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Title: Electrochemical and thermal investigation of Li{sub 3}Ti{sub 5/3}O{sub 4} spinel.

Abstract

We have studied the electrochemical and thermal properties of Li{sub 4/3}T{sub 5/3}O{sub 4} spinel as a promising anode material for lithium ion batteries. The spinel/rock-salt two-phase transition process was interpreted using a core-shell model, which provided a good explanation of the different area-specific impedance behaviors during the charge and discharge processes. The constant dE/dT during the spinel/rock-salt phase transition was calculated from the heat-flow profile by isothermal microcalorimeter results and found to be around -0.04 mV/K. This very low and constant entropy change indicates that Li{sub 4/3}T{sub 5/3}O{sub 4} is a good anode material in terms of thermal stability. Also, we propose that there is a new phase generation when more than one lithium atom is inserted into Li{sub 4/3}T{sub 5/3}O{sub 4}. According to the discontinuity of dE/dT results, the order/disorder transition at the low-voltage region (around 0.6 V vs Li) occurs during further lithium insertion.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
EE
OSTI Identifier:
935913
Report Number(s):
ANL/CMT/JA-57039
Journal ID: ISSN 0013-4651; JESOAN; TRN: US0804763
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Electrochem. Soc.; Journal Volume: 154; Journal Issue: 2 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ANODES; ATOMS; ENTROPY; HEAT FLUX; IMPEDANCE; LITHIUM; LITHIUM IONS; SPINELS; STABILITY; THERMODYNAMIC PROPERTIES

Citation Formats

Lu, W., Belharouak, I., Liu, J., Amine, K., and Chemical Engineering. Electrochemical and thermal investigation of Li{sub 3}Ti{sub 5/3}O{sub 4} spinel.. United States: N. p., 2007. Web. doi:10.1149/1.2402117.
Lu, W., Belharouak, I., Liu, J., Amine, K., & Chemical Engineering. Electrochemical and thermal investigation of Li{sub 3}Ti{sub 5/3}O{sub 4} spinel.. United States. doi:10.1149/1.2402117.
Lu, W., Belharouak, I., Liu, J., Amine, K., and Chemical Engineering. Mon . "Electrochemical and thermal investigation of Li{sub 3}Ti{sub 5/3}O{sub 4} spinel.". United States. doi:10.1149/1.2402117.
@article{osti_935913,
title = {Electrochemical and thermal investigation of Li{sub 3}Ti{sub 5/3}O{sub 4} spinel.},
author = {Lu, W. and Belharouak, I. and Liu, J. and Amine, K. and Chemical Engineering},
abstractNote = {We have studied the electrochemical and thermal properties of Li{sub 4/3}T{sub 5/3}O{sub 4} spinel as a promising anode material for lithium ion batteries. The spinel/rock-salt two-phase transition process was interpreted using a core-shell model, which provided a good explanation of the different area-specific impedance behaviors during the charge and discharge processes. The constant dE/dT during the spinel/rock-salt phase transition was calculated from the heat-flow profile by isothermal microcalorimeter results and found to be around -0.04 mV/K. This very low and constant entropy change indicates that Li{sub 4/3}T{sub 5/3}O{sub 4} is a good anode material in terms of thermal stability. Also, we propose that there is a new phase generation when more than one lithium atom is inserted into Li{sub 4/3}T{sub 5/3}O{sub 4}. According to the discontinuity of dE/dT results, the order/disorder transition at the low-voltage region (around 0.6 V vs Li) occurs during further lithium insertion.},
doi = {10.1149/1.2402117},
journal = {J. Electrochem. Soc.},
number = 2 ; 2007,
volume = 154,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • A series of twelve Li/sub 1-//sub x/Ta/sub 1-3//sub x/Ti/sub 4//sub x/O/sub 3/ solid solution ceramics was sintered following the low-temperature metal alkoxide routes. Measurements of dielectric constants, dielectric losses, and heat capacities as functions of temperature and frequency are presented. The Curie temperature (T/sub C/) in comparison to LiTaO/sub 3/ was reduced from 620 /sup 0/C to about 358 /sup 0/C in the Li/sub 0.91/Ta/sub 0.73/Ti/sub 0.36/O/sub 3/ ceramics. The heat capacity data showed no dependence on the bulk density or grain size. Also the mechanical properties of the undoped crystals appear to stay undisturbed. On the other hand, anmore » apparently abnormal dependence of the Curie temperature on density was found. Heat capacity and dielectric loss decreased while the dielectric constant increased with the addition of Ti/sup +4/ doping in the LiTaO/sub 3/ structure. Overall, a good detector performance might indeed be obtained from these ceramic materials if they can be poled reproducibly.« less
  • Spinel-type lithium titanium oxide (LTO; Li{sub 4}Ti{sub 5}O{sub 12}) is a negative electrode material for lithium-ion batteries. Revealing the atomic-scale surface structure of LTO in liquid is highly necessary to investigate its surface properties in practical environments. Here, we reveal an atomic-scale image of the LTO(111) surface in LiCl aqueous solution using frequency-modulation atomic force microscopy. Atomically flat terraces and single steps having heights of multiples of 0.5 nm were observed in the aqueous solution. Hexagonal bright spots separated by 0.6 nm were also observed on the flat terrace part, corresponding to the atomistic contrast observed in the ultrahigh vacuum condition, whichmore » suggests that the basic atomic structure of the LTO(111) surface is retained without dramatic reconstruction even in the aqueous solution.« less
  • Highlights: • Spinel Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive potential of valence band and wider band gap than TiO{sub 2}. • Spinel Li{sub 4}Ti{sub 5}O{sub 12} displays typical n-type semiconductor characteristic and excellent UV-excitateded photocatalysis activity. • Our preliminary study will open new perspectives in investigation of other lithium-based compounds for new photocatalysts. - Abstract: Energy band structure, photoelectrochemical performances and photocatalysis activity of spinel Li{sub 4}Ti{sub 5}O{sub 12} are investigated for the first time in this paper. Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive valence band potential and wider band gap than TiO{sub 2} due to its valencemore » band consisting of Li{sub 1s} and Ti{sub 3d} orbitals mixed with O{sub 2p}. Li{sub 4}Ti{sub 5}O{sub 12} shows typical photocatalysis material characteristics and excellent photocatlytic activity under UV irradiation.« less