Uncovering Full-Cell Cycling Morphology Through a Rechargeable Sodium Ion Battery Based on Tungsten Oxide and Sodium Prussian Blue Intercalation Chemistry

Abstract

Half-cells have been employed to investigate the intrinsic electrochemical behavior of the cathode material, as the chemical potential of the alkali metal reference electrode remains relatively constant during discharge. However, in full cells, the discharge mechanism is anode-dependent. Herein, a rechargeable nonaqueous sodium ion battery (SIB) is fabricated using tungsten trioxide (WO₃) nanopowder on a graphite substrate as the anode and a nickel-hexacyanoferrate Prussian blue (PB) cathode to understand the dominant discharge mechanism. The battery cells are evaluated for reversibility and durability and exhibit reversible charge–discharge plateaus, confirming sodium-ion intercalation/deintercalation in both electrodes. The sodium-ion diffusion coefficient of 5.3 × 10⁻¹³cm².s⁻¹ calculated using electrochemical impedance spectroscopy (EIS) is consistent with a planar finite space diffusion mechanism. Cyclic voltammetry (CV) shows a broad reversible redox peak on the WO₃ anode, owing to its multiple valence states, also observed in potential versus differential capacitance (dQ/dV) and simulated density of states (DOS). The full cell demonstrates an open-circuit voltage (OCV) of 2.2 V (charged), a discharge capacity of 79 mAh.g⁻¹ at 0.1C rate, and retains 69% of its capacity after 500 cycles, indicating promising durability and reversibility for sodium-ion storage. The charge carrier concentration (ccc), DOS, electrical and thermal conductivities, and chemical potential simulations for the charged and discharged phases, in both electrodes, reveal that the anode determines the shape of the discharge curve and the cathode the capacity of the cell. This study paves the way to predicting the behavior of a full cell, including cycling curve shape, process, dependencies, and thermal runaway.

Keywords

DFT simulated discharge curves / full cell batteries / sodium ion batteries / sodium Prussian blue cathodes / tungsten trioxide anodes

References

[1] M. Amir, R. G. Deshmukh, H. M. Khalid, et al., “Energy Storage Technologies: An Integrated Survey of Developments, Global Economical/Environmental Effects, Optimal Scheduling Model, and Sustainable Adaption Policies,” Journal of Energy Storage72 (2023): 108694.

[2] V. Karol, P. Sharma, A. Singh, D. Goel, and S. Kaur, “Review of Energy Storage Devices: Fuel Cells, Hydrogen Storage Fuel Cells, Rechargeable Batteries, PV Solar Cells,” Materials for Boosting Energy Storage. Volume 3: Advances in Sustainable Energy Technologies, Vol. 1488, 1-15 (2025). ACS Publications.

[3] B. S. Nishchith, S. Ashoka, M. P. Bhat, et al., “Reversible Surface Reconstruction of Na₃NiCO₃PO₄: A Battery Type Electrode for Pseudocapacitor Applications,” Journal of Power Sources520 (2022): 230903.

[4] H. Ajibade, C. O. Ujah, K. C. Nnakwo, and D. V. V. Kallon, “Improvement in Battery Technologies as Panacea for Renewable Energy Crisis,” Discover Applied Sciences6 (2024): 374.

[5] G. G. Njema, R. B. O. Ouma, and J. K. Kibet, “A Review on the Recent Advances in Battery Development and Energy Storage Technologies,” Journal of Renewable Energy32 (2024): 35.

[6] Z. Lina and Y. Zou, “Energy Efficiency of Lithium-Ion Batteries: Influential Factors and Long-Term Degradation,” Journal of Energy Storage74 (2023): 109356.

[7] B. S. Nishchith, Y. Kalegowda, S. Ashoka, et al., “Electrochemical Kinetic Study and Performance Evaluation of Surface-Modified Mesoporous Sodium Carbonophosphates Nanostructures for Pseudocapacitor Applications,” Journal of Alloys and Compounds 939 (2023): 168711.

