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Title: One-step hydrothermal synthesis and electrochemical performance of sodium-manganese-iron phosphate as cathode material for Li-ion batteries

Abstract

The sodium-manganese-iron phosphate Na2Mn1.5Fe1.5(PO4)3 (NMFP) with alluaudite structure was obtained by a one-step hydrothermal synthesis route. The physical properties and structure of this material were obtained through XRD and Mössbauer analyses. X-ray diffraction Rietveld refinements confirm a cationic distribution of Na+ and presence of vacancies in A(2)’, Na+ and small amounts of Mn2+ in A(1), Mn2+ in M(1) , 0.5 Mn2+ and Fe cations (Mn2+,Fe2+ and Fe3+) in M(2), leading to the structural formula Na2Mn(Mn0.5Fe1.5)(PO4)3. The particles morphology was investigated by SEM. Several reactions with different hydrothermal reaction times were attempted to design a suitable synthesis protocol of NMFP compound. The time of reaction was varied from 6 to 48 hours at 220°C. The pure phase of NMFP particles was firstly obtained when the hydrothermal reaction of NMFP precursors mixture was maintained at 220°C for 6 hours. When the reaction time was increased from 6 to 12, 24 and 48 hours, the dandelion structure was destroyed in favor of NMFP micro-rods. The combination of NMFP (NMFP-6H, NMFP-12H, NMFP-24H and NMFP-48H) structure refinement and Mössbauer characterizations shows that the increase of the reaction time leads to the progressive increment of Fe(III) and the decrease of the crystal size. The electrochemical testsmore » indicated that NMFP is a 3 V sodium intercalating cathode. The comparison of the discharge capacity evolution of studied NMFP electrode materials at C/5 current density shows different capacities of 48, 40, 34 and 34 mAhg-1 for NMFP-6H, NMFP-12H, NMFP-24H and NMFP-48H respectively. Interestingly, all samples show excellent capacity retention of about 99 % during 50 cycles.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Univ. of Liege, (Belgium)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1376510
Alternate Identifier(s):
OSTI ID: 1550207
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 253; Journal Issue: C; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Karegeya, Claude, Mahmoud, Abdelfattah, Vertruyen, Bénédicte, Hatert, Frédéric, Hermann, Raphaël P., Cloots, Rudi, and Boschini, Frédéric. One-step hydrothermal synthesis and electrochemical performance of sodium-manganese-iron phosphate as cathode material for Li-ion batteries. United States: N. p., 2017. Web. doi:10.1016/j.jssc.2017.06.021.
Karegeya, Claude, Mahmoud, Abdelfattah, Vertruyen, Bénédicte, Hatert, Frédéric, Hermann, Raphaël P., Cloots, Rudi, & Boschini, Frédéric. One-step hydrothermal synthesis and electrochemical performance of sodium-manganese-iron phosphate as cathode material for Li-ion batteries. United States. https://doi.org/10.1016/j.jssc.2017.06.021
Karegeya, Claude, Mahmoud, Abdelfattah, Vertruyen, Bénédicte, Hatert, Frédéric, Hermann, Raphaël P., Cloots, Rudi, and Boschini, Frédéric. Fri . "One-step hydrothermal synthesis and electrochemical performance of sodium-manganese-iron phosphate as cathode material for Li-ion batteries". United States. https://doi.org/10.1016/j.jssc.2017.06.021. https://www.osti.gov/servlets/purl/1376510.
@article{osti_1376510,
title = {One-step hydrothermal synthesis and electrochemical performance of sodium-manganese-iron phosphate as cathode material for Li-ion batteries},
author = {Karegeya, Claude and Mahmoud, Abdelfattah and Vertruyen, Bénédicte and Hatert, Frédéric and Hermann, Raphaël P. and Cloots, Rudi and Boschini, Frédéric},
abstractNote = {The sodium-manganese-iron phosphate Na2Mn1.5Fe1.5(PO4)3 (NMFP) with alluaudite structure was obtained by a one-step hydrothermal synthesis route. The physical properties and structure of this material were obtained through XRD and Mössbauer analyses. X-ray diffraction Rietveld refinements confirm a cationic distribution of Na+ and presence of vacancies in A(2)’, Na+ and small amounts of Mn2+ in A(1), Mn2+ in M(1) , 0.5 Mn2+ and Fe cations (Mn2+,Fe2+ and Fe3+) in M(2), leading to the structural formula Na2Mn(Mn0.5Fe1.5)(PO4)3. The particles morphology was investigated by SEM. Several reactions with different hydrothermal reaction times were attempted to design a suitable synthesis protocol of NMFP compound. The time of reaction was varied from 6 to 48 hours at 220°C. The pure phase of NMFP particles was firstly obtained when the hydrothermal reaction of NMFP precursors mixture was maintained at 220°C for 6 hours. When the reaction time was increased from 6 to 12, 24 and 48 hours, the dandelion structure was destroyed in favor of NMFP micro-rods. The combination of NMFP (NMFP-6H, NMFP-12H, NMFP-24H and NMFP-48H) structure refinement and Mössbauer characterizations shows that the increase of the reaction time leads to the progressive increment of Fe(III) and the decrease of the crystal size. The electrochemical tests indicated that NMFP is a 3 V sodium intercalating cathode. The comparison of the discharge capacity evolution of studied NMFP electrode materials at C/5 current density shows different capacities of 48, 40, 34 and 34 mAhg-1 for NMFP-6H, NMFP-12H, NMFP-24H and NMFP-48H respectively. Interestingly, all samples show excellent capacity retention of about 99 % during 50 cycles.},
doi = {10.1016/j.jssc.2017.06.021},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 253,
place = {United States},
year = {Fri Jun 23 00:00:00 EDT 2017},
month = {Fri Jun 23 00:00:00 EDT 2017}
}

