Abstract
The Li4Ti5O12 is applied in lithium ion batteries as anode material, which can be synthesized by various synthesis techniques. In this study, the molten salt synthesis technique at low temperatures, i.e. 350 °C, was applied to synthesize Li4Ti5O12. Surprisingly, the Li4Ti5O12 was not formed according to XRD analysis, which raised question about the stability range of Li4Ti5O12. To investigate the stability of Li4Ti5O12 at low temperatures, the high-temperature calcined Li4Ti5O12 powder was equilibrated in the LiCl-KCl eutectic salt at 350 °C. The result of experiment revealed that the Li4Ti5O12 is not decomposed. Results of ab initio calculations also indicated that the Li4Ti5O12 phase is a stable phase at 0 K. The products of molten salt synthesis technique were then annealed at 900 °C, which resulted in the Li4Ti5O12 formation. It was concluded that the Li4Ti5O12 is a stable phase at low temperatures and the reasons for not forming the Li4Ti5O12 by molten salt technique at low temperature are possibly related to activation energy and kinetic barriers. The Li4Ti5O12 formation energy is also very small, due to the results of ab initio calculations.
This is a preview of subscription content, access via your institution.



References
Armand M, Tarascon J-M (2008) Building better batteries. Nature 451:652–657
Vijayakumar M, Kerisit S, Yang Z, Graff GL, Liu J, Sears JA et al (2009) Combined 6, 7Li NMR and molecular dynamics study of Li diffusion in Li2TiO3. J Phys Chem C 113:20108–20116
Bai Y, Wang F, Wu F, Wu C, Bao L-y (2008) Influence of composite LiCl–KCl molten salt on microstructure and electrochemical performance of spinel Li4Ti5O12. Electrochim Acta 54:322–327
Zhao L, Hu YS, Li H, Wang Z, Chen L (Mar 18 2011) Porous Li4Ti5O12 coated with N-doped carbon from ionic liquids for Li-ion batteries. Adv Mater 23:1385–1388
Wang YQ, Gu L, Guo YG, Li H, He XQ, Tsukimoto S et al (May 9 2012) Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. J Am Chem Soc 134:7874–7879
Sorensen EM, Barry SJ, Jung H-K, Rondinelli JM, Vaughey JT, Poeppelmeier KR (2006) Three-dimensionally ordered macroporous Li4Ti5O12: effect of wall structure on electrochemical properties. Chem Mater 18:482–489
Nasara RN, Tsai P-C, Lin S-K (2017) One-step synthesis of highly oxygen-deficient lithium titanate oxide with conformal amorphous carbon coating as anode material for lithium ion batteries. Adv Mater Interfaces. doi:10.1002/admi.201700329
Panero S, Reale P, Ronci F, Albertini VR, Scrosati B (2000) Structural and electrochemical study on Li(Li1/3Ti5/3)O4 anode material for lithium ion batteries. Ionics 6:461–465
Ohzuku T, Ueda A, Yamamoto N (1995) Zero-strain insertion material of Li[Li1/3Ti5/3]O4 for rechargeable lithium cells. J Electrochem Soc 142:1431–1435
Kleykamp H (2002) Phase equilibria in the Li–Ti–O system and physical properties of Li2TiO3. Fusion engineering and design 61:361–366
Izquierdo G, West AR (1980) Phase equilibria in the system Li2O-TiO2. Mater Res Bull 15:1655–1660
Veljkovic I, Poleti D, Karanovic L, Zdujic M, Brankovic G (2011) Solid state synthesis of extra phase-pure Li4Ti5O12 spinel. Sci Sinter 43:343–351
Cheng L, Liu H-J, Zhang J-J, Xiong H-M, Xia Y-Y (2006) Nanosized Li4Ti5O12 prepared by molten salt method as an electrode material for hybrid electrochemical supercapacitors. J Electrochem Soc 153:A1472–A1477
Ceder G, Aydinol M, Kohan A (1997) Application of first-principles calculations to the design of rechargeable Li-batteries. Comput Mater Sci 8:161–169
Tsai P-c, Hsu W-D, Lin S-k (2014) Atomistic structure and ab initio electrochemical properties of Li4Ti5O12 defect spinel for Li ion batteries. J Electrochem Soc 161:A439–A444
Asadikiya M, Rudolf C, Zhang C, Boesl B, Agarwal A, Zhong Y (2017) Thermodynamic modeling and investigation of the oxygen effect on the sintering of B4C. J Alloys Compd 699:1022–1029
Asadikiya M, Rudolf C, Zhang C, Boesl B, Zhong Y (2016) The role of CALPHAD approach in the sintering of B4C with SiC as a sintering aid by spark plasma sintering technique. In: Additive manufacturing and strategic technologies in advanced ceramics: ceramic transactions, pp 185–191
Asadikiya M, Sabarou H, Chen M, Zhong Y (2016) Phase diagram for a nano-yttria-stabilized zirconia system. RSC Adv 6:17438–17445
Asadikiya M et al (2017) The effect of sintering parameters on spark plasma sintering of B4C. Ceram Int 43(14):11182–11188
Koudriachova M (2008) Ramsdellite-structured LiTiO2: a new phase predicted from ab initio calculations. Chem Phys Lett 458:108–112
Ouyang C, Zhong Z, Lei M (2007) Ab initio studies of structural and electronic properties of Li4Ti5O12 spinel. Electrochem Commun 9:1107–1112
Lippens P-E, Womes M, Kubiak P, Jumas J-C, Olivier-Fourcade J (2004) Electronic structure of the spinel Li4Ti5O12 studied by ab initio calculations and X-ray absorption spectroscopy. Solid State Sci 6:161–166
Kataoka K, Takahashi Y, Kijima N, Hayakawa H, Akimoto J, Ohshima K-i (2009) A single-crystal study of the electrochemically Li-ion intercalated spinel-type Li4Ti5O12. Solid State Ionics 180:631–635
Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169
Kohn W, Sham LJ (1965) Self-consistent equations including exchange and correlation effects. Phys Rev 140:A1133
Perdew JP, Yue W (1986) Accurate and simple density functional for the electronic exchange energy: generalized gradient approximation. Phys Rev B 33:8800
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865
Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953
Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188
Jain A, Ong SP, Hautier G, Chen W, Richards WD, Dacek S et al (2013) Commentary: the materials project: a materials genome approach to accelerating materials innovation. APL Materials 1:011002
Ong SP, Richards WD, Jain A, Hautier G, Kocher M, Cholia S et al (2013) Python materials genomics (pymatgen): a robust, open-source python library for materials analysis. Comput Mater Sci 68:314–319
Raghavachari K, Strout DL, Odom GK, Scuseria GE, Pople JA, Johnson BG, Gill PMW (1993) Isomers of C20. Dramatic effect of gradient corrections in density functional theory. Chem Phys Lett 214(3–4):357–361
Bo S, Ping Z (2008) First-principles local density approximation (LDA) + U and generalized gradient approximation (GGA) + U studies of plutonium oxides. Chinese Physics B 17:1364
Kamiya T, Nomura K, Hosono H (2009) Electronic structure of the amorphous oxide semiconductor a-InGaZnO4–x: Tauc–Lorentz optical model and origins of subgap states. Phys Status Solidi A 206:860–867
Loschen C, Carrasco J, Neyman KM, Illas F (2007) First-principles LDA + U and GGA + U study of cerium oxides: dependence on the effective U parameter. Phys Rev B 75:035115
Gopalan S, Mehta K, Virkar AV (1996) Synthesis of oxide perovskite solid solutions using the molten salt method. J Mater Res 11:1863–1865
Gopalan S, Virkar AV (1993) Thermodynamic stabilities of SrCeO3 and BaCeO3 using a molten salt method and galvanic cells. J Electrochem Soc 140:1060–1065
Hanaor DAH, Sorrell CC (2010) Review of the anatase to rutile phase transformation. J Mater Sci 46:855–874
Shen Y, Søndergaard M, Christensen M, Birgisson S, Iversen BB (2014) Solid state formation mechanism of Li4Ti5O12 from an anatase TiO2 source. Chem Mater 26:3679–3686
Shin J-W, Hong C-H, Yoon D-H (2012) Effects of TiO2 starting materials on the solid-state formation of Li4Ti5O12. J Am Ceram Soc 95:1894–1900
Acknowledgements
S.K.L., Y.C.C., P.C.T, and R.N.N. wish to thank the financial support from the Ministry of Science and Technology (MOST), Taiwan, with the contract numbers of 105-2221-E-006-189-MY3 and 105-3113-E-006-019-CC2. M.A. is greatly appreciated of the Doctoral Evidence Acquisition (DEA) Fellowship from Graduate School of Florida International University.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
The authors declare that they have no conflicts of interest.
Rights and permissions
About this article
Cite this article
Asadikiya, M., Zhu, Y., Gopalan, S. et al. Integrated investigation of the Li4Ti5O12 phase stability. Ionics 24, 707–713 (2018). https://doi.org/10.1007/s11581-017-2248-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11581-017-2248-x