High-Resolution In-Situ Structural Measurements of the Li4/3Ti5/3O4 “Zero-Strain” Insertion Material

Ronci, F.; Reale, P.; Scrosati, B.; Panero, S.; Albertini, V. Rossi; Perfetti, P.; Michiel, Marco Di; Merino, J. M.

doi:10.1021/jp013240p

Cited by 154 publications

(122 citation statements)

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“…These results indicate structural changes of the nano-sized Li 4 has a smaller lattice parameter than the Li 4+x Ti 5 O 12 lattice due to the replacement of lithium ion from the 8a to 16c sites. 4,22 Therefore, the phases with the larger and smaller lattice parameters might correspond to the spinel phase and the ordered rock-salt phase, respectively. The intensity of the diffraction peak of the spinel phase decreased from 1.4 to 1.0 V, while the diffraction peak of the ordered rock-salt phase showed an increase in intensity.…”

Section: ¹3mentioning

confidence: 99%

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

et al. 2012

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Electrochemical properties and structure changes of nano-sized Li 4 Ti 5 O 12 during lithium (de)intercalation were investigated using a two-dimensional thin film electrode. Li 4 Ti 5 O 12 thin films were deposited on a Nb:SrTiO 3 (110) substrate by a pulsed laser deposition technique. X-ray diffraction and reflectometry measurements confirmed the epitaxial growth of 27.6-nm-thick Li 4 Ti 5 O 12 (110) films. Galvanostatic charge-discharge curves showed a large discharge capacity of 217 mAh g −1 at the initial discharge cycle, although the reversible capacity decreased in subsequent cycles. In situ X-ray diffraction measurements clarified the drastic structural changes of the Li 4 Ti 5 O 12 film upon soaking in the electrolyte and during the first intercalation and deintercalation processes. The surface region of Li 4 Ti 5 O 12 had a different structure from the bulk during electrochemical cycling and could cause the nanosized Li 4 Ti 5 O 12 electrodes to have high capacities and poor stabilities.

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Section: ¹3mentioning

confidence: 99%

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

et al. 2012

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“…This is because Li 4 Ti 5 O 12 shows exceptionally high rate performance, excellent cycling stability, and good Li-insertion electrochemistry with a formal potential of ~1.55 V vs. Li + /Li as an anode in LIBs. [2][3][4][5][6] As a result of the high redox potential of Li 4 Ti 5 O 12 , the formation of a solid electrolyte interface layer [7][8][9][10] and Li-metal deposition or electroplating 11 on the surface of the anode, all detrimental to LIB use, can be prevented. It is generally accepted that the Li (de)intercalation reaction in Li 4 Ti 5 O 12 proceeds through a reversible two-phase reaction (Eq.…”

Section: ■ Introductionmentioning

confidence: 99%

Lithium Migration in Li₄Ti₅O₁₂ Studied Using in Situ Neutron Powder Diffraction

et al. 2014

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We used in situ neutron powder diffraction (NPD) to study the migration of Li in Li4Ti5O12 anodes with different particle sizes during battery cycling. The motivation of this work was to uncover the mechanism of the increased capacity of the battery made with a smaller-particle-sized anode. In real time, we monitored the anode lattice parameter, Li distribution, and oxidation state of the Ti atom, and these suggested an increase in the rate of Li incorporation into the anode rather than a change in the migration pathway as a result of the particle size reduction. The lattice of these anodes during continuous lithiation undergoes expansion followed by a gradual contraction and then expansion again. The measured lattice parameter changes were reconciled with Li occupation at specific sites within the Li4Ti5O12 crystal structure, where Li migrates from the 8a to 16c sites. Despite these similar Li-diffusion pathways, in larger-particle-sized Li4Ti5O12 the population of Li at the 16c site is accompanied by Li depopulation from the 8a site, which is in contrast to the smaller-particlesized anode where our results suggest that Li at the 8a site is replenished faster than the rate of transfer of Li to the 16c site. Fourier-difference nuclear density maps of both anodes suggest that 32e sites are involved in the diffusion pathway of Li. NPD is again shown to be an excellent tool for the study of electrode materials for Liion batteries, particularly when it is used to probe real-time crystallographic changes of the materials in an operating battery during charge-discharge cycling. KEYWORDS: in-situ neutron diffraction, lithium ion battery, lithium titanium oxide, particle size, lithiation and delithiation mechanism.ABSTRACT: We use in-situ neutron powder diffraction (NPD) to study the migration of Li in Li 4 Ti 5 O 12 anodes with different particle sizes during battery cycling. The motivation of this work was to uncover the mechanism for increased capacity of the battery made with a smaller particle-sized anode. We monitor in real time the anode lattice parameter, Li distribution, and the oxidation state of the Ti atom, with these suggesting an increase in the rate of Li incorporation into the anode rather than a change in migration pathway as a result of the particle size reduction. The lattice of these anodes during continuous lithiation undergoes expansion, followed by a gradual contraction, and lastly expansion again. The measured lattice parameter changes are reconciled with Li occupation at specific sites within the Li 4 Ti 5 O 12 crystal structure, where Li migrates from the 8a to 16c sites. Despite these similar Li diffusion pathways, in the larger particle-sized Li 4 Ti 5 O 12 the population of Li at the 16c site is accompanied by Li depopulation from the 8a site, in contrast to the smaller particle-sized anode where our results suggest that the Li at the 8a site is replenished faster that the rate of transfer of Li to the 16c site. Fourier-difference nuclear density maps of both anodes suggest that 32...

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“…Lithium titanate (Li 4 Ti 5 O 12 , LTO) was a spinel structure and known as a zero strain material (Ohzuku et al, 1995;Ronci et al, 2002). 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).…”

Section: Introductionmentioning

confidence: 99%

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

Ahn

Xiao

2015

Front. Energy Res.

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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.

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High-Resolution In-Situ Structural Measurements of the Li_4/3Ti_5/3O₄ “Zero-Strain” Insertion Material

Cited by 154 publications

References 11 publications

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

Lithium Migration in Li₄Ti₅O₁₂ Studied Using in Situ Neutron Powder Diffraction

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

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High-Resolution In-Situ Structural Measurements of the Li4/3Ti5/3O4 “Zero-Strain” Insertion Material

Cited by 154 publications

References 11 publications

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

Lithium Migration in Li4Ti5O12 Studied Using in Situ Neutron Powder Diffraction

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

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Product

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High-Resolution In-Situ Structural Measurements of the Li_4/3Ti_5/3O₄ “Zero-Strain” Insertion Material

Lithium Migration in Li₄Ti₅O₁₂ Studied Using in Situ Neutron Powder Diffraction