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An investigation into the temperature phase transitions of synthesized materials with Al- and Mg-doped lithium manganese oxide spinels by in situ powder X-ray diffraction

Published online by Cambridge University Press:  23 December 2016

C. D. Snyders ,
E. E. Ferg  and
D. Billing
C. D. Snyders*
Affiliation:
Department of Chemistry, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031, South Africa
E. E. Ferg
Affiliation:
Department of Chemistry, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031, South Africa
D. Billing
Affiliation:
School of Chemistry, University of the Witwatersrand, Private Bag 3, Johannesburg 2000, South Africa
*
a)Author to whom correspondence should be addressed. Electronic mail: Charmelle.Snyders@nmmu.ac.za
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Abstract

Three spinel materials were prepared and characterized by in situ powder X-ray diffraction (PXRD) techniques to track their phase changes that occurred in the typical batch synthesis process from a sol–gel mixture to the final crystalline spinel oxide. The materials were also characterized by thermal gravimetric analysis, whereby the materials decomposition mechanisms that were observed as the precursor, was gradually heated to the final oxide. The results showed that all the materials achieved their total weight loss at about 400 °C. The in situ PXRD analysis showed the progression of the phase transitions where certain of the materials changed from a crystalline precursor to an amorphous intermediate phase and finally to the spinel cathode oxide (Li1.03Mg0.2Mn1.77O4). For other materials, the precursor would start as an amorphous phase and upon heating, convert into an impure intermediate phase (Mn2O3) before forming the final spinel oxide (Li1.03Mn1.97O4). On the other hand, the LiAl0.4Mn1.6O4 would start with an amorphous precursor, with no intermediate phases and immediately formed the final spinel oxide phase. The in situ PXRD study also showed the increases in the materials respective lattice parameters of the crystalline unit cells upon heating and the significant increases in their crystallite sizes when heated above 600 °C.

Keywords

in-situ powder X-ray diffractionAl- and Mg-doped LiMn2O4lattice parameteramorphous and crystalline precursorsintermediate Mn2O3
Type
Technical Articles
Information
Powder Diffraction , Volume 32 , Issue 1 , March 2017 , pp. 23 - 30
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Copyright
Copyright © International Centre for Diffraction Data 2016 

