: In this study, Na₂MnPO₄F/C cathode materials were synthesized using a solid-state method with carbon coating derived from citric acid and coconut shell charcoal at concentrations of 0, 3, 5, and 7 wt.%. Findings: Structural characterization confirmed the successful formation of the Na₂MnPO₄F phase, where citric acid at 7 wt.% produced the highest phase purity (99.9%), while coconut shell charcoal achieved the highest purity at 3 wt.% (90.066%). SEM-EDX analysis revealed that increasing carbon concentration influenced particle morphology, elemental distribution, and surface porosity, while FTIR analysis confirmed the presence of Mn–O, PO₄, and C–C bonding within the composites. Electrochemical characterization using EIS demonstrated that carbon coating significantly improved charge-transfer behavior, with the 7 wt.% citric acid sample exhibiting the lowest resistance and the best electron transport capability. Conclusion: These findings indicate that carbon coating, particularly using citric acid, effectively enhances the structural stability and electrochemical performance of Na₂MnPO₄F cathodes, highlighting its potential for sustainable sodium-ion battery applications. Novelty/Originality oh this article: The use of carbon coating derived from citric acid and coconut shell charcoal at concentrations of 0, 3, 5, and 7 wt.% on Na₂MnPO₄F/C cathode materials successfully improved charge-transfer behavior, structural stability, and electron transport capability, particularly in the 7 wt.% citric acid sample which exhibited the lowest resistance and the best electron transport capability.
References
Ahsan, Z., Cai, Z., Wang, S., Moin, M., Wang, H., Liu, D., Ma, Y., Song, G., & Wen, C. (2024). Recent development of phosphate based polyanion cathode materials for sodium-ion batteries. Advanced Energy Materials. https://doi.org/10.1002/aenm.202400373
Broux, T., Fauth, F., Hall, N., Chatillon, Y., Bianchini, M., Bamine, T., Leriche, J.-B., Suard, E., Carlier, D., Reynier, Y., Simonin, L., Masquelier, C., & Croguennec, L. (2018). High rate performance for carbon-coated Na₃V₂(PO₄)₂F₃ in Na-ion batteries. Small Methods. https://doi.org/10.1002/smtd.201800215
Chen, L., Feng, W., Pu, Z., Wang, X., Su, W., Li, M., Song, C., Shi, Z., & Zheng, Y. (2019). Effects of citric acid on the preparation of a LiFePO₄@C cathode material assisted by biomineralization. International Journal of Electrochemical Science, 14, 8048–8057. https://doi.org/10.20964/2019.08.78
Dacek, S. T., Richards, W. D., Kitchaev, D. A., & Ceder, G. (2016). Structure and dynamics of fluorophosphate Na-ion battery cathodes. Chemistry of Materials, 28(15), 5450–5460. https://doi.org/10.1021/acs.chemmater.6b01989
Gaddam, R. R., Katzenmeier, L., Lamprecht, X., & Bandarenka, A. S. (2021). Review on physical impedance models in modern battery research. Physical Chemistry Chemical Physics, 23(23), 12926–12944. https://doi.org/10.1039/D1CP00673H
Guo, J.-Z., Gu, Z.-Y., Du, M., Zhao, X.-X., Wang, X.-T., & Wu, X.-L. (2023). Emerging characterization techniques for delving polyanion-type cathode materials of sodium-ion batteries. Materials Today. https://doi.org/10.1016/j.mattod.2023.03.020
Harper, G., Sommerville, R., Kendrick, E., Driscoll, L., Slater, P., Stolkin, R., Walton, A., Christensen, P., Heidrich, O., Lambert, S., Abbott, A., Ryder, K., Gaines, L., & Anderson, P. (2019). Recycling lithium-ion batteries from electric vehicles. Nature, 575(7781), 75–86. https://doi.org/10.1038/s41586-019-1682-5
Hu, Y., Wu, L., Liao, G., Yang, Y., Ye, F., Chen, J., Zhu, X., & Zhong, S. (2018). Electrospinning synthesis of Na₂MnPO₄F/C nanofibers as a high voltage cathode material for Na-ion batteries. Ceramics International, 44(15), 17577–17584. https://doi.org/10.1016/j.ceramint.2018.06.236
Huang, H.-B., Liu, C.-L., Yang, Y., & Luo, S. (2022). Citric acid-assisted synthesis of Na₃V₂(PO₄)₃/C composite as high-performance electrode material for sodium-ion batteries. Ionics, 28(10), 4631–4639. https://doi.org/10.1007/s11581-022-04696-z
Jin, T., Li, H., Zhu, K., Wang, P.-F., Liu, P., & Jiao, L. (2020). Polyanion-type cathode materials for sodium-ion batteries. Chemical Society Reviews, 49(8), 2342–2377. https://doi.org/10.1039/C9CS00846B
Kim, S.-W., Seo, D.-H., Kim, H., Park, K.-Y., & Kang, K. (2012). A comparative study on Na₂MnPO₄F and Li₂MnPO₄F for rechargeable battery cathodes. Physical Chemistry Chemical Physics, 14(10), 3299–3303. https://doi.org/10.1039/C2CP40082K
Kim, T., Choi, W., Shin, H.-C., Choi, J.-Y., Kim, J. M., Park, M.-S., & Yoon, W.-S. (2020). Applications of voltammetry in lithium ion battery research. Journal of Electrochemical Science and Technology, 11(1), 14–25. https://doi.org/10.33961/jecst.2019.00619
Langford, J. I., & Wilson, A. J. C. (1978). Scherrer after sixty years: A survey and some new results in the determination of crystallite size. Journal of Applied Crystallography, 11(2), 102–113. https://doi.org/10.1107/S0021889878012844
Lin, X., et al. “Exploiting Na₂MnPO₄F as a High-Capacity and Well-Reversible Cathode Material for Na-Ion Batteries.” RSC Advances 4, no. 77 (2014): 40985–40993. https://doi.org/10.1039/C4RA05336B.
