Anatase as a cathode material in lithium—organic electrolyte rechargeable batteries

Bonino, F.; Busani, L.; Lazzari, M.; Manstretta, M.; Rivolta, B.; Scrosati, B.

doi:10.1016/0378-7753(81)80031-6

Cited by 128 publications

(104 citation statements)

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“…However, diffusion in rutile is highly anisotropic and abnormally fast along c [22]. One would therefore expect structures involving c occupancy to be accessible at all temperatures and therefore this model fails to explain the absence of intercalation along c at room temperature [12,13]. The interpretation of the OCV resulting from the current work is very different.…”

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confidence: 43%

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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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confidence: 43%

“…Lithium intercalation into both forms has been studied extensively. In Li x TiO 2 the reported maximum electrochemical insertion varies between x 0.1 and 1 for rutile [8][9][10][11] and 0.5 and 1 for anatase [10,[12][13][14]. One likely reason for the large variation in these studies is the effect of temperature.…”

mentioning

confidence: 89%

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

2001

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“…4(a, b). After the 60 min anodization process, the mesh retained sufficient void regions, and the [4,26]. A similar observation has been previously reported, and it has been ascribed to an activation effect during the initial cycling of the TiO 2 nanotubes [27].…”

Section: Resultssupporting

confidence: 71%

Tuning three-dimensional TiO2 nanotube electrode to achieve high utilization of Ti substrate for lithium storage

Zhang

Qing-yuan

Chou

et al. 2014

Electrochimica Acta

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. (2014). Tuning three-dimensional TiO2 nanotube electrode to achieve high utilization of Ti substrate for lithium storage. Electrochimica Acta, 133 570-577.Tuning three-dimensional TiO2 nanotube electrode to achieve high utilization of Ti substrate for lithium storage AbstractThree-dimensional (3D) TiO2 nanotube arrays grown on Ti mesh were prepared via the anodization process. The diameters of the Ti and TiO 2/Ti wires and the length of the TiO2 nanotubes have linear relationships with the anodization processing time. When the anodization processing time is 600 min, the TiO2/Ti mesh anode materials showed good capacity retention and high specific area capacity, without the need for a current collector or binder, due to their high surface area, high substrate utilization, and large active material loading rate per unit area. At the current density of 50 μA cm-2, TiO2/Ti mesh with 600 min anodization processing time has a stable discharge platform at 1.78 V, and the specific area capacity is 1745.5 μAh cm-2 over 100 cycles. By tuning the geometric parameters of the TiO2/Ti mesh and the anodization processing time, we can pave the way to finding TiO2/Ti mesh electrodes for lithium-ion batteries with high capacity per unit area and outstanding mechanical behaviour.Keywords substrate, three, lithium, dimensional, storage, achieve, tio2, ti, nanotube, utilization, high, electrode, tuning Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsZhang, Z., Zeng, Q., Chou, S., Li, X., Li, H., Ozawa, K., Liu, H. & Wang, J. (2014). Tuning three-dimensional TiO2 nanotube electrode to achieve high utilization of Ti substrate for lithium storage. Electrochimica Acta, 133 570-577. nanotubes have linear relationships with the anodization processing time. When the anodization processing time is 600 min, the TiO 2 /Ti mesh anode materials showed good capacity retention and high specific area capacity, without the need for a current collector or binder, due to their high surface area, high substrate utilization, and large active material loading rate per unit area. At the current density of 50 µA cm -2 , TiO 2 /Ti mesh with 600 min anodization processing time has a stable discharge platform at 1.78 V, and the specific area capacity is 1745.5 µAh cm -2 over 100 cycles. By tuning the geometric parameters of the TiO 2 /Ti mesh and the anodization processing time, we can pave the way to finding TiO 2 /Ti mesh electrodes for lithium-ion batteries with high capacity per unit area and outstanding mechanical behaviour. Authors

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“…8 However, diffusion in rutile is highly anisotropic and abnormally fast along c. 36 In light of this one would expect structures involving occupancy of the c channels to be accessible at all temperatures and therefore this model fails to explain the absence of intercalation along c at room temperature. 8,38 The interpretation of the OCV resulting from the current work is very different. We find that structures with ions arranged along the c channels have energies higher than those of the ab-layered structures ͓Figs.…”

Section: The Open Circuit Voltage Profilementioning

confidence: 96%

“…Thus there is no significant intercalation into rutile at ambient temperatures even in the ideal electrode orientation ͑001͒. 6,8,38,39,40 At elevated temperatures in-plane diffusion is considerably enhanced, unblocking the c channels and intercalation proceeds. In fact at 120°C Li is observed to intercalate up to full loading.…”

Section: Diffusionmentioning

confidence: 99%

Density-functional simulations of lithium intercalation in rutile

2002

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Density-functional simulations of lithium intercalation into rutile structured titanium dioxide are presented. Full relaxation of structures for a wide range of insertion concentrations is used to identify the thermodynamically most stable configurations and Li-ion site preferences. The host lattice is found to undergo large deformations upon Li insertion, which can be related to the excitation of soft vibrational modes. The dominant screening interaction is found to be due to these elastic distortions of the lattice rather than to dielectric screening. This leads to highly anisotropic and concentration-dependent effective Li-Li interactions, which are not easily amenable to empirical parametrization. The anisotropic volume expansion is found to be largely due to the increase in the radii of reduced Ti ions as they accommodate charge donated to the lattice. The computed open circuit voltage ͑OCV͒ reproduces the characteristic features of experimental discharge curves at elevated temperature. The computed Li-ion energy surfaces reveal highly anisotropic diffusion. A model of Li intercalation is proposed, which takes account of both the thermodynamic and kinetic properties computed here. This model is used to resolve apparent contradictions in the current interpretation of the measured OCV and its dependence on temperature. Predicted changes in the electronic structure and their relationship to the interaction between structural, charge, and spin degrees of freedom are discussed in detail.

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Anatase as a cathode material in lithium—organic electrolyte rechargeable batteries

Cited by 128 publications

References 4 publications

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide

Tuning three-dimensional TiO2 nanotube electrode to achieve high utilization of Ti substrate for lithium storage

Density-functional simulations of lithium intercalation in rutile

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