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References

Arora, P., Popov, B. N., and White, R. E. (1998). “Electrochemical investigations of cobalt-doped LiMn2O4 as cathode material for lithium-ion batteries,” J. Electrochem. Soc. 145, 807–815.CrossRefGoogle Scholar
Bruker, A. X. S. (2009). Topas Manual, Version 4.2 (Computer Software) (Bruker Software, West Germany).Google Scholar
Chung, K. Y., Ryu, C. W., and Kim, K. B. (2005). “Onset mechanism of Jahn-Teller distortion in 4 V LiMn2O4 and its suppression by LiM0.05Mn1.95O4 (M = Co, Ni) coating,” J. Electrochem. Soc. 152, A791–A795.Google Scholar
Fu, L. J., Liu, H., Li, C., Wu, Y. P., Rahm, E., Holze, R., and Wu, H. Q. (2005). “Electrode materials for lithium secondary batteries prepared by sol-gel methods,” Progr. Mater. Sci. 50, 881–928.Google Scholar
Gummow, R. J., de Kock, A., and Thackeray, M. M. (1994). “Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells,” Solid State Ion. 69, 59–67.Google Scholar
Guohua, L., Ikuto, H., Uchida, T., and Wakihara, M. (1996). “The spinel phases LiMyMn2−yO4 (M = Co, Cr, Ni) as the cathode for rechargeable lithium batteries,” J. Electrochem. Soc. 143, 178–182.Google Scholar
Hernán, L., Morales, J., Sánchez, L., and Santos, J. (1999). “Use of Li-M-Mn-O [M = Co, Cr, Ti] spinels prepared by a sol-gel method as cathodes in high-voltage lithium batteries,” Solid State Ion. 118, 179–185.Google Scholar
Huang, X., Lin, M., Tong, Q., Li, X., Ruan, Y., and Yang, Y. (2012). “Synthesis of LiCoMnO4 via a sol-gel method and its application in high power LiCoMnO4/Li4Ti5O12 lithium-ion batteries,” J. Power Sources 202, 352–356.CrossRefGoogle Scholar
Hwang, B. J., Santhanam, R., and Liu, D. G. (2001a). “Characterization of nanoparticles of LiMn2O4 synthesized by citric acid sol-gel method,” J. Power Sources 97, 443–446.Google Scholar
Hwang, B. J., Santhanam, R., and Liu, D. G. (2001b). “Effect of various synthetic parameters on purity of LiMn2O4 spinel synthesized by sol-gel method at low temperature,” J. Power Sources 101, 86–89.CrossRefGoogle Scholar
Jang, D. H., Shin, Y. J., and Oh, S. M. (1996). “Dissolution of spinel oxides and capacity losses in 4 V Li/Li x Mn2O4 cells,” J. Electrochem. Soc. 143, 2204–2211.Google Scholar
Jugovic, D. and Uskokovic, D. (2009). “A review of recent developments in the synthesis procedures of lithium iron phosphate powders,” J. Power Sources 190, 538–544.Google Scholar
Kebede, M. A., Phasha, M. J., Kunjuzwa, N., Mathe, M. K., and Ozoemena, K. I. (2015). “Solution-combustion synthesized aluminium-doped spinel (LiAl x Mn2−x O4) as a high-performance lithium-ion battery cathode material,” Appl. Phys. A 121, 51–57.CrossRefGoogle Scholar
Kim, D. K., Zhang, Y., Voit, W., Rao, K. V., and Muhammed, M. (2001). “Synthesis and characterization of surfactant-coated superparamagnetic monodispersed iron oxide nanoparticles,” J. Magn. Magn. Mater. 225, 30–36.Google Scholar
Lee, S. W., Kim, K. S., Moon, H. S., Kim, H. J., Cho, B. W., Cho, W. I., Ju, J. B., and Park, J. W. (2004). “Electrochemical characteristics of Al2O3-coated lithium manganese spinel as a cathode material for a lithium secondary battery,” J. Power Sources 126, 150–155.Google Scholar
Lee, Y. S., Sun, Y. K., and Nahm, K. S. (1998). “Synthesis of spinel LiMn2O4 cathode material prepared by an adipic acid-assisted sol-gel method for lithium secondary batteries,” Solid State Ion. 109, 285–294.Google Scholar
Li, C., Zhang, H. P., Fu, L. J., Liu, H., Wu, Y. P., Rahm, E., Holze, R., and Wu, H. Q. (2006). “Cathode materials modified by surface coating for lithium ion batteries,” Electrochim. Acta 51, 3872–3883.Google Scholar
Li, G., Yamada, A., Fukushima, Y., Yamaura, K., Saito, T., Endo, T., Azuma, H., Sekai, K., and Nishi, Y. (2000). “Phase segregation of Li x Mn2O4 (0.6 < x < 1) in non-equilibrium reduction processes,” Solid State Ion. 130, 221–228.Google Scholar
Li, X., Xu, Y. and Wang, C. (2009). “Suppression of Jahn-Teller distortion of spinel LiMn2O4 cathode,” J. Alloys Compd. 479, 310–313.Google Scholar
Liu, H., Wu, Y. P., Rahm, E., Holze, R., and Wu, H. Q. (2004). “Cathode materials for lithium ion batteries prepared by sol-gel methods,” J. Solid State Electrochem. 8, 450–466.Google Scholar
Lui, Q., Wang, S., Tan, H., Yang, Z., and Zeng, J. (2013). “Preparation and doping mode of doped LiMn2O4 for Li-ion batteries,” Energies 6, 1718–1730.Google Scholar
Manev, V., Banov, B., Momchiler, A., and Nassalevska, A. (1995). “LiMn2O4 for 4 V lithium-ion batteries,” J. Power Sources 57, 99–103.Google Scholar
Meier, M. (2004). Crystallite Size Measurement Using X-ray Diffraction (University of California, Davis).Google Scholar
Ohzuku, T., Kitagawa, M., and Hirai, T. (1990). “Electrochemistry of manganese dioxide in lithium nonaqueous cell”, J. Electrochem. Soc. 137, 769–775.CrossRefGoogle Scholar
Palomares, V., Rojo, T., and Belharouak, I. (eds) (2012). Synthesis Process for Li-ion Battery Electrodes from Solid State Reaction to Solvothermal Self-assembly Methods, in Lithium ion Batteries-New Developments (InTech, Croatia Europe).Google Scholar
Rehani, B. R., Joshi, P. B., Lad, K. N., and Pratap, A. (2006). “Crystallite size estimation of elemental and composite silver nano-powders using XRD principles,” Indian J. Pure Appl. Phys. 44, 157–161.Google Scholar
Rossouw, M. H., de Kock, A., de Picciotto, L. A., Thackeray, M. M., David, W. I. F., and Ibberson, R. M. (1990). “Structural aspects of lithium-manganese-oxide electrodes for rechargeable lithium batteries,” Mater. Res. Bull. 25, 173–182.Google Scholar
Seyedahmadian, M., Houshyarazar, S., and Amirshaghaghi, A. (2013). “Synthesis and characterization of nanosized spinel LiMn2O4 via Sol-gel and freeze drying methods,” Bull. Korean Chem. Soc. 34, 622–628.Google Scholar
Singh, P., Sil, A., Nath, M., and Ray, S. (2010). “Preparation and characterization of lithium manganese oxide cubic spinel Li1.03Mn1.97O4 doped with Mg and Fe,” Physica B 405, 649–654.Google Scholar
Sun, Y. K. (1997). “Synthesis and electrochemical studies of spinel Li1.03Mn2O4 cathode materials prepared by a sol-gel method for lithium secondary batteries,” Solid State Ion. 100, 115–125.Google Scholar
Sun, Y. K., Oh, I. H., and Kim, K. Y. (1997). “Synthesis of spinel LiMn2O4 by the Sol-Gel method for a cathode-active material in lithium secondary batteries,” Ind. Eng. Chem. Res. 36, 4839–4846.CrossRefGoogle Scholar
Sun, Y. K., Kim, D. W., and Choi, Y. M. (1999). “Synthesis and characterization of spinel LiMn2−x Ni x O4 for lithium/polymer battery applications,” J. Power Sources 79, 231–237.Google Scholar
Tarascon, J. M. and Guyomard, D. (1991). “Li metal-free rechargeable batteries based on Li1+x Mn2O4 cathodes (0 ≤ x ≤ 1) and carbon anodes,” J. Electrochem. Soc., 138, 2864–2868.Google Scholar
Tarascon, J. M. and Guyomard, D. (1993). “The Li1+x Mn2O4/C rocking-chair system: a review,” Electrochim. Acta 38, 1221–1231.Google Scholar
Thackeray, M. M., David, W. I. F., Bruce, P. G., and Goodenough, J. B. (1983). “Li-insertion into manganese spinels,” Mater. Res. Bull. 18, 461–472.CrossRefGoogle Scholar
Thackeray, M. M., Johnson, P. J., de Picciotto, L. A., Bruce, P. G., and Goodenough, J. B. (1984). “Electrochemical extraction of lithium from LiMn2O4 ,” Mater. Res. Bull. 19, 179–187.Google Scholar
Thackeray, M. M., de Kock, A., Rossouw, M. H., Liles, D. C., Hoge, D., and Bittihn, R. (1992). “Spinel electrodes from the Li-Mn-O system for rechargeable lithium battery applications,” J. Electrochem. Soc. 139, 363–366.Google Scholar
Thirunakaran, R., Sivashanmugam, A., Gopukumar, S., Dunnill, C. W., and Gregory, D. H. (2008). “Studies on chromium/aluminium-doped manganese spinel as cathode materials for lithium-ion batteries-A novel chelated sol-gel synthesis,” J. Mater. Process. Technol. 208, 520–531.Google Scholar
Wang, J. L., Li, Z. H., Yang, J., Tang, J. J., Yu, J. J., Nie, W. B., Lei, G. T., and Xiao, Q. Z. (2012). “Effect of Al-doping on the electrochemical properties of a three-dimensionally porous lithium manganese oxide for lithium-ion batteries,” Electrochim. Acta 75, 115–122.CrossRefGoogle Scholar
Wang, X., Chen, X., Gao, L., Zheng, H., Shen, M. I. T., and Zhang, Z. (2003). “Citric acid-assisted sol-gel synthesis of nanocrystalline LiMn2O4 spinel as cathode material,” J. Cryst. Growth 256, 123–127.CrossRefGoogle Scholar
Wu, S. and Chen, H. (2003). “The effects of heat-treatment temperature on the retention capacities of spinels prepared by the Pechini process,” J. Power Sources 119–121, 134–138.Google Scholar
Yamada, A. (1996). “Lattice instability in Li(Li x Mn2−x )O4 ,” J. Solid State Chem. 122, 160–165.Google Scholar
Yi, T., Dai, C., Gao, K., and Hu, X. (2006a). “Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method,” J. Alloys Compd. 425, 343–347.Google Scholar
Yi, T., Hu, X., and Gao, K. (2006b). “Synthesis and physicochemical properties of LiAl0.05Mn1.95O4 cathode material by ultrasonic-assisted sol-gel method,” J. Power Sources 162, 636–643.Google Scholar
Zhong, Q., Bonakdarpour, A., Zhang, M., Gao, Y., and Dahn, J. R. (1997). “Synthesis and electrochemistry of LiNi x Mn2−x O4 ,” J. Electrochem. Soc. 144, 205–213.CrossRefGoogle Scholar
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