Lithium insertion and extraction properties of hollandite-type KxTiO2 with different K content in the tunnel space

Sakao, Mitsumasa; Kijima, Norihito; Akimoto, Junji; Okutani, Takeshi

doi:10.1016/j.ssi.2013.04.013

Cited by 25 publications

(19 citation statements)

References 34 publications

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“…Understanding transport limitations and available diffusion pathways is critical for several classes of 1D materials, including materials structurally 34 and compositionally 35 related to the silver hollandite material, and has been an active area of experimental and theoretical study for 1D diffusion in LiFePO 4 (ref. 36 ).…”

Section: Discussionmentioning

confidence: 99%

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Meng

et al. 2017

Nat Commun

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Multiple lithium-ion transport pathways and local phase changes upon lithiation in silver hollandite are revealed via in situ microscopy including electron diffraction, imaging and spectroscopy, coupled with density functional theory and phase field calculations. We report unexpected inter-nanorod lithium-ion transport, where the reaction fronts and kinetics are maintained within the neighbouring nanorod. Notably, this is the first time-resolved visualization of lithium-ion transport within and between individual nanorods, where the impact of oxygen deficiencies is delineated. Initially, fast lithium-ion transport is observed along the long axis with small net volume change, resulting in two lithiated silver hollandite phases distinguishable by orthorhombic distortion. Subsequently, a slower reaction front is observed, with formation of polyphase lithiated silver hollandite and face-centred-cubic silver metal with substantial volume expansion. These results indicate lithium-ion transport is not confined within a single nanorod and may provide a paradigm shift for one-dimensional tunnelled materials, particularly towards achieving high-rate capability.

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Section: Discussionmentioning

confidence: 99%

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Meng

et al. 2017

Nat Commun

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“…This phase is less dense than rutile, anatase and brookite phases (respectively 3.73-3.75 g/cm 3 [11,12], 4.26 g/ cm 3 [13], 3.92 g/cm 3 [13], 4.12 g/cm 3 [14]) which can explain its efficiency for Li-batteries. Also, there are numerous theoretical and experimental studies on the intercalation of lithium in rutile and anatase [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33], there is an increasing number of studies on TiO 2 -B [3][4][5][6][7]23,32,[34][35][36][37][38], few studies on other phases of titania [39][40][41][42][43], rarer on brookite [6,[44][45]…”

Section: Introductionmentioning

confidence: 99%

Lithium migration at low concentration in TiO 2 polymorphs

Arrouvel

Peixoto

Valério

et al. 2015

Computational and Theoretical Chemistry

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We report an atomistic simulation study at low concentration of lithium in scanning all the possible pathways for Li migration in TiO 2 polymorphs. We are particularly interested in showing the effects of the structural properties on the intercalation energies and on the energy barriers for ion diffusion. The most favourable directions for Li + transport are highlighted and we observe an anisotropic diffusion in rutile, brookite and TiO 2-B whereas the diffusion is isotropic in the case of anatase. The lowest energy barrier is calculated in rutile but it is not a key factor to determine the efficiency of Li-battery materials. Intercalation energies of stable and transition states are however important data to take into account as well as the Li pathway in order to evaluate the potentiality of each polymorph for Li migration.

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“…[1][2][3][4][5][6] Among the numerous hollandites, titaniumbased materials have attracted considerable attention due to their improved light scattering properties, chemical stability, biological inertness, ion exchangeability, and good ionic conduction, 7,8 enabling the development of a series of new functional ceramic materials. [9][10][11][12][13] In addition to the use of solid matrices for the immobilization of radioactive cesium and anode materials for lithium-ion batteries, [14][15][16][17] hollandite K x Ti 8 O 16 with large (2 × 2) tunnels could accommodate a large number of sodium ions and facilitate Na + diffusion in sodium ion batteries. [18][19][20] Moreover, hollandite-type oxides also exhibit good performance in the catalysis field.…”

Section: Introductionmentioning

confidence: 99%

Temperature‐dependent electrical transport behavior and structural evolution in hollandite‐type titanium‐based oxide

Feng

et al. 2019

J Am Ceram Soc

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Electrical transport behavior and structural characteristics directly determine the use of functional ceramic materials in electronic information storage, catalytic conversion, and energy field applications. However, these properties are poorly understood because most of the relevant experiments were performed in a rather narrow temperature range. Herein, we used hollandite‐type KxTi8O16 as an example to systematically study the temperature‐dependent structure and electrical transport properties in a wide temperature range from 25 to 900°C. The electrical transport involves both potassium ionic conduction and electronic conduction. With increasing temperature, the ionic conductivity increases below 800°C and decreases above 800°C. The electronic conductivity displays two maxima at 0.15 S/cm at 400°C and 5.2 × 10−4 S/cm at 800°C. These interesting variations in the conductivities are related to the presence of Ti3+ and the structural transformation from hollandite to a mixture of rutile and jeppeite. The findings reported herein support the potential application of titanium‐based hollandites and provide an understanding of the electrical transport properties of functional ceramic materials.

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Lithium insertion and extraction properties of hollandite-type KxTiO2 with different K content in the tunnel space

Cited by 25 publications

References 34 publications

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Lithium migration at low concentration in TiO 2 polymorphs

Temperature‐dependent electrical transport behavior and structural evolution in hollandite‐type titanium‐based oxide

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