Cation Distribution in Ordered Spinels of the Li2O–TiO2–Fe2O3System

Scharner, S.; Weppner, W.; Schmid‐Beurmann, Peter

doi:10.1006/jssc.1997.7572

Cited by 52 publications

(43 citation statements)

References 21 publications

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“…The X-ray powder diffraction pattern of the non-milled (0h) mixture shows the peaks characteristic of the initial reactants. The very low peak-intensities of the rutile and Li 2 CO 3 components relative to those of α-Fe 2 O 3 reflects both their small quantities as well as the low scattering factors of both Ti 4+ and Li + relative to that of Fe 3+ [5]. After milling for 3h, the peaks corresponding to Li 2 CO 3 and rutileTiO 2 almost disappear, while those attributable to α-Fe 2 O 3 start to broaden and decrease in intensity indicating a significant decrease in the crystallite size for all components.…”

Section: 1a Milling the Rutile-containing Mixturementioning

confidence: 99%

“…As a remedy, it has been pointed out that to avoid the drawbacks associated with high temperature-sintering, substituted lithium ferrites should be synthesized at or below 850ºC [10]. We note that although a substantial literature has accumulated on the use of mechanical milling for lowering the temperatures of formation for many ferrites [11], there is only limited information on the use of the technique to synthesize pure or substituted lithium ferrites [4,5,12]. Of particular interest is an earlier investigation [5] which reported the formation of Ti-substituted Li 0.5 Fe 2.5 O 4 at 870 ºC by milling a mixture of the anatase polymorph of TiO 2 , α-Fe 2 O 3 and Li 2 O followed by double sintering under oxygen flow for 36h.…”

Section: Introductionmentioning

confidence: 99%

“…We note that although a substantial literature has accumulated on the use of mechanical milling for lowering the temperatures of formation for many ferrites [11], there is only limited information on the use of the technique to synthesize pure or substituted lithium ferrites [4,5,12]. Of particular interest is an earlier investigation [5] which reported the formation of Ti-substituted Li 0.5 Fe 2.5 O 4 at 870 ºC by milling a mixture of the anatase polymorph of TiO 2 , α-Fe 2 O 3 and Li 2 O followed by double sintering under oxygen flow for 36h. However, the influence of other polymorphs of TiO 2 on the formation of the material was not investigated and the role of the milling process in lowering the material temperature of formation was not identified.…”

Section: Introductionmentioning

confidence: 99%

“…The incorporation of Ti 4+ in the spinel-related structure of Li 0. [1,5,6]. Normally, the material is prepared by the conventional ceramic double sintering method in which solid state reactions between oxides and/or carbonates of Li, Fe(III) and Ti(IV) require prolonged heat exposure at elevated temperatures (typically ∼1200ºC) [1,7,8].…”

Section: Introductionmentioning

confidence: 99%

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The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

2006

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Single-phased spinel-related titanium-substituted Li 0.5 Fe 2.5 O 4 has been synthesized by sintering in air a mechanically pre-milled mixture of lithium carbonate, corundum-related iron (III) oxide and the rutile polymorph of titanium (IV) oxide at 700ºC (12h). This temperature is ca. 450-500ºC less than the temperatures at which the material is normally prepared by conventional ceramic techniques. On replacing the rutile polymorph of titanium (IV) oxide in the pre-milled mixture by the anatase form the formation of single-phased titanium substituted Li 0.5 Fe 2.5 O 4 was not achieved even after sintering the mixture at 1000 o C (12h).2

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Section: 1a Milling the Rutile-containing Mixturementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

2006

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“…Algunas de las espinelas que hemos preparado como posibles precursores de ramsdellitas son compuestos que han sido previamente descritos por lo que la síntesis de éstas se ha llevado a cabo siguiendo la información disponible (10)(11)(12) 3 , operación que es realizada en el interior de una caja seca bajo atmósfera de argón. Finalmente la mezcla es introducida en una ampolla de cuarzo previamente forrada con una lámina de cobre de alta pureza.…”

Section: Parte Experimentalunclassified

La transformación espinela-ramsdelita: una nueva ruta de obtención de materiales para baterías recargables de litio

Garcı́a-Alvarado¹,

Kühn²,

Martín-Gil³

2002

Bol. Soc. Esp. Ceram. Vidr.