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Works referenced in this record:

Synthesis and Structure of NaMn3(PO4)(HPO4)2, an Unoxidized Variant of the Alluaudite Structure Type
journal, February 1995

  • Leroux, F.; Mar, A.; Payen, C.
  • Journal of Solid State Chemistry, Vol. 115, Issue 1
  • DOI: 10.1006/jssc.1995.1127

Hydrothermal Synthesis, Structure, and Characterization of a Mixed-Valent Iron(II/III) Phosphate, NaFe3.67(PO4)3: A New Variation of the Alluaudite Structure Type
journal, August 1998

  • Korzenski, Michael B.; Schimek, George L.; Kolis, Joseph W.
  • Journal of Solid State Chemistry, Vol. 139, Issue 1
  • DOI: 10.1006/jssc.1998.7823

The Crystal Chemistry of Lithium in the Alluaudite Structure: A Study of the (Na1−xLix)CdIn2(PO4)3 Solid Solution (x=0 to 1)
journal, January 2002

  • Hatert, Frédéric; Antenucci, Diano; Fransolet, André-Mathieu
  • Journal of Solid State Chemistry, Vol. 163, Issue 1
  • DOI: 10.1006/jssc.2001.9392

Combined Experimental and Computational Analyses on the Electronic Structure of Alluaudite-Type Sodium Iron Sulfate
journal, October 2016

  • Oyama, Gosuke; Kiuchi, Hisao; Chung, Sai Cheong
  • The Journal of Physical Chemistry C, Vol. 120, Issue 41
  • DOI: 10.1021/acs.jpcc.6b05569

A structural, magnetic, and M�ssbauer spectral study of several Na?Mn?Fe-bearing alluaudites
journal, October 2004


Electrical Behavior of New Orthophosphates Na2M3(PO4)3 (M3=GaMn2, GaCd2, InMn2 and FeMnCd) with Alluaudite-Like Structure
journal, October 2002

  • Durio, C.; Daidouh, A.; Chouaibi, N.
  • Journal of Solid State Chemistry, Vol. 168, Issue 1
  • DOI: 10.1006/jssc.2002.9712

Phosphate-stabilized lithium intercalation compounds
journal, June 2003


Unveiling the sodium intercalation properties in Na1.86□0.14Fe3(PO4)3
journal, August 2016


Self-Assembled Alluaudite Na 2 Fe 3− x Mn x (PO 4 ) 3 Micro/Nanocompounds for Sodium-Ion Battery Electrodes: A New Insight into Their Electronic and Geometric Structure
journal, November 2014

  • Huang, Weifeng; Li, Biao; Saleem, Muhammad Farooq
  • Chemistry - A European Journal, Vol. 21, Issue 2
  • DOI: 10.1002/chem.201403062

Study of a Layered Iron(III) Phosphate Phase Na[sub 3]Fe[sub 3](PO[sub 4])[sub 4] Used as Positive Electrode in Lithium Batteries
journal, January 2010

  • Trad, Khiem; Carlier, Dany; Wattiaux, Alain
  • Journal of The Electrochemical Society, Vol. 157, Issue 8
  • DOI: 10.1149/1.3442365

Research Development on Sodium-Ion Batteries
journal, October 2014

  • Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500192f

Topochemical Synthesis of Sodium Metal Phosphate Olivines for Sodium-Ion Batteries
journal, August 2011

  • Lee, Kyu Tae; Ramesh, T. N.; Nan, F.
  • Chemistry of Materials, Vol. 23, Issue 16
  • DOI: 10.1021/cm200450y

Room-temperature stationary sodium-ion batteries for large-scale electric energy storage
journal, January 2013

  • Pan, Huilin; Hu, Yong-Sheng; Chen, Liquan
  • Energy & Environmental Science, Vol. 6, Issue 8
  • DOI: 10.1039/c3ee40847g

Effect of particle size on LiMnPO4 cathodes
journal, December 2007


Hydrothermal and Solvothermal Process Towards Development of LiMPO4 (M = Fe, Mn) Nanomaterials for Lithium-Ion Batteries
journal, March 2012

  • Devaraju, Murukanahally Kempaiah; Honma, Itaru
  • Advanced Energy Materials, Vol. 2, Issue 3
  • DOI: 10.1002/aenm.201100642

Direct Experimental Evidence for Atomic Tunneling of Europium in Crystalline Eu 8 Ga 16 Ge 30
journal, July 2006


A structural, infrared, and Mossbauer spectral study of rosemaryite, NaMnFe3+Al(PO4)3 [A structural, infrared, and Mossbauer spectral study of rosemaryite, NaMnFe3+Al(PO4)3]
journal, December 2006


The chemical reduction of nitrate in aqueous solution
journal, April 2000


Structure and Stability of Sodium Intercalated Phases in Olivine FePO 4
journal, July 2010

  • Moreau, P.; Guyomard, D.; Gaubicher, J.
  • Chemistry of Materials, Vol. 22, Issue 14
  • DOI: 10.1021/cm101377h

NaMnFe 2 (PO 4 ) 3 Alluaudite Phase: Synthesis, Structure, and Electrochemical Properties As Positive Electrode in Lithium and Sodium Batteries
journal, October 2010

  • Trad, Khiem; Carlier, Dany; Croguennec, Laurence
  • Chemistry of Materials, Vol. 22, Issue 19
  • DOI: 10.1021/cm1015614

Works referencing / citing this record:

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
  • Journal of Superconductivity and Novel Magnetism, Vol. 32, Issue 8
  • DOI: 10.1007/s10948-018-4964-5

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
  • DOI: 10.1007/s10904-018-0956-y