Chemical and Electrochemical Li-Insertion into the Li4Ti5O12 Spinel

Aldon, Laurent; Kubiak, Pierre; Womes, M.; Jumas, J.‐C.; Olivier‐Fourcade, J.; Tirado, J.L.; Corredor, Juan I.; Vicente, C.

doi:10.1021/cm0488837

Cited by 315 publications

(189 citation statements)

References 22 publications

Supporting

Mentioning

173

Contrasting

Order By: Relevance

“…Subsequent Rietveld refinement using a single-phase model resulted in a gradual change of the lattice parameter and a shift of the mixed Li occupation from 8a to 16c, as shown in Figure 1b and c. Detailed fitting of the Li occupations did not confirm the partial migration of Li from 8a to 16c in Li 4 Ti 5 O 12 at room temperature as suggested by Pecharroman et al, and there appeared to be no significant temperature dependence of these occupations between 10 and 300 K. [9] Also, no Li 48f occupation was found, which was suggested to be the result of chemical lithiation. [12] The 1/6 substitution of Ti with Li on the 16d site was confirmed, and the absence of any superstructure peaks implies that Li and Ti are randomly distributed over the 16d positions. Subsequently, temperature-dependent neutron and X-ray diffraction (XRD) measurements were performed, in particular looking at the X-ray data, which has a better resolution.…”

mentioning

confidence: 83%

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

et al. 2006

View full text Add to dashboard Cite

Advances in Li-ion batteries for energy storage have facilitated the success of mobile electronic equipment. In particular, high power densities in combination with low-price materials may also make Li-ion batteries attractive for more heavy-duty automotive applications. To facilitate such developments it is essential to understand the material properties that are responsible for the kinetic performance of Li-ion-battery electrodes. In general it is believed that two-phase reactions in electrode materials, responsible for the flat potential upon (dis)charging, lead to relatively low (dis)charge rates, hence limiting the power density. In this context, spinel Li 4 -Ti 5 O 12 [1][2][3][4][5] is very interesting because it has the unusual combination of fast (dis)charge rates [6] and an extremely flat potential, [3,7] the latter being due to the two-phase reaction be- [8] respectively). As a result the twophase reaction will not lead to substantial structural strain, a favorable property because lattice strains upon cycling are among the main causes of capacity loss in lithium battery electrodes. Although it is established in the literature that at room temperature the (dis)charging in Li 4+x Ti 5 O 12 proceeds through a two-phase equilibrium, [3,8] which is responsible for the very flat potential for 0.09 < x < 2.91, the absence of strain and the observation of partial 16c occupation at room temperature [9] and at elevated temperatures [10] indicate that solid-solution behavior could occur close to room temperature. The aim of this contribution is to study the Li 4+x Ti 5 O 12 structure in detail to gain more understanding of its performance as a battery electrode. The unexpected results completely change our understanding of this material. In contrast to common knowledge, Li 4+x Ti 5 O 12 as a two-phase system (consisting of the end members Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 ) appears to be unstable at room temperature, and relaxes to a homogeneous solid-solution phase for the whole concentration range. True two-phase separation in equilibrium is only observed below 100 K. The relaxation towards equilibrium takes place on the timescale of spontaneous Li-ion diffusion (in absence of an applied gradient), and reveals that faster Li insertion will lead to a kinetically induced effective two-phase reaction, which is commonly observed for Li 4 Ti 5 O 12 . However, unlike previous assumptions, the present results demonstrate that this is actually a nonequilibrium situation. The solid-solution-induced disorder, resulting from the mixed 8a/16c occupation, is most likely responsible for the high rate-capabilities in Li 4+x Ti 5 O 12 .Room-temperature neutron diffraction of chemically lithiated materials, given in Figure 1a, show that only subtle changes take place in the spinel structure upon lithiation. Although hardly visible in Figure 1a, the high intensity and large d-spacing range probed by neutron diffraction on the General Materials Diffractometer (GEM, ISIS, Didcot, UK), lead to a large number of resolved reflectio...

show abstract

mentioning

confidence: 83%

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

et al. 2006

View full text Add to dashboard Cite

show abstract

“…In LTO, a redox couple from Ti 4+ to Ti 3+ reversibly delivered the electron and the two-phase transition process between spinel and rock salt was occurred at 1.55 V vs. Li/Li + (Aldon et al, 2004;Takami et al, 2011). Since it has very low-volume expansion and higher working potential, LTO is an emerging anode material that can solve the above mentioned problems.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Rate Capability of Oxide Coated Lithium Titanate within Extended Voltage Ranges

Ahn

Xiao

2015

Front. Energy Res.

View full text Add to dashboard Cite

Lithium titanate (Li 4 Ti 5 O 12 or LTO) is a promising negative electrode material of high-power lithium-ion batteries, due to its superior rate capability and excellent capacity retention. However, the specific capacity of LTO is less than one half of that of graphite electrode. In this work, we applied ultrathin oxide coating on LTO by the atomic layer deposition technique, aiming for increasing the energy density by extending the cell voltage window and specific capacity of LTO. We demonstrated that a few nanometer thick Al 2 O 3 coating can suppress the mechanical distortion of LTO cycled at low potential, which enable the higher specific capacity and excellent capacity retention. Furthermore, the surface coating can facilitate the charge transfer, leading to significantly improved rate capabilities, comparing with the uncoated LTO.

show abstract

“…[1][2][3] Compared to graphite, lithium titanate-based materials reveal a higher Li-ion insertion-extraction potential of approximately 1.55 V (vs. Li/Li ＋ ), which is above the reduction potential of electrolyte solvents, therefore they can avoid the formation of a solid electrolyte interface. [4][5][6] In addition, the nanocrystalline Li 4 Ti 5 O 12 exhibits excellent cycling stability and high rate capability for applications of Li-ion battery.…”

Section: Introductionmentioning

confidence: 99%

Low‐temperature Synthesis of Peony‐like Spinel Li₄Ti₅O₁₂ as a High‐performance Anode Material for Lithium Ion Batteries

Xia

Jiao

et al. 2011

Chin. J. Chem.

View full text Add to dashboard Cite

Peony-like spinel Li 4 Ti 5 O 12 was synthesized via calcination of precursor at the temperature of 400 ℃, and the precursor was prepared through a hydrothermal process in which the reaction of hydrous titanium oxide with lithium hydroxide was conducted at 180 ℃. The as-prepared product was investigated by SEM, TEM and XRD, respectively. As anode material for lithium ion battery, the Li 4 Ti 5 O 12 obtained was also characterized by galvanostatic tests and cyclic voltammetry measurements. It is found that the peony-like Li 4 Ti 5 O 12 exhibited high rate capability of 119.7 mAh•g -1 at 10 C and good capacity retention of 113.8 mAh•g -1 after 100 cycles at 5 C, and these results indicate the peony-like Li 4 Ti 5 O 12 has promising applications for lithium ion batteries with high performance.

show abstract

Chemical and Electrochemical Li-Insertion into the Li₄Ti₅O₁₂ Spinel

Cited by 315 publications

References 22 publications

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

Enhanced Rate Capability of Oxide Coated Lithium Titanate within Extended Voltage Ranges

Low‐temperature Synthesis of Peony‐like Spinel Li₄Ti₅O₁₂ as a High‐performance Anode Material for Lithium Ion Batteries

Contact Info

Product

Resources

About

Chemical and Electrochemical Li-Insertion into the Li4Ti5O12 Spinel

Cited by 315 publications

References 22 publications

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li4+xTi5O12

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li4+xTi5O12

Enhanced Rate Capability of Oxide Coated Lithium Titanate within Extended Voltage Ranges

Low‐temperature Synthesis of Peony‐like Spinel Li4Ti5O12 as a High‐performance Anode Material for Lithium Ion Batteries

Contact Info

Product

Resources

About

Chemical and Electrochemical Li-Insertion into the Li₄Ti₅O₁₂ Spinel

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

A Kinetic Two‐Phase and Equilibrium Solid Solution in Spinel Li₄₊_xTi₅O₁₂

Low‐temperature Synthesis of Peony‐like Spinel Li₄Ti₅O₁₂ as a High‐performance Anode Material for Lithium Ion Batteries