Journal of Applied Electrochemistry

, Volume 49, Issue 2, pp 207–216 | Cite as

Investigation of electrochemical reaction mechanism for antimony selenide nanocomposite for sodium-ion battery electrodes

  • Jeong-Hee ChoiEmail author
  • Min-Ho Lee
  • Hae-Young Choi
  • Cheol-Min ParkEmail author
  • Sang-Min Lee
  • Jin-Hyeok Choi
Research Article


Antimony selenide and its carbon composite were synthesized through a mechanochemical process and investigated as anode materials for sodium-ion secondary batteries. X-ray diffraction (XRD) with rietveld refinement and transmission electron microscopy (TEM) analyses confirm that Sb2Se3 were composed of agglomerated highly crystalline nanocrystallites and the Sb2Se3/C composite consisted of nanocrystalline Sb2Se3 dispersed homogeneously throughout an amorphized carbon matrix. The initial Coulombic efficiency, rate capability, and cycle performance of the Sb2Se3/C composite were superior to those of Sb, or Sb2Se3. The Sb2Se3/C composite, in particular, showed excellent cycle stability, with 98.2% of initial capacity at 200 mA g−1 after 200 cycles. Based on the reaction potentials, ex situ XRD patterns and ex situ HR-TEM analysis of the Sb2Se3/C composite electrode revealed the structural changes which occurred reversibly within the Sb2Se3/C composite by conversion and recombination reaction during sodiation and desodiation process. Furthermore, XPS analysis study was carried out for identifying the surface films formed on both the electrodes and their effects on the performances.

Graphical abstract


Sodium-ion secondary batteries Anode materials Antimony selenide composite Mechanochemical process Electrochemical performances Reaction mechanism 



This work was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (No. 20152020105420). This research was supported by Technology Development Program to Solve Climate Changes through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (No. 2018M1A2A2063343).