[8] Z. J. Baum, R. E. Bird, X. Yu, and J. Ma, “Lithium-Ion Battery Recycling Overview of Techniques and Trends,” ACS Energy Letters7, no. 2 (2022): 712-719.

[9] F. M. N. U. Khan, M. G. Rasul, A. S. M. Sayem, and N. K. Mandal, “Design and Optimization of Lithium-Ion Battery as an Efficient Energy Storage Device for Electric Vehicles: A Comprehensive Review,” Journal of Energy Storage71 (2023): 108033.

[10] A. Manthiram, “An Outlook on Lithium-Ion Battery Technology,” ACS Central Science3 (2017): 1063-1069.

[11] P. U. Nzereogu, A. D. Omah, F. I. Ezema, E. I. Iwuoha, and A. C. Nwanya, “Anode Materials for Lithium-Ion Batteries: A Review,” Applied Surface Science Advances9 (2022): 100233.

[12] Q. Li, J. Chen, L. Fan, X. Kong, and Y. Lu, “Progress in Electrolytes for Rechargeable Li-Based Batteries and Beyond,” Green Energy & Environment (2016): 18-42.

[13] H. Zhang, Y. Huang, H. Ming, et al., “Recent Advances in Nanostructured Carbon for Sodium-Ion Batteries,” Journal of Materials Chemistry A8 (2020): 1604-1630.

[14] W. Zuo, A. Innocenti, M. Zarrabeitia, D. Bresser, Y. Yang, and S. Passerini, “Layered Oxide Cathodes for Sodium-Ion Batteries: Storage Mechanism, Electrochemistry, and Techno-Economics,” Accounts of Chemical Research56 (2023): 284-296.

[15] W. Zhang, F. Zhang, F. Ming, and H. N. Alshareef, “Sodium-Ion Battery Anodes: Status and Future Trends,” EnergyChem1 (2019): 100012.

[16] S. Mukherjee, S. Bin Mujib, D. Soares, and G. Singh, “Electrode Materials for High-Performance Sodium-Ion Batteries,” Materials1952 (2019): 12.

[17] W. Luo, F. Shen, C. Bommier, H. Zhu, X. Ji, and L. Hu, “Na Ion Battery Anodes: Materials and Electrochemistry,” Accounts of Chemical Research49 (2016): 231-240.

[18] A. L. Santhosha, S. K. Das, and A. J. Bhattacharyya, “Tungsten Trioxide (WO₃) Nanoparticles as a New Anode Material for Sodium-Ion Batteries,” Journal of Nanoscience and Nanotechnology16 (2016): 4131-4135.

[19] Y. E. Durmus, H. Zhang, F. Baakes, et al., “Side by Side Battery Technologies With Lithium-Ion Based Batteries,” Advanced Energy Materials2000089 (2020): 1614-6832.

[20] M. Rastgoo-Deylami, M. Javanbakht, H. Omidvar, K. Hooshyari, P. Salarizadeh, and M. B. Askari, “Nickel-Doped Monoclinic WO₃ as High Performance Anode Material for Rechargeable Lithium Ion Battery,” Journal of Electroanalytical Chemistry894 (2021): 115383.

[21] C. Xu, Z. Yang, X. Zhang, et al., “Prussian Blue Analogues in Aqueous Batteries and Desalination Batteries,” Nano-Micro Letters13 (2021): 166.

[22] Y. Wu, W. Shuang, Y. Wang, et al., “Recent Progress in Sodium Ion Batteries: Advanced Materials, Reaction Mechanisms and Energy Applications,” Electrochemical Energy Reviews7 (2024): 17.

[23] K. Hurlbutt, S. Wheeler, I. Capone, and M. Pasta, “Prussian Blue Analogs as Battery Materials,” Joule2, no. 10: 1950-1960.

[24] Y. Xiao, J. Xiao, H. Zhao, et al., “Prussian Blue Analogues for Sodium-Ion Battery Cathodes: A Review of Mechanistic Insights, Current Challenges, and Future Pathways,” Small20 (2024): 2401957.

