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Title: Alluaudite Na2Co2 Fe(PO4)3 as an electroactive material for sodium ion batteries

Abstract

The electroactive orthophosphate Na2Co2Fe(PO4)3 was synthesized using a solid state reaction. Its crystal structure was solved using the combination of powder X-ray-and neutron-diffraction data. This material crystallizes according to the alluaudite structure (S.G. C2/c). The structure consists of edge sharing [MO6] octahedra (M = Fe, Co) resulting in chains parallel to [-101]. These chains are linked together via the [PO4] tetrahedra to form two distinct tunnels in which sodium cations are located. The electrochemical properties of Na2Co2Fe(PO4)3 were evaluated by galvanostatic charge-discharge cycling. During the first discharge to 0.03 V, Na2Co2Fe(PO4)3 delivers a specific capacity of 604 mA h g(-1). This capacity is equivalent to the reaction of more than seven sodium ions per formula unit. Hence, this is a strong indication of a conversion-type reaction with the formation of metallic Fe and Co. The subsequent charge and discharge involved the reaction of fewer Na ions as expected for a conversion reaction. When discharged to 0.9 V, the material intercalated only one Na+-ion leading to the formation of a new phase Na3Co2Fe(PO4)3. This phase could then be cycled reversibly with an average voltage of 3.6 V vs. Na+/Na and a capacity of 110 mA h g(-1). This result is inmore » good agreement with the theoretical capacity expected from the extraction/insertion of two sodium atoms in Na2Co2Fe(PO4)3.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [4];  [5]
+ Show Author Affiliations
  1. Qatar Foundation, Doha (Qatar). Qatar Environment and Energy Research Inst.
  2. Univ. del País Vasco, Bilbao (Spain). Dept. de Física de la Materia Condensada
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
  4. Nankai Univ., Tianjin (China). Inst. of New Energy Material Chemistry
  5. Hanyang Univ., Seongdong-gu, Seoul (Korea). Dept. of Energy Engineering
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1338506
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 17; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Essehli, R., Belharouak, I., Ben Yahia, H., Maher, K., Abouimrane, A., Orayech, B., Calder, S., Zhou, X. L., Zhou, Z., and Sun, Y-K. Alluaudite Na2Co2 Fe(PO4)3 as an electroactive material for sodium ion batteries. United States: N. p., 2015. Web. doi:10.1039/C5DT00971E.
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Essehli, R., Belharouak, I., Ben Yahia, H., Maher, K., Abouimrane, A., Orayech, B., Calder, S., Zhou, X. L., Zhou, Z., & Sun, Y-K. Alluaudite Na2Co2 Fe(PO4)3 as an electroactive material for sodium ion batteries. United States. https://doi.org/10.1039/C5DT00971E
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Essehli, R., Belharouak, I., Ben Yahia, H., Maher, K., Abouimrane, A., Orayech, B., Calder, S., Zhou, X. L., Zhou, Z., and Sun, Y-K. Mon . "Alluaudite Na2Co2 Fe(PO4)3 as an electroactive material for sodium ion batteries". United States. https://doi.org/10.1039/C5DT00971E. https://www.osti.gov/servlets/purl/1338506.
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@article{osti_1338506,
title = {Alluaudite Na2Co2 Fe(PO4)3 as an electroactive material for sodium ion batteries},
author = {Essehli, R. and Belharouak, I. and Ben Yahia, H. and Maher, K. and Abouimrane, A. and Orayech, B. and Calder, S. and Zhou, X. L. and Zhou, Z. and Sun, Y-K.},
abstractNote = {The electroactive orthophosphate Na2Co2Fe(PO4)3 was synthesized using a solid state reaction. Its crystal structure was solved using the combination of powder X-ray-and neutron-diffraction data. This material crystallizes according to the alluaudite structure (S.G. C2/c). The structure consists of edge sharing [MO6] octahedra (M = Fe, Co) resulting in chains parallel to [-101]. These chains are linked together via the [PO4] tetrahedra to form two distinct tunnels in which sodium cations are located. The electrochemical properties of Na2Co2Fe(PO4)3 were evaluated by galvanostatic charge-discharge cycling. During the first discharge to 0.03 V, Na2Co2Fe(PO4)3 delivers a specific capacity of 604 mA h g(-1). This capacity is equivalent to the reaction of more than seven sodium ions per formula unit. Hence, this is a strong indication of a conversion-type reaction with the formation of metallic Fe and Co. The subsequent charge and discharge involved the reaction of fewer Na ions as expected for a conversion reaction. When discharged to 0.9 V, the material intercalated only one Na+-ion leading to the formation of a new phase Na3Co2Fe(PO4)3. This phase could then be cycled reversibly with an average voltage of 3.6 V vs. Na+/Na and a capacity of 110 mA h g(-1). This result is in good agreement with the theoretical capacity expected from the extraction/insertion of two sodium atoms in Na2Co2Fe(PO4)3.},
doi = {10.1039/C5DT00971E},
journal = {Dalton Transactions},
number = 17,
volume = 44,
place = {United States},
year = {Mon Mar 23 00:00:00 EDT 2015},
month = {Mon Mar 23 00:00:00 EDT 2015}
}
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Journal Article:
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https://doi.org/10.1039/C5DT00971E
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Cited by: 46 works
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Figures / Tables:

Fig. S1 Fig. S1: Final observed, calculated and difference plots for XRPD (Cu-Kα radiation) refinement of Na2Co2Fe(PO4)3. The inset corresponds to a zoom of the 2$θ$ = 13 to 40 ° area
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    Works referencing / citing this record:

    Challenges and Perspectives for NASICON-Type Electrode Materials for Advanced Sodium-Ion Batteries
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    Polyanionic Insertion Materials for Sodium-Ion Batteries
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    Synthesis, Structure, and Conductivity of Alluaudite-Related Phases in the Na 2 MoO 4 -Cs 2 MoO 4 -CoMoO 4 System : Synthesis, Structure, and Conductivity of Alluaudite-Related Phases in the Na
    journal, December 2018

    • Yudin, Vasiliy N.; Zolotova, Evgeniya S.; Solodovnikov, Sergey F.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 2
    • DOI: 10.1002/ejic.201801307

    A new sodium ferrous orthophosphate Na x Fe4(PO4)3 as anode materials for sodium-ion batteries
    journal, February 2018

    Synthesis, Crystal Structure and Properties of a New Phosphate, Na2Co2Cr(PO4)3
    journal, September 2018

    • Hadouchi, Mohammed; Assani, Abderrazzak; Saadi, Mohamed
    • Journal of Inorganic and Organometallic Polymers and Materials, Vol. 28, Issue 6
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    Synthesis, Characterization, and Magnetic Properties of A2Co2Fe(VO4)3 (A = Ag or Na) Alluaudite-Type Vanadates
    journal, December 2018

    • Hadouchi, Mohammed; Assani, Abderrazzak; Saadi, Mohamed
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    Na 3 V 2 (PO 4 ) 3 : an advanced cathode for sodium-ion batteries
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      Figures / Tables found in this record:

      Fig. S1 (p. 4)figure
      Table 1 (p. 5)table
      Fig. 1 (p. 7)figure
      Table 2 (p. 7)table
      Table 3 (p. 8)table
      Fig. 2 (p. 9)figure
      Fig. 3 (p. 10)figure
      Fig. 4 (p. 11)figure
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