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Structural stabilities and electrochemistry of Na2FeSiO4 polymorphs: first-principles calculations

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Abstract

Searching for new cathode materials is very important in the field of Na-ion batteries. Transition metal sodium orthosilicates have attracted much attention due to the significant progress made in its analog of lithium orthosilicates. In this work, density functional theory (DFT) calculations are performed to study the structural stabilities, electronic and electrochemical properties of Na2FeSiO4 polymorphs, and their corresponding desodiated products Na x FeSiO4. Our results show that formation energies of all the calculated structures differ substantially upon removal of Na, indicating that phase transformations should happen during the desodiation for different polymorphs. NaFeSiO4 is the only energetically stable intermediate phase among the cases, leading to two theoretically voltage plateaus, i.e., ~ 2.0 V (2 ≥ x ≥ 1) and ~ 4.5 V (1 ≥ x ≥ 0) in Na x FeSiO4, respectively. Moreover, the oxidation of Fe2+ to Fe3+ ions is observed during the removal of the first Na ion, while both the oxidation of O and Fe ions occur during the further desodiation.

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Acknowledgments

This work is supported by the National Key R&D Program of China under Grant Nos. 2016YFA0202601 and 2016YFB0901502, the National Natural Science Foundation of China under Grant Nos. NSFC-DFG (21761132030), and the Scientific Research Foundation of the Education Department of Fujian Province under Grant No. JK2011045.

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Authors and Affiliations

  1. Department of Physics and Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen University, Xiamen, 361005, China

    S. Yu, J. Q. Hu, M. B. Hussain, S. Q. Wu & Z. Z. Zhu

  2. State Key Lab for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, 361005, China

    Y. Yang

  3. Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen University, Xiamen, 361005, China

    Z. Z. Zhu

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  1. S. Yu
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  2. J. Q. Hu
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  3. M. B. Hussain
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  4. S. Q. Wu
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  5. Y. Yang
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  6. Z. Z. Zhu
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Correspondence to S. Q. Wu or Z. Z. Zhu.

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Yu, S., Hu, J.Q., Hussain, M.B. et al. Structural stabilities and electrochemistry of Na2FeSiO4 polymorphs: first-principles calculations. J Solid State Electrochem 22, 2237–2245 (2018). https://doi.org/10.1007/s10008-018-3931-1

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  • DOI: https://doi.org/10.1007/s10008-018-3931-1

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