Got TiO<sub>2</sub> Nanotubes? Lithium Ion Intercalation Can Boost Their Photoelectrochemical Performance

Meekins, Benjamin H.; Kamat, Prashant V.

doi:10.1021/nn900897r

Cited by 260 publications

(194 citation statements)

References 66 publications

(107 reference statements)

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“…24 According to equations both for reversible and irreversible electrochemical reactions, the slope of logi p vs. logυ should be 0.5 ( Figure 9a). At 25…”

Section: Resultsmentioning

confidence: 99%

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Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Zec

Cvjetićanin

Bešter‐Rogač

et al. 2017

J. Electrochem. Soc.

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Ternary electrolyte composed of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid (PYR 14 TFSI), γ-butyrolactone (GBL) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and anatase TiO 2 nanotube arrays (NTAs) electrode are investigated for the application in new generation of lithium-ion batteries (LIBs). The electrical conductivity and viscosity are measured in the whole composition range at several temperatures. Also, cyclic voltammetry experiments are performed at different temperatures and scan rates. At all scan rates, up to 100 mV · s −1 Ti 4+ /Ti 3+ redox peaks appear designating exceptionally fast intercalation/deintercalation reaction. At the end of cycling the intercalation/deintercalation capacity was 144.8/140.7 mAh · g −1 at current rate 3 C. The diffusion coefficient for Li + extraction from TiO 2 nanotubes (NTs) have been calculated for temperatures from (25 to 55) • C. Activation energy for diffusion was found to be 54.7 kJ/mol (0.57 eV The rapid development of portable electronic devices and technologies significantly increased demand for the next generation of energy storage systems.1 Because of enhanced energy and power density, efficiency and long life, LIBs are currently one of the most promising energy storage devices.2,3 Improvement of safety standards and low impact on human health and environment is essential for large-scale application of LIBs. 4 Safety concerns related to utilization of highly volatile and flammable organic solvents in commercial cells can be addressed by introducing ionic liquids (ILs) as emerging class of fluids.5 Numerous advantages of ILs such as negligible vapor pressure and high chemical and thermal stability make them ideal candidates for their application in LIBs. Potential application of ILs based on a combination of the pyrrolidinium (PYR + ) cation and bis(trifluoromethanesulfonyl)imide (TFSI -) anion as electrolytes in LIBs with long term cycling stability and very good capacity utilization, has been confirmed by several research groups. [6][7][8][9][10][11][12] Nevertheless, the utilization of IL-based electrolytes is usually limited by their high viscosity, which reduces transport capabilities and slows down the chemical processes that occur in these solvents. Mixing of ionic liquids with molecular solvents such as organic carbonates or lactones can reduce viscosity of applied electrolyte. 12-15Among other aprotic solvents, γ-butyrolactone (GBL) is usually applied in new generation of LIBs and other electrochemical devices. Besides its low cost, GBL has wide liquidus range and better thermal stability comparing to alkyl carbonate solvents. 16 In our previous papers we demonstrated that binary mixture of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, (IM 14 TFSI), and GBL has around 20% higher specific conductivity at low IL mole fractions compared to IM 14 TFSI + propylene carbonate (PC) binary mixture.15,17 Xu et al. observed similar trend in the case of 1-ethyl-3-methylimidazolium dicyanamide (IM 12 DC...

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“…24 According to equations both for reversible and irreversible electrochemical reactions, the slope of logi p vs. logυ should be 0.5 ( Figure 9a). At 25…”

Section: Resultsmentioning

confidence: 99%

“…[22][23][24][25] TiO 2 NTAs anodically grown on Ti-foil represent a unique electrode which merges intercalation compound with current collector without addition of electronically conductive and adhesive additives. Therefore, such electrode may be very suitable for testing new electrolytes for LIBs.…”

Section: 21mentioning

confidence: 99%

Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Zec

Cvjetićanin

Bešter‐Rogač

et al. 2017

J. Electrochem. Soc.

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Nature of N 2p, Ti 3d, O 2p Hybridization of N‐Doped TiO₂ Nanotubes and Superior Photovoltaic Performance through Selective Atomic N Doping