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Monte (Madrid).Se han investigado las posibles transformaciones a alta temperatura de diversas espinelas del tipo LiTi 2-x M x O 4 con M = V, Cr, Fe y Co, habiéndose determinado que es posible la obtención de nuevas rasmdellitas LiTi 2-x V x O 4 y LiTi 2-x Cr x O 4 con 0 ≤ x ≤ 1. La caracterización estructural mediante difracción de rayos X y las medidas de susceptibilidad magnética realizadas para el caso del cromo, en unión de los datos aportados por el estudio electroquímico realizado, han permitido establecer que la sustitución catiónica lleva a compuestos del tipo Li(Ti. El comportamiento electroquímico de LiTi 2-x V x O 4 permite proponer su posible uso como electrodo negativo en baterías de ion litio, ya que estos nuevos electrodos desarrollan capacidades de 160 mAh/g a un potencial medio de 1.5 V, valores que resultan similares a los del compuesto sin sustituir, la ramsdellita LiTi 2 O 4 (166 mAh/g). Hay que destacar el comportamiento versátil de una nueva familia de ramsdellitas, LiTi 2-x Cr x O 4 . El estudio presentado sobre el miembro de esta familia con x = 1, la composición que se ha considerado más relevante, ha permitido proponer a este nuevo material como un buen candidato a electrodo negativo en baterías recargables de litio. Además de poder desarrollar en reducción, una capacidad máxima de 157 mAh/g a un potencial medio de 1.5 V, el material puede desarrollar en oxidación una capacidad de unos 90 mAh/g bajo una densidad de corriente de 0.1 mA/cm 2 , por lo que podría actuar como el electrodo positivo, ya que en este caso el potencial medio de trabajo sería de 4 V. . The electrochemical behaviour of the series LiTi 2-x V x O 4 makes these oxides useful as negative electrode in rechargeable lithium ion batteries. Electrodes consisting of LiTi 2-x V x O 4 would develop at 1.5 volts reversible capacities of about 160 mAh/g, value which is close to that described for the parent LiTi 2 O 4 . We would like to remark the versatile behaviour of the new ramsdellite series LiTi 2-x Cr x O 4 . A detailed study of the intercalation electrochemistry of the member with x = 1, e.g. LiTiCrO 4 , shows that this new material may be useful as the negative electrode in rechargeable lithium ion batteries. A maximal theoretical capacity of 157 mAh/g is developed at an average potential of 1.5 Volts When an electrochemical oxidation under a density current of 0.1 mA/cm 2 is performed on LiTiCrO 4 , the compound develops a capacity of 90 mAh/g at an average potential of 4 Volts. Hence, this ramsdellite may also be useful for the positive electrode in lithium batteries. Palabras clave: ramsdellita, baterías recargables de litio, intercalación electroquímica de litio, nuevos materiales para electrodo Spinel -ramsdellite transition: A new synthesis route to materials useful as electrodes in rechargeable lithium batteries INTRODUCCIÓNEn 1991 la compañía Sony comercializó la primera batería recargable de ion litio y desde entonces, siguiendo la configuración de ésta, la mayoría de los dispositivos usan el óxido LiCoO 2 co...

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Lithium‐Ion Transport in Li₄Ti₅O₁₂ Epitaxial Thin Films vs. State of Charge

Pagani

Döbeli

Battaglia

2020

Batteries & Supercaps

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We investigate the electrochemical lithiation of epitaxial Li4Ti5O12 thin‐film model electrodes grown on epitaxial platinum current collectors. Structure and composition of Li4Ti5O12 films are confirmed by out‐of‐plane and in‐plane X‐ray diffraction and elastic recoil detection analysis. Employing different cell configurations, we deconvolute electrochemical impedance spectra and extract for the first time the lithium‐ion conductivity as a function of electrochemical lithiation. Lithium‐ion conductivity increases monotonously by more than two orders of magnitude from 2.6 ⋅ 10−9 S/cm in Li4Ti5O12 to above 3 ⋅ 10−7 S/cm between Li4.5Ti5O12 and Li6Ti5O12 and drops again to 1.3 ⋅ 10−9 S/cm in Li7Ti5O12. We discuss our results in light of nuclear magnetic resonance studies and theoretical models reported previously and derive important implications for fast‐charging applications of lithium‐ion batteries with Li4Ti5O12 anodes.

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Cation Distribution in Ordered Spinels of the Li2O–TiO2–Fe2O3System

Cited by 52 publications

References 21 publications

The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

La transformación espinela-ramsdelita: una nueva ruta de obtención de materiales para baterías recargables de litio

Lithium‐Ion Transport in Li₄Ti₅O₁₂ Epitaxial Thin Films vs. State of Charge

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Cation Distribution in Ordered Spinels of the Li2O–TiO2–Fe2O3System

Cited by 52 publications

References 21 publications

The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

The influence of TiO2 polymorph, mechanical milling and subsequent sintering on the formation of Ti-substituted spinel-related Li0.5Fe2.5O4

La transformación espinela-ramsdelita: una nueva ruta de obtención de materiales para baterías recargables de litio

Lithium‐Ion Transport in Li4Ti5O12 Epitaxial Thin Films vs. State of Charge

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Product

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Lithium‐Ion Transport in Li₄Ti₅O₁₂ Epitaxial Thin Films vs. State of Charge