[25] X. Zhao, N. Liu, M. Zheng, et al., “Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries,” ACS Energy Letters9 (2024): 2748-2757.

[26] Z. Zhang, M. Avdeev, H. Chen, W. Yin, W. H. Kan, and G. He, “Lithiated Prussian Blue Analogues as Positive Electrode Active Materials for Stable Non-Aqueous Lithium-Ion Batteries,” Nature Communications13 (2022): 7790.

[27] C. D. Wessells, R. A. Huggins, and Y. Cui, “Copper Hexacyanoferrate Battery Electrodes With Long Cycle Life and High Power,” Nature Communications2 (2011): 550.

[28] Y. Xiao, J. Xiao, H. Zhao, et al., “Prussian Blue Analogues for Sodium-Ion Battery Cathodes: A Review of Mechanistic Insights, Current Challenges, and Future Pathways,” Small Methods8 (2024): 24001957.

[29] R. Rehman, J. Peng, H. Yi, et al., “Highly Crystalline Nickel Hexacyanoferrate as a Long-Life Cathode Material for Sodium-Ion Batteries,” RSC Advances10 (2020): 27033-27041.

[30] S. Chong, J. Yang, L. Sun, S. Guo, Y. Liu, and H. K. Liu, “Potassium Nickel Iron Hexacyanoferrate as Ultra-Long-Life Cathode Material for Potassium-Ion Batteries With High Energy Density,” ACS Nano14 (2020): 9807-9818.

[31] X. H. Ma, Y. Y. Wei, Y. D. Wu, et al., “High Crystalline Na₂Ni[Fe(CN)₆] Particles for a High-Stability and Low-Temperature Sodium-Ion Batteries Cathode,” Electrochimica Acta297 (2019): 392-397.

[32] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters77, no. 18 (1996): 3865-3868, https://doi.org/10.1103/PhysRevLett.77.3865.

[33] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes Forab Initiototal-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B54 (1996): 11169-11186.

[34] K. Parlinski, Z. Q. Li, and Y. Kawazoe, “First-Principles Determination of the Soft Mode in Cubic ZrO₂,” Physical Review Letters78 (1997): 4063-4066.

[35] G. K. H. Madsen and D. J. Singh, “BoltzTraP. A Code for Calculating Band-Structure Dependent Quantities,” Computer Physics Communications175 (2006): 67-71.

[36] B. Yang, P. Miao, and J. Cui, “Characteristics of Amorphous WO₃ Thin Films as Anode Materials for Lithium-Ion Batteries,” Journal of Materials Science: Materials in Electronics31 (2020): 11071-11076, https://doi.org/10.1007/s10854-020-03656-5.

[37] X. Dong, Y. Liu, S. Zhu, et al., “Architecting Hierarchical WO₃ Agglomerates Assembled With Straight and Parallel Aligned Nanoribbons Enabling High Capacity and Robust Stability of Lithium Storage,” Frontiers in Chemistry9 (2022): 834418, https://doi.org/10.3389/fchem.2021.834418.

[38] B. A. Maia, B. M. Gomes, A. N. Guerreiro, R. M. Santos, and M. H. Braga, “Cathodes Pinpoints for the Next Generation of Energy Storage Devices: The LiFePO₄ Case Study,” JPhys Materials7, no. 2, (2024): 025001, https://doi.org/10.1088/2515-7639/ad218c.

[39] B. M. Gomes, M. C. Baptista, A. Orue, et al., “All-Solid-State Lithium Batteries With NMC955 Cathodes: PVDF-Free Formulation With SBR and Capacity Recovery Insights,” Energy Materials5 (2025): 500091, https://doi.org/10.20517/energymater.2024.297.

[40] B. M. Gomes, J. F. R. Moutinho, and M. H. Braga, “A Perspective on the Building Blocks of a Solid-State Battery: From Solid Electrolytes to Quantum Power Harvesting and Storage,” Journal of Materials Chemistry A12 (2024): 690-722, https://doi.org/10.1039/D3TA04228F.

RIGHTS & PERMISSIONS

2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.