Ling, R., Cai, S., Shen, K., Sang, Z., Xie, D., Sun, J., Xiong, K., Guo, J., & Sun, X. (2019). Dual carbon-confined Na₂MnPO₄F nanoparticles as a superior cathode for rechargeable sodium-ion battery. Ceramics International. https://doi.org/10.1016/j.ceramint.2019.06.235
Niu, Y., Zhao, Y., & Xu, M. (2023). Manganese-based polyanionic cathodes for sodium-ion batteries. Carbon Neutralization, 2(2), 150–168. https://doi.org/10.1002/cnl2.48
Patterson, A. L. (1939). The Scherrer formula for X-ray particle size determination. Physical Review, 56(10), 978–982. https://doi.org/10.1103/PhysRev.56.978
Rojo, T., Forsyth, M., Lee, H. S., Zhang, W., & Armand, M. (2018). Sodium-ion batteries. Advanced Energy Materials, 8(17), 1800880. https://doi.org/10.1002/aenm.201800880
Safitri, M., Zainuri, M., Subhan, A., Putri, S. S. H., & Putri, F. L. V. P. (2023). The influence of variations carbon content on the structure of Na₂MnPO₄F/C cathode material. Journal of Physics: Conference Series, 2498, 012029. https://doi.org/10.1088/1742-6596/2498/1/012029
Siburian, R., Raja, S. L., Supeno, M., & Simanjuntak, C. (2019). Application of coconut battery waste to graphic as an alternative electrode on primary battery cells. Abdimas Talenta: Jurnal Pengabdian Kepada Masyarakat, 4(2), 668–673. https://doi.org/10.32734/abdimastalenta.v4i2.4202
Sui, Y., Shi, Z., Hu, Y., Zhang, X., Wu, X., & Wu, L. (2021). A pre-oxidation strategy to improve architecture stability and electrochemical performance of Na₂MnPO₄F particles-embedded carbon nanofibers. Journal of Colloid and Interface Science. https://doi.org/10.1016/j.jcis.2021.06.081
Sun, Y., Shi, X.-L., Yang, Y.-L., Suo, G., Zhang, L., Lu, S., & Chen, Z.-G. (2022). Biomass-derived carbon for high-performance batteries: From structure to properties. Advanced Functional Materials. https://doi.org/10.1002/adfm.202201584
Wu, L., Hu, Y., Zhang, X., Liu, J., Zhu, X., & Zhong, S. (2018). Synthesis of carbon-coated Na₂MnPO₄F hollow spheres as a potential cathode material for Na-ion batteries. Journal of Power Sources, 374, 40–47. https://doi.org/10.1016/j.jpowsour.2017.11.029
Wu, X., Zheng, J., Gong, Z., & Yang, Y. (2011). Sol–gel synthesis and electrochemical properties of fluorophosphates Na₂Fe₁−xMnₓPO₄F/C (x = 0, 0.1, 0.3, 0.7, 1) composite as cathode materials for lithium ion battery. Journal of Materials Chemistry, 21, 18630–18637. https://doi.org/10.1039/C1JM13578C
Yao, Q., Zheng, C., Liu, K., Wang, M., Song, J., Cui, L., Dou, S. X., Bai, Z., & Yang, J. (2024). Bi nanospheres embedded in N-doped carbon nanowires facilitate ultrafast and ultrastable sodium storage. Advanced Science, 11(28), e2401730. https://doi.org/10.1002/advs.202401730
Zhang, J. (2017). Development of property prediction methods for sodium-ion battery electrolytes. Queen’s University Belfast Research Portal. https://pure.qub.ac.uk/en/studentTheses/development-of-property-prediction-methods-for-sodium-ion-battery
Zhang, L., Dai, Y., Li, C., Dang, Y., Zheng, R., Wang, Z., Wang, Y., Cui, Y., Arandiyan, H., Shao, Z., Sun, H., Zhuang, Q., & Liu, Y. (2024). Recent advances in electrochemical impedance spectroscopy for solid-state batteries. Energy Storage Materials. https://doi.org/10.1016/j.ensm.2024.103378
Zhang, S., Gong, G., Wang, H., Chen, S., Wang, J., & Qi, J. (2025). Advances and challenges of the spray drying technology: Towards accurately constructing inorganic multi-functional materials and related applications. Sustainable Materials and Technologies. https://doi.org/10.1016/j.susmat.2025.e01250
Zheng, Y., Zhang, P., Wu, S. Q., Wen, Y. H., Zhu, Z. Z., & Yang, Y. (2013). First-principles investigations on the Na₂MnPO₄F as a cathode material for Na-ion batteries. Journal of The Electrochemical Society, 160(6), A927–A932. https://doi.org/10.1149/2.127306jes
Zhong, Y., Wu, Z., Tang, Y., Xiang, W., Guo, X., & Zhong, B. (2015). Micro-nano structure Na₂MnPO₄F/C as cathode material with excellent sodium storage properties. Materials Letters. https://doi.org/10.1016/j.matlet.2015.01.110
Zhu, X., Li, Q., Fang, Y., Liu, X., Xiao, L., Ai, X., Yang, H., & Cao, Y. (2016). Graphene-modified TiO₂ microspheres synthesized by a facile spray-drying route for enhanced sodium-ion storage. Particle & Particle Systems Characterization, 33(11), 1–8. https://doi.org/10.1002/ppsc.201500216
Downloads
Published
How to Cite
Issue
Section
Citation Check
License
Copyright (c) 2026 Nugraha Ramadhan
This work is licensed under a Creative Commons Attribution 4.0 International License.
