The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4 spinel, and Li2Ti2O4

Cava, R. J.; Murphy, D. W.; Zahurak, S. M.; Santoro, A.; Roth, Robert

doi:10.1016/0022-4596(84)90228-7

Cited by 326 publications

(359 citation statements)

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“…The starting material is crystalline with the cubic phase (Fd 3m). The cell parameter of the unit cell of fully lithiated c-TiO 2 at ambient pressure corresponds to 8.31 Å that is somewhat smaller than the one previously reported for chemically prepared bulk Li 2 Ti 2 O 4 (a ¼ 8:376 A) [25] of the same symmetry. Geometric optimization using density functional theory calculations gives an optimized lattice constant of 8.27 Å , suggesting a good balance of electrostatic forces in electrochemically synthesized lithiated c-TiO 2 [16].…”

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confidence: 54%

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

et al. 2013

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confidence: 54%

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

et al. 2013

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“…[24][25][26][27][28][29][30][31][32][33] The principal reaction that governs the electrochemical processes in a TiO 2 /Li half-cell is thought to be: TiO 2 + xLi + + xeLi x TiO 2 (1), with the maximum insertion coefficient x determined to be about 0.5. [34][35][36][37] This leads to a theoretical charge storage capacity of 167.5 mA h g -1 . 28 It is known Interestingly, it can be observed that the intensity of both peaks increases during the subsequent scans, suggesting a possible activating process in the electrode material.…”

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Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO₂ Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage

et al. 2010

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Synthesis of nanocrystals with exposed high-energy facets is a well-known challenge in many fields of science and technology. The higher reactivity of these facets simultaneously makes them desirable catalysts for sluggish chemical reactions and leads to their small populations in an equilibrated crystal. Using anatase TiO 2 as an example, we demonstrate a facile approach for creating high surface area, stable nanosheets comprised of nearly 100% exposed (001) facets. Our approach relies on spontaneous assembly of the nanosheets into three-dimensional, hierarchical spheres that stabilizes them from collapse. We show that the high surface density of exposed TiO 2 (001) facets leads to fast lithium insertion/deinsertion processes in batteries that mimic features seen in high power electrochemical capacitors.2

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“…However, only a single lithium concentration was considered and the relaxation of the lattice was restricted either by imposing rigid cluster boundary conditions [15] or by considering only isotropic variations of the cell [16]. As is clear from neutron diffraction studies of anatase [17], and will become evident below, unconstrained structural relaxation is vital in these systems.In the current study fully relaxed first principles simulations have been used to compute the thermodynamics of lithium intercalation in the rutile and anatase structures for a wide range of concentrations and possible configurations. Lithium ion diffusion pathways and barriers have also been determined.…”

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“…Intercalation is observed to proceed as a single phase reaction up to x 0.05 0.1 with further insertion producing a two phase equilibrium of Li-poor and Li-rich regions. The Li-rich phase is observed to be an orthorhombic distortion of anatase with composition Li 0.5 TiO 2 [17,23]. Low-energy structures for lithiated anatase were sought for x 1͞16, 1͞8, 1͞4, 1͞2, 3͞4, and 1.…”

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Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

2001

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A new model of Li intercalation into rutile and anatase structured titania has been developed from first principles calculations. The model includes both thermodynamic and kinetic effects and explains the observed differences in intercalation behavior and their temperature dependence. The important role of strong local deformations of the lattice and elastic screening of interlithium interactions is demonstrated. In addition, a new phase of LiTiO 2 is reported. DOI: 10.1103/PhysRevLett.86.1275 Transition metal oxides are promising electrode materials in advanced high-energy density batteries [1]. The performance of an electrode depends on its ability to intercalate lithium reversibly into the host lattice. The transition metal oxides have open structures capable of accommodating guest ions and a flexible electronic structure which can accommodate donated electrons and provide sufficient ionic and electronic conductivity. These properties result in a number of low-energy sites for guest ions within the lattice and the potential for high capacity lithium ion intercalation.Battery performance is usually characterized by low current discharge curves which approximate the equilibrium voltage difference between the electrodes, often referred to as the open circuit voltage (OCV). The key factors in applications are high-energy density and reversible structural changes on Li intercalation for a large range of the insertion concentration.For a material in thermodynamic equilibrium the OCV is fully determined by the difference in the chemical potential of lithium between the anode and the cathode which is determined by the ordering of the lithium ions in the host structure. However, in practical applications the OCV is also often limited by lithium ion diffusion which prevents ions from reaching thermodynamically stable sites. The design of new battery materials requires a microscopic understanding of the stable sites and diffusion pathways which is very difficult to obtain from experiment. Therefore, first principles simulation, which provides accurate and reliable energy surfaces, has a key role to play in identifying and characterizing prospective electrode materials.Previous simulations, based on a combination of first principles energetics and a Monte Carlo treatment of the statistical mechanics, have focused on the thermodynamics of lithium insertion. Thus, phase diagrams and equilibrium OCV's have been computed for Li . This methodology requires the representation of configurational energies using effective interaction parameters which are assumed to be valid over a wide range of insertion concentrations.Another interesting electrode material is nanostructured TiO 2 which is currently used in solar cell applications [6]. It has a number of practical advantages as it is readily available, chemically stable, semiconducting, inexpensive, and nontoxic [7]. The most common natural forms of TiO 2 are rutile and anatase. Lithium intercalation into both forms has been studied extensively. In Li x TiO 2 the reported maximum...

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The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4 spinel, and Li2Ti2O4

Cited by 326 publications

References 9 publications

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO₂ Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

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The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4 spinel, and Li2Ti2O4

Cited by 326 publications

References 9 publications

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure

Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

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Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO₂ Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage