Electrical Properties of Li-based NASICON Structured Ceramic Electrolytes Substituted With Chromium
Keywords:Lithium, NASICON, Electrolytes, Chromium, Conductivity
Electrical properties of Li - ion conducting Li1+xCrxSn2-x(PO4)3 ceramic electrolytes with 0 < x < 1 were studied using electrical impedance spectroscopy in the frequency range of 1 Hz to 10 MHz at room temperature. Impedance analysis showed an increase in bulk and grain boundary conductivity with the increment of x up to x = 0.7. The highest bulk and grain boundary conductivity were 6.52 Ã—10-6 S cm-1 and 1.62 Ã—10-6 S cm-1 in the system of Li1.7Cr0.7Sn1.3(PO4)3 at room temperature. The charge carrier concentration, mobile ion concentration, ionic hopping rate and ionic mobility were calculated by fitting the AC conductivity spectra. The ionic hopping rate and ionic mobility of the compound increased with the substitution of chromium due to the extra interstitial Li+ ions in the system. Additionally, the highest conducting sample with x = 0.7 had a negligible electronic conductivity based on transference number measurements. These results imply that the Li1+xCrxSn2-x(PO4)3 electrolytes obtained in this work can be considered as future candidates for solid state electrolytes.
 Takada, K., â€œProgress in solid electrolytes toward realizing solid-state lithium batteriesâ€, Journal of Power Sources, Vol 394 (2018) pp 74-85.
 Hong, H.Y.P., â€œCrystal structures and crystal chemistry in the system Na1+ xZr2SixP3âˆ’ xO12â€, Materials Research Bulletin, Vol 11, No 2, (1976) pp 173-182.
 Goodenough, J.B., H.Y.-P. Hong, and J.A. Kafalas, â€œFast Na+-ion transport in skeleton structuresâ€, Materials Research Bulletin, Vol 11, No 2, (1976) pp 203-220.
 Aono, H. , Sugimoto, E. , Sadaoka, Y. , Imanaka, N, and Adachi, G. â€œIonic conductivity and sinterability of lithium titanium phosphate systemâ€, Solid State Ionics, Vol 40, (1990) pp 38-42.
 Hallopeau, L., Bregiroux, D., Rousse, G., Portehault, D., Stevens, P., Toussaint, G., and Laberty-Robert, C, â€œMicrowave-assisted reactive sintering and lithium ion conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyteâ€ Journal of Power Sources, Vol 378 , (2018), pp 48-52.
 Ramar, V., Kumar, S., Sivakkumar, S. R., and Balaya, P., â€œNASICON-type La3+substituted LiZr2(PO4)3 with improved ionic conductivity as solid electrolyteâ€, Electrochimica Acta, Vol 271, (2018), pp120-126.
 Zhang, Y., Chen, K., Shen, Y., Lin, Y., and Nan, Ce-W, â€œEnhanced lithium-ion conductivity in a LiZr2(PO4)3 solid electrolyte by Al dopingâ€, Ceramics International, Vol 43, (2017), pp S598-S602.
 Mustaffa, N.A., Adnan, S. B. R. S., Sulaiman, M., and Mohamed, N. S., â€œLow-temperature sintering effects on NASICON-structured LiSn2P3O12 solid electrolytes prepared via citric acid-assisted sol-gel methodâ€ , Ionics, Vol 21, No 4, (2015) pp 955-965.
 Mustaffa, N. A. and Mohamed, N. S. , â€œProperties of stannum-based Li-NASICON-structured solid electrolytes for potential application in electrochemical devicesâ€, Int J Electrochem Sci, Vol 10, (2015), pp 5382-5394.
 Mustaffa, N.A., and Mohamed, N. S., â€œZirconium-substituted LiSn2P3O12 solid electrolytes prepared via solâ€“gel methodâ€, Journal of Sol-Gel Science and Technology, Vol 77, No 3, (2016), pp 585-593.
 Fergus, J.W., â€œIon transport in sodium ion conducting solid electrolytesâ€, Solid State Ionics, Vol 227, (2012) pp. 102-112.
 Knauth, P., â€œInorganic solid Li ion conductors: An overviewâ€, Solid State Ionics, Vol 180, No 14, (2009) pp 911-916.
 Padma Kumar, P. and S. Yashonath, â€œLithium ion motion in LiZr2(PO4) 3â€The Journal of Physical Chemistry B, Vol 105, No 29 (2001) pp 6785-6791.
 Martinez, A. , Rojo, J. M. , Iglesias, J. E. , Sanz, J. , and Rojas, R. M, â€œFormation process of LiSn2(PO4)3, a monoclinically distorted NASICON-type structure.â€ , Chemistry of materials, Vol 6, No 10 (1994) pp 1790-1795.
