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Operando monitoring the nanometric morphological evolution of TiO2 nanoparticles in a Na-ion battery.

ABSTRACT: Na-ion batteries are nowadays receiving renewed attention because of its propitiousness for large-scale stationary applications. Although the Na storage mechanism is still not completely understood, TiO2 nanoparticles are very promising active anode materials in Na-ion batteries provided that a correct dispersion is achieved within the battery electrode. Whilst the structural changes, either in crystallinity or crystalline phase, that occur during operation are receiving much recent attention, the nanometric morphological evolution of the TiO2 nanoparticles within the electrode is yet to be thoroughly addressed, despite its implication in battery efficiency. In the present work, operando small-angle x-ray scattering studies on TiO2/Na-ion batteries show that whereas the nanoparticle size is preserved during the discharge-charge cycles, the mean distance between nanoparticles increases. The observed morphological changes are consistent with electrode swelling and nanoparticle aggregation during operation, being one phenomenon dominant over the other depending on the applied density current; thus, depending on the differences in ion diffusion within the electrode.

SUBMITTER: Santoro G

PROVIDER: S-EPMC6404958 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Operando monitoring the nanometric morphological evolution of TiO<sub>2</sub> nanoparticles in a Na-ion battery.

Santoro Gonzalo G Amarilla José Manuel JM Tartaj Pedro P Vázquez-Santos María Beatriz MB

Materials today. Energy 20180824

Na-ion batteries are nowadays receiving renewed attention because of its propitiousness for large-scale stationary applications. Although the Na storage mechanism is still not completely understood, TiO<sub>2</sub> nanoparticles are very promising active anode materials in Na-ion batteries provided that a correct dispersion is achieved within the battery electrode. Whilst the structural changes, either in crystallinity or crystalline phase, that occur during operation are receiving much recent a ...[more]

PMID: 30854498

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Project description:A new synthetic method to grow O-deficient rutile TiO2(s) nanorods (NRs) and nanowires (NWs) by a vapor-solid reaction growth method is developed. TiCl4(g) was employed to react with commercially supplied CaTiO3(s) (size 2-4 ?m) at 973 K under atmospheric pressure to generate TiO2(s) NRs (diameters 80-120 nm, lengths 1-4 ?m). The reaction employing TiCl4(g) and CaO(s) at 973 K also generated CaTiO3(s) (size 4-13 ?m) as the intermediate which reacted further with TiCl4(g) to produce NWs (diameters 80-120 nm, lengths 4-15 ?m). This is the first report of 1D rutile TiO2(s) nanostructure with such a high aspect ratio. Both of the NRs and the NWs, with compositions TiO1.81 and TiO1.65, respectively, were single crystals grown in the [001] direction. Their morphology was affected by the reaction temperature, the concentration of TiCl4(g), and the particle size of CaTiO3(s). The NRs and the NWs were investigated as anode materials for Li+-ion batteries. At constant current rates 1, 2, and 5 C (1 C = 170 mA g-1) for 100 cycles, the cycling (1.0-3.0 V) performance data of the NRs were 146, 123, and 104 mA h g-1, respectively. On the other hand, the cycling performance data of the NWs were 120, 80, and 52 mA h g-1, respectively. This is attributed to the high Li+ ion diffusion rate (D Li+ ) of the NRs (29.52 × 10-15 cm2 s-1), which exceeds that of the NWs (8.61 × 10-15 cm2 s-1). Although the [001] growth direction of the NR crystals would provide the fastest channels for the diffusion of Li+ ions and enhance the battery capacity, the extremely long channels in the NWs could hamper the diffusion of the Li+ ions. The O-deficiency in the structure would increase the conductivity of the electrode material and improve the stable cycling stability of the batteries also. The long-term cycling test at 2 C for the battery constructed from the NRs retained 121 mA h g-1 after 200 cycles and 99.2 mA h g-1 after 800 cycles. The device has an excellent long-term cycling stability with a loss of only 0.04% per cycle.

Dataset Information

Operando monitoring the nanometric morphological evolution of TiO2 nanoparticles in a Na-ion battery.

Publications

Operando monitoring the nanometric morphological evolution of TiO<sub>2</sub> nanoparticles in a Na-ion battery.

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