Abstract
Silicate materials have been proposed as alternative cathodes for Li-ion battery applications. A novel mixture of silicates, labelled Li6MnSi5, based on the molar ratio among the Li/Mn/Si precursors, with promising electrochemical properties as positive electrode material is synthesized through a solid-state reaction. The results indicate the proposed synthetic method as effective for preparation of nanostructured silicate powders with average particle diameter of 30 nm. Structural morphology of the samples was determined using X-ray powder diffraction (XRPD), XPS and FESEM analysis. A joint analysis by XRPD data and by density functional theory (DFT) identified LiHMn4Si5O15, Li2Mn4Si5O15, Li2Si2O5 and Li0.125Mn0.875SiO4 as components of Li6MnSi5 mixture. The electrochemical performance of Li6MnSi5 was evaluated by charge/discharge testing at constant current mode. Li6MnSi5 discharge behaviour is characterized by high capacity value of 480 mA h g−1, although such capacity fades gradually on cycling. Ex situ XPS studies carried out on the electrode in both full charged and discharged states pointed out that Li2Si2O5 is decisive for achieving such high capacity. The discharge/charge plateau is most probably related to the change in the oxidation state of silicon at the surface of the silica material.
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Fisher CAJ, Kuganathan N, Islam MS (2013) J Mater Chem A 1:4207–4214
Ferrari S, Capsoni D, Casino S, Destro M, Gerbaldi G, Bini M (2014) Phys Chem Chem Phys 16:10353–10366
Wang Y-C, Zhao S-X, Zhai P-Y, Li F, Nan C-W (2014a) J Alloys and Compounds 614:271–276
Bini M, Ferrari S, Capsoni D, Spreafico C, Tealdi C, Mustarelli P (2013) J Solid State Chemistry 200:70–75
Ni J, Zhang L, Fu S, Savilov SV, Aldoshin SM, Lu L (2015) Carbon 92:15–25
Muraliganth T, Stroukoff KR, Manthiram A (2010) Chem Mater 22(20):5754–5761
Dominko R (2008) J Power Sources 184:462–468
Rangappa D, Murukanahally KD, Tomai T, Unemoto A, Honma I (2012) Nano Lett 12:1146–1151
Dominko R, Bele M, Gaberšček M, Meden A, Remškar M, Jamnik J (2008) Electrochem Commun 8:217–222
Zhang S, Deng C, Liu FL, Wu Q, Zhang M, Meng FL, Gao H (2013) J Electroanal Chem 689:88–95
Liu S, Xu J, Li D, Hu Y, Liu X, Xie K (2013) J Power Sources 232:258–263
Devaraj S, Kuezma M, Ng CT, Balaya P (2013) Electrochim Acta 102:290–298
Wagner N, Svensson A-M, Vullum-Bruer F (2015) Solid State Ionics 276:26–32
Wagner NP, Vullum PE, Nord MK, Svensson AM, Vullum-Bruer F (2016) J Phys Chem C 120:11359–11371
Świętosławski M, Molenda M, Gajewska M (2016) Functional Materials Letter 9:1641003–1641007
He G, Manthiram A (2014) Adv Funct Mater 24:5277–5283
Eames C, Armstrong AR, Bruce PG, Islam MS (2012) Chem Mater 24:2155–2161
Li Y-X, Gong Z-L, Yang Y (2007) J Power Sources 174:528–532
Saracibar A, Wang Z, Carroll KJ, Meng YS, Arroyo-de Dompablo ME (2015) J Mater Chem a 3:6004–6011
Zhang S, Li Y, Xu G, Li S, Lu Y, Toprakci O, Zhang X (2012) J Power Sources 213:10–15
Saiful Islam M, Dominko R, Masquelier C, Sirisopanaporn C, Armstrong AR, Bruce PG (2011) J Mater Chem 21:9811–9818
Ramar V, Balaya P (2016) J Power Sources 306:552–558
Wang H, Hou T, Sun D, Huang X, He H, Tang Y, Liu Y (2014b) J Power Sources 247:497–502
Altomare A, Corriero N, Cuocci C, Falcicchio A, Moliterni A, Rizzi R (2015) J Appl Crystallogr 48:598–603
Dovesi R, Saunders VR, Roetti C, Orlando R, Zicovich-Wilson CM, Pascale F, Doll K, Harrison NM, Civalleri B, Bush I (2014) J CRYSTAL14 User’s manual. Università di Torino, Torino
Hay PJ, Wadt WR (1985) J Chem Phys 82:299
Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865
Aravindan V, Karthikeyan K, Kang KS, Yoon WS, Kim WS, Lee YS (2011) Mater Chem 21:2470–2475
Liu W, Xu Y, Yang R (2009) J Alloys and Compounds 480:L1–L4
Nytén A, Abouimrane A, Armand M, Gustafsson T, Thomas JO (2005) Electrochem Commun 7:156–160
Escande V, Petit E, Garoux L, Boulanger C, Grison C (2015) ACS Sustain Chem Eng 3:2704–2715
Grosvenor AP, Bellhouse EM, Korinek A, Bugnet M, McDermid JR (2016) Appl Surf Sci 379:242–248
Fabrizioli P, Burgi T, Baiker A (2002) J Catalysis 207:88–100
Sharma P, Lazar A, Singh PA (2012) Applied Catal A: General 439-440:101–110
Ilton ES, Post JE, Heaney PJ, Ling FT, Kerisit SN (2016) Appl Surf Sci 376:475–485
Takei H (1976) J Crystal Growth 34:125–131
Ryabov D (2011) Phys Chem Minerals 38:177–184
Świętosławski M, Molenda M, Furczoń K, Dziembaj R (2013) J Power Sources 244:510–514
Kuezma M, Devaraj S, Balay P (2012) J Mater Chem 22:21279–21284
Yan N, Wang F, Zhong H, Li Y, Wang Y, Hu L, Chen Q (2013) Scientific Reports 3:1568
Kibel M, Leech P (1996) Surf Interface Anal 24:605–610
Rueda F, Mendialdua J, Rodriguez A, Casanova R, Barbaux Y, Gengembre L, Jalowiecki L (1996) J Electron Spectrosc Relat Phenom 82:135–143
Dang T, Chau C (1996) J Electrochem Soc 143:302–305
Aarnik W, Weishaupt A, Van Silfhout A (1990) Appl Surf Sci 45:37–48
Alfonsetti R, Lozzi L, Passacantando M, Picozzi P, Santucci S (1993) Appl Surf Sci 70/71:222–225
Alfonsetti R, De Simone G, Lozzi L, Passacantando M, Picozzi P, Santucci S (1994) Surf Interf Anal 22:89–92
Nakazawa M, Kawase S, Sekiyama H (1989a) J Appl Phys 65:4014–4018
ICDD (2003) The powder diffraction file. International Center for Diffraction Data, Pennsylvania, pp 19073–13273
Nakazawa M, Nishioka Y, Sekiyama H, Kawase S (1989b) J Appl Phys 65:4019–4023
Acknowledgements
Financial support was provided by European Union Seventh Framework Programme FP7 GC.NMP.2013-1 2013-2017 MARS EV-GA 609201. The authors sincerely thank Mr. Mauro Raimondo for the FESEM analyses.
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Vankova, S., Versaci, D., Amici, J. et al. A high-capacity cathode based on silicates material for advanced lithium batteries. J Solid State Electrochem 21, 3381–3388 (2017). https://doi.org/10.1007/s10008-017-3663-7
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DOI: https://doi.org/10.1007/s10008-017-3663-7