 Martinez-Juarez, A. , Rojo, J. M., Iglesias, J. E., and Sanz, J, â€œReversible monoclinic-rhombohedral transformation in LiSn2(PO4)3 with NASICON-type structureâ€, Chemistry of Materials, Vol 7, No 10, (1995) pp 1857-1862.
 Norhaniza, R., R.H.Y. Subban, and N.S. Mohamed,â€ Effects of Sintering Temperature on the Structure and Conductivity of LiSn2P3O12 Prepared by Mechanical Milling Methodâ€, Advanced Materials Research, Vol 129 m- 131, (2010) pp 338 - 342.
 Cui, W-J. , Yi, J. , Chen, L. , Wang, C-X. , and Xia, Y-Y., â€œSynthesis and electrochemical characteristics of NASICON-structured LiSn2(PO4)3 anode material for lithium-ion batteriesâ€, Journal of Power Sources, Vol 217, (2012) pp. 77-84.
 Lazarraga, M. G. , IbaÃ±ez, J. , Tabellout, M. , and Rojo, J. M., â€œOn the aggregation process of ceramic LiSn2P3O12 particles embedded in Teflon matrixâ€, Composites science and technology, Vol 64, No 5, (2004) pp 759-765.
 Aono, H. , Sugimoto, E. , Sadaoka, Y. , Imanaka, N. , and Adachi, G, â€œElectrical properties of sintered lithium titanium phosphate ceramics (Li1+ xMxTi2-x (PO4)3, M3+= Al3+, Sc3+, or Y3+)â€, Chemistry Letters, Vol 10, (1990) pp 1825-1828.
 Aono, H. , Sugimoto, E. , Sadaoka, Y. , Imanaka, N. ,and Adachi, G, â€œElectrical property and sinterability of LiTi2(PO4)3 mixed with lithium salt (Li3PO4 or Li3BO3)â€, Solid State Ionics, Vol 47, No 3-4, (1991) pp 257-264.
 Jenkins, R., X-Ray Techniques: Overview, Encyclopedia of analytical chemistry. 2000: Wiley Online Library.
 Jenkins, R. and R.L. Snyder, Diffraction theory. Introduction to X-ray Powder Diffractometry, Volume 138, 1996, pp 47-95.
 PÃ©rez-EstÃ©banez, M., Isasi-MarÃn, J., TÃ¶bbens, D. M., Rivera-Calzada, A., and LeÃ³n, C., â€œA systematic study of Nasicon-type Li1 + xMxTi2 âˆ’ x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopyâ€, Solid State Ionics, Vol 266, (2014) pp 1-8.
 Mariappan, C.R. and Govindaraj, G., â€œConductivity and ion dynamic studies in the Na4.7+ xTi1.3âˆ’ x(PO4)3.3âˆ’ x (0â‰¤ xâ‰¤ 0.6) NASICON materialâ€, Solid State Ionics, Vol 176, No 13, (2005) pp 1311-1318.
 Yadav, P. and Bhatnagar, M. C., â€œStructural studies of NASICON material of different compositions by solâ€“gel methodâ€, Ceramics International, Vol 38, No 2, (2012) pp 1731-1735.
 Xu, X. , Wen, Z. , Gu, Z. , Xu, X. , and Lin, Z., â€œPreparation and characterization of lithium ion-conducting glass-ceramics in the Li1+ xCrxGe2âˆ’ x(PO4)3 systemâ€, Electrochemistry Communications, Vol 6, No 12, (2004) pp 1233-1237.
 Fu, J., â€œFast Li+ Ion Conduction in Li2O-Al2O3-TiO2p-SiO2-P2O2 Glass-Ceramicsâ€, Journal of the American Ceramic Society, Vol 80, No 7, (1997) pp 1901-1903.
 Chowdari, B. V. R. , Rao, G. V. S., and Lee, G. Y. H, â€œXPS and ionic conductivity studies on Li2Oâ€“Al2O3â€“(TiO2 or GeO2)â€“P2O5 glassâ€“ceramicsâ€, Solid State Ionics, Vol 136, (2000) pp 1067-1075.
 Chang, C-M. , Hong, S-H. , and Park, H-M., â€œSpark plasma sintering of Al substituted LiHf2(PO4)3 solid electrolytesâ€, Solid State Ionics, Vol 176, No 35, (2005) pp 2583-2587.
 Jonscher, A.K., Chelsea Dielectric Press, 1983, London.
 Almond, D.P., G.K. Duncan, and A.R. West, â€œThe determination of hopping rates and carrier concentrations in ionic conductors by a new analysis of ac conductivityâ€, Solid State Ionics, Vol 8, No 2, (1983) pp159-164.
 Teo, L. P. , Buraidah, M. H. , Nor, A. F. M. , and Majid, S. R., â€œConductivity and dielectric studies of Li2SnO3â€, Ionics, Vol 18, No 7, (2012) pp 655-665.
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