Percolating networks of TiO2 nanorods and carbon for high power lithium insertion electrodes

Bresser, Dominic; Paillard, Elie; Binetti, Enrico; Krueger, Steffen; Striccoli, Marinella; Winter, Martin; Passerini, Stefano

doi:10.1016/j.jpowsour.2011.12.051

Cited by 86 publications

(76 citation statements)

References 52 publications

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“…This value is a little higher than for hard carbon-based electrodes, 6 which might be related to a catalytic effect of titanium oxide. 52 After this plateau-like feature, the potential decrease is again very sloped and no significant additional feature is observed. The series of XRD scans performed simultaneously with the galvanostatic discharge clearly reveals that the crystallinity of the active material decreases upon discharge (sodiation) and finally completely vanishes at the end of the discharge process (Figure 4b).…”

Section: 42mentioning

confidence: 96%

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Wu¹,

Bresser²,

Buchholz³

et al. 2014

J. Electrochem. Soc.

Self Cite

110

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High surface area, nanostructured, and phase-pure TiO 2 (B) noodles-like secondary particles were successfully synthesized by a facile one-pot synthesis, based on the hydrolysis of TiCl 3 using a mixture of ethylene glycol and water at moderate temperature. The primary nanoparticles have a uniform size and are about 15 nm in diameter as determined by TEM analysis and exhibit an increased exposure of the (010) facet as indicated by XRD analysis. Unlike the electrochemical reaction with lithium, the application as sodiumion electrode material reveals substantial differences, including the initial amorphization of the TiO 2 (B) particles, accompanied by a partial irreversibility of the sodium storage, presumably related to sodium trapping inside the active material particles and the absence of a stable solid electrolyte interphase, as indicated by galvanostatic cycling and electrochemical impedance spectroscopy, respectively. Besides, TiO 2 (B)-based electrodes show a stabilized reversible capacity of about 100 mAh g −1 and a very good C rate capability. While sodium-ion batteries were initially considered only as lowcost alternative for lithium-ion batteries with a particular focus on their application as stationary energy storage devices, 1-3 recent developments indicated that such devices might provide even similar energy densities in case suitable cathode and anode active materials are combined. [4][5][6] However, particularly regarding the anode side, the identification of long-term stable, environmentally friendly, and abundant active materials, providing high specific capacities and operating at a reasonably low potential, is still considered to be one of the major challenges for this technology. 4,6,7 47 Among these, the best results in terms of specific capacity, long-term cycling stability, and high rate capability were certainly reported for anatase TiO 2 . [40][41][42][43] However, the reversible sodium storage mechanism is obviously different from the classic (de-)insertion mechanism known for lithium, [48][49][50][51][52][53] as an initial reduction of TiO 2 to metallic titanium and an amorphous sodium titanate occurs. 42 TiO 2 (B) is a very well performing anode material for lithium-ion applications, 54-60 but so far -to the best of our knowledge -only one study reported its application as sodium-ion active material. The electrochemical performance, which might be best described by a rather rapid initial capacity fading and a low reversible capacity of about 50 mAh g −1 , is certainly not that promising, 47 although this might be also related to the cut-off potentials of 3.0 and 0.8 V vs. Na/Na + . Besides, the authors observed a rather huge expansion of the (001) 3+ and Ti 4+ at the nanotubes surface, while the general morphology of the tubes remained after sodiation. Consequently, a solid solution mechanism for the reversible sodium ion (de-)insertion comparable to the lithium ion storage mechanism was proposed.Herein, however, we show that TiO 2 (B) -similarly to anatase TiO 2 -presents a rath...

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Section: 42mentioning

confidence: 96%

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Wu¹,

Bresser²,

Buchholz³

et al. 2014

J. Electrochem. Soc.

Self Cite

110

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“…The low-columbic efficiency often displayed by high-surface TiO 2 materials is typically ascribed to SEI (Bresser et al, 2012), the formation of which can only be prevented above 1.2 V vs. Li/Li + as been shown for high-surface anatase TiO 2 nanorods (Bresser et al, 2012). This indicates that the SEI will be formed under the present conditions, galvanostatic cycling with a lower cut-off voltage of 0.8 V vs. Li/Li + .…”

Section: Frontiers In Energy Researchmentioning

confidence: 56%

Improving Reversible Capacities of High-Surface Lithium Insertion Materials â€“ The Case of Amorphous TiO2

et al. 2014

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Chemisorbed water and solvent molecules and their reactivity with components from the electrolyte in high-surface nano-structured electrodes remains a contributing factor toward capacity diminishment on cycling in lithium ion batteries due to the limit in maximum annealing temperature. Here, we report a marked improvement in the capacity retention of amorphous TiO 2 by the choice of preparation solvent, control of annealing temperature, and the presence of surface functional groups. Careful heating of the amorphousTiO 2 sample prepared in acetone under vacuum lead to complete removal of all molecular solvent and an improved capacity retention of 220 mAh/g over 50 cycles at a C/10 rate. Amorphous TiO 2 when prepared in ethanol and heated under vacuum showed an even better capacity retention of 240 mAh/g. From Fourier transform infra-red spectroscopy and electron energy loss spectroscopy measurements, the improved capacity is attributed to the complete removal of ethanol and the presence of very small fractions of residual functional groups coordinated to oxygen-deficient surface titanium sites. These displace the more reactive chemisorbed hydroxyl groups, limiting reaction with components from the electrolyte and possibly enhancing the integrity of the solid electrolyte interface. The present research provides a facile strategy to improve the capacity retention of nano-structured electrode materials.

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“