Han

Lee

et al. 2011

Chemistry A European J

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TiO 2 nanotube arrays have great potentials due to good electron transport along the axis and prospective applications, such as photovoltaic cells, [1][2][3][4][5][6][7] electrochemical devices, [8][9][10] and photocatalysts. [11][12][13][14][15][16] Moreover, more advanced applications would be allowed if the band gap could be controlled to efficiently absorb visible light. Recent reports reveal that nitrogen doping with ion implantation or thermal annealing in ammonia gas can be used to modify the band gap of pure TiO 2 . [17][18][19] Despite these great achievements, the possibility to introduce a large portion of chemisorbed N 2 instead of atomic N states, which could lead to the destruction [20] of the crystal structure of a pure TiO 2 nanotube, still exist.Herein, we report the facile method to selectively introduce atomic N states into a highly ordered TiO 2 nanotube array through plasma-assisted nitrogen doping with minimized chemisorbed molecular N 2 states. This selective atomic N doping preserves the original crystal structure and also gives enhanced photovoltaic performance. After the atomic N doping, the partial density of states (PDOS) near to the Fermi energy level were also changed. N 2p states became predominant near the Fermi level, which is a discrete energy level at the top edge of a valence band, whereas the strong hybridization between Ti 3d and O 2p was lost.The ordered TiO 2 nanotubes were fabricated by electrochemical oxidation in NH 4 F (0.3 wt %) containing an ethylene glycol solution with DC 60 voltage. Figure 1 shows hexagonally organized TiO 2 nanotubes with % 120-150 nm outer diameters and % 100-120 nm hollow holes. The amorphous phase of the as-prepared nanotubes was converted to the crystalline phase through annealing. The crystalline phase was confirmed by the high-resolution TEM (HRTEM) image of a nanotube wall and the Fourier transform image (insets of Figure 1 d). Figure 1 e also shows the crystal structures of nanotubes with different annealing conditions ranging from 500 to 800 8C. The sample annealed at 500 8C for 3 h is in a pure anatase phase. However, the portion of the rutile TiO 2 phase is found to increase as the temperature increases. For the selective atomic nitrogen mediation in TiO 2 nanotubes, the samples were exposed to nitrogen plasma with 500 and 700 W microwave plasma powers.Incorporation of nitrogen into TiO 2 nanotubes treated with the 500 W nitrogen plasma for 3 min was confirmed through the energy dispersive X-ray spectroscopy (EDS) analysis (see Figure 2 a). Figure 2 b,c shows the nitrogenbinding nature confirmed by X-ray photoelectron spectroscopy (XPS). Before the TiO 2 nanotubes were treated with nitrogen plasma, Ti 2p XPS spectra showed two signals at Figure 1. SEM images of a TiO 2 nanotube array after electrochemical oxidation, showing a) top and b) magnified views, HRTEM images of c) an as-prepared TiO 2 nanotube wall and d) a crystallized TiO 2 nanotube wall at 500 8C, and e) XRD patterns of TiO 2 nanotubes crystallized at % 500-800 8C for 3 h.

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“…173,174 In contrast, incident photocurrent efficiency spectra for electrochemically doped TiO 2 did not show any extension of the absorption into the visible range. 168,172 This is probably due to the different extent of structure modification in the two cases. Zhang et al report on a self-doping process achieved by microwave assisted reduction of Ti 4+ to Ti 3+ , demonstrating a tenfold increase in the photocurrent, accompanied by detection of incident photocurrent efficiencies from visible light of 1-2% out to 400-500 nm.…”

Section: 125mentioning

confidence: 99%

Titania Nanotubes by Electrochemical Anodization for Solar Energy Conversion

Tsui

Zangari

2014

J. Electrochem. Soc.

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TiO 2 nanotube arrays (NTs) are a promising platform for the conversion of sunlight to electricity in photovoltaic systems or to fuels in photoelectrochemical solar cells. We overview the properties and functionality of the various components of TiO 2 NT-based devices, discuss their integration in the energy conversion system and summarize recent advances in the field. In particular, we discuss the electronic and charge transport properties of TiO 2 NTs that govern the device performance and efficiency. Since the main challenge for the practical use of TiO 2 is the inability to absorb visible light, particular attention is paid to available techniques for TiO 2 sensitization, extending absorption beyond the UV portion of the solar spectrum. These techniques include doping to alter the bandgap and pairing TiO 2 with dyes, inorganic narrow band-gap semiconductors, or metal nanoparticles that exhibit plasmonic behavior. Various catalysts have been successfully paired with TiO 2 to accelerate the photocatalytic reactions of interest; materials, synthesis methods and catalytic mechanisms will also be discussed. Finally, we give a prospective outlook on the future of TiO 2 nanotubes for photoelectrochemical applications and identify areas for future research.

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Got TiO₂ Nanotubes? Lithium Ion Intercalation Can Boost Their Photoelectrochemical Performance

Cited by 260 publications

References 66 publications

Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Nature of N 2p, Ti 3d, O 2p Hybridization of N‐Doped TiO₂ Nanotubes and Superior Photovoltaic Performance through Selective Atomic N Doping

Titania Nanotubes by Electrochemical Anodization for Solar Energy Conversion

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Got TiO2 Nanotubes? Lithium Ion Intercalation Can Boost Their Photoelectrochemical Performance

Cited by 260 publications

References 66 publications

Electrochemical Performance of Anatase TiO2Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Electrochemical Performance of Anatase TiO2Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Nature of N 2p, Ti 3d, O 2p Hybridization of N‐Doped TiO2 Nanotubes and Superior Photovoltaic Performance through Selective Atomic N Doping

Titania Nanotubes by Electrochemical Anodization for Solar Energy Conversion

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Got TiO₂ Nanotubes? Lithium Ion Intercalation Can Boost Their Photoelectrochemical Performance

Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Electrochemical Performance of Anatase TiO₂Nanotube Arrays Electrode in Ionic Liquid Based Electrolyte for Lithium Ion Batteries

Nature of N 2p, Ti 3d, O 2p Hybridization of N‐Doped TiO₂ Nanotubes and Superior Photovoltaic Performance through Selective Atomic N Doping