  1. 1.
    Bruce PG, Scrosati B, Tarascon JM (2008) Nanomaterials for rechargeable lithium batteries. Angew Chem Int Ed 47(16):2930–2946CrossRefGoogle Scholar
  2. 2.
    Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657CrossRefGoogle Scholar
  3. 3.
    Park CM, Kim JH, Kim H, Sohn HJ (2010) Li-alloy based anode materials for Li secondary batteries. Chem Soc Rev 39:3115–3141CrossRefGoogle Scholar
  4. 4.
    Dunn B, Kamath G, Tarascon JM (2012) Electrical energy storage for the grid: a battery of choices. Science 334:928–935CrossRefGoogle Scholar
  5. 5.
    Grosjean C, Herrera PH, Perrin M, Poggi P (2012) Assessment of world lithium resources and consequences of their geographic distribution on the expected development of the electric vehicle industry. Renew Sustain Energy Rev 16(3):1735–1744CrossRefGoogle Scholar
  6. 6.
    Hong SY, Kim Y, Park Y, Choi A, Choi NS, Lee KT (2013) Charge carriers in rechargeable batteries: Na ions vs. Li ions. Energy Environ Sci 6:2067–2081CrossRefGoogle Scholar
  7. 7.
    Palomares V, Serras P, Villaluenga I, Hueso KB, Gonzalez JC, Rojo T (2012) Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Envrion Sci 5:5884–5901CrossRefGoogle Scholar
  8. 8.
    Komaba S, Murata W, Ishikawa T, Yabuuchi N, Ozeki T, Nakayama T, Ogata A, Gotoh K, Fujiwara K (2011) Electrochemical Na insertion and solid electrolyte interphase for hard-carbon electrodes and application to Na-ion batteries. Adv Funct Mater 21(20):3859–3867CrossRefGoogle Scholar
  9. 9.
    Kim SW, Seo DH, Ma X, Ceder G, Kang K (2012) Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries. Adv Energy Mater 2(7):710–721CrossRefGoogle Scholar
  10. 10.
    Yabuuchi N, Kajiyama M, Iwatate J, Nishikawa H, Hitomi S, Okuyama R, Usui R, Yamada Y, Komaba S, Nat Mater 11:512–517Google Scholar
  11. 11.
    Komaba S, Takei C, Nakayama T, Ogata A, Yabuuchi N (2010) Electrochemical intercalation activity of layered NaCrO2 vs. LiCrO2. Electrochem Commun 12(3):355–358CrossRefGoogle Scholar
  12. 12.
    Park YU, Seo DH, Kwon HS, Kim B, Kim J, Kim H, Kim I, Yoo HI, Kang K (2013) A new high-energy cathode for a Na-ion battery with ultrahigh stability. J Am Chem Soc 135(37):13870–13878CrossRefGoogle Scholar
  13. 13.
    Lee HW, Wang RT, Pasta M, Lee SW, Liu N, Cui Y (2014) Manganese hexacyanomanganate open framework as a high-capacity positive electrode material for sodium-ion batteries. Nat Commun 5:5280CrossRefGoogle Scholar
  14. 14.
    Cao Y, Xiao L, Sushko ML, Wang W, Schwenzer B, Xiao J, Nie Z, Saraf LV, Yang Z, Liu Z (2012) Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Lett 12(7):3783–3787CrossRefGoogle Scholar
  15. 15.
    Wen Y, He K, Zhu Y, Han F, Xu Y, Matsuda I, Ishii Y, Cummings J, Wang C (2014) Expanded graphite as superior anode for sodium-ion batteries. Nat Commun 5:4033CrossRefGoogle Scholar
  16. 16.
    Thomas P, Billaud D (2001) Sodium electrochemical insertion mechansims in various carbon fibres. Electrochim Acta 46(22):3359–3366CrossRefGoogle Scholar
  17. 17.
    Alcantara R, Lavela P, Ortiz GF, Tirado JL (2005) Carbon microspheres obtained from resorcinol-formaldehyde as high-capacity electrodes for sodium-ion batteries. Electrochem Solid-State Lett 8(4):A222–A225CrossRefGoogle Scholar
  18. 18.
    Kim Y, Park Y, Choi A, Choi NS, Kim J, Lee J, Rut J, Oh SM, Lee KT (2013) An amorphous red phosphorus/carbon composite as a promising anode material for sodium ion batteries. Adv Mater 25(22):3045–3049CrossRefGoogle Scholar
  19. 19.
    Qian J, Wu X, Cao Y, Ai X, Yang H (2013) High capacity and rate capability of amorphous phosphorus for sodium ion batteries. Angew Chem Int Ed 125(17):4731–4734CrossRefGoogle Scholar
  20. 20.
    Komaba S, Matsuura Y, Ishikawa T, Yabuuchi N, Murataand W, Kuze S (2012) Redox reaction of Sn-polyacrylate electrodes in aprotic Na cell. Electrochem Commun 21:65–68CrossRefGoogle Scholar
  21. 21.
    Baggetto L, Ganesh P, Meisner RP, Unocic RR, Jumas J, Bridges CA, Veith GM (2013) Characterization of sodium ion electrochemical reaction with tin anodes: experimental and theory. J Power Sources 234:48–59CrossRefGoogle Scholar
  22. 22.
    Darwiche A, Marino C, Sougrati MT, Fraisse B, Stievano L, Monconduit L (2012) Better cycling performances of bulk Sb in Na-ion batteries compared to Li-ion systems: an unexpected electrochemical mechanism. J Am Chem Soc 134(51):20805–20811CrossRefGoogle Scholar
  23. 23.
    Hu M, Jiang Y, Sun W, Wang H, Jin C, Yan M (2014) Reversible conversion-alloying of Sb2O3 as a high-capacity, high-rate, and durable anode for sodium ion batteries. ACS Appl Mater Interfaces 6(21):19449–19455CrossRefGoogle Scholar
  24. 24.
    Yu DYU, Prikhodchenko PV, Mason CW, Batabyal SK, Gun J, Sladkevich S, Medvedv AG, Lev O (2013) High-capacity antimony sulphide nanoparticle-decorated graphene composite as anode for sodium-ion batteries. Nat Commun 4:2922CrossRefGoogle Scholar
  25. 25.
    Zhu Y, Nie P, Shen L, Dong S, Sheng Q, Li H, Luo H, Zhang X (2015) High rate capability and superior cycle stability of a flower-like Sb2S3 anode for high-capacity sodium ion batteries. Nanoscale 7:3309–3315CrossRefGoogle Scholar
  26. 26.
    Yue JL, Sun Q, Fu ZW (2013) Cu2Se with facile synthesis as a cathode material for rechargeable sodium batteries. Chem Commun 49:5868–5870CrossRefGoogle Scholar
  27. 27.
    Zhang K, Hu Z, Liu X, Tao Z, Chen J (2015) FeSe2 microspheres as a high-performance anode material for Na-ion batteries. Adv Mater 27:3305–3309CrossRefGoogle Scholar
  28. 28.
    Ko YN, Choi SH, Park SB, Kang YC (2014) Hierarchical MoSe2 yolk–shell microspheres with superior Na-ion storage properties. Nanoscale 6:10511–10515CrossRefGoogle Scholar
  29. 29.
    Ou X, Yang C, Xiong X, Zheng F, Pan Q, Jin C, Liu M, Huang K (2017) A new rGO-overcoated Sb2Se3 nanorods anode for Na+ battery: in-situ X-ray diffraction study on a live sodiation/desodiation process. Adv Funct Mater 27:1606242CrossRefGoogle Scholar
  30. 30.
    Zhao W, Li CM (2017) Mesh-structured N-doped graphene@Sb2Se3 hybrids as an anode for large capacity sodium-ion batteries. J Colloid Interface Sci 488:356–364CrossRefGoogle Scholar
  31. 31.
    Luo W, Calas A, Tang C, Li F, Zhou L, Mai L (2016) Ultralong Sb2Se3 nanowire-based free-standing membrane anode for lithium/sodium ion batteries. ACS Appl Mater Interfaces 8:35219–35226CrossRefGoogle Scholar
  32. 32.
    Li W, Zhou M, Li H, Wang K, Cheng S, Jiang K (2015) Cabon-coated Sb2Se3 composite as anode material for sodium ion batteries. Electrochem Commun 60:74–77CrossRefGoogle Scholar
  33. 33.
    Baggetto L, Ganesh P, Sun CN, Meisner RA, Zawodzinski TA, Veith GM (2013) Intrinsic thermodynamic and kinetic properties of Sb electrodes for Li-ion and Na-ion batteries: experiment and theory. J Mater Chem A 1:7985–7994CrossRefGoogle Scholar
  34. 34.
    Bodenes L, Darwiche A, Monconduit L, Martinez H (2015) The solid electrolyte interphase a key parameter of the high performance of Sb in sodium-ion batteries: comparative X-ray photoelectron spectroscopy study of Sb/Na-ion and Sb/Li-ion batteries. J Power Sources 273:14–24CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Battery Research CenterKorea Electrotechnology Research InstituteChangwonRepublic of Korea
  2. 2.School of Materials Science and EngineeringKumoh National Institute of TechnologyGumiRepublic of Korea
  3. 3.Creative Future LaboratoryKorea Electric Power Corporation Research InstituteDaejeonRepublic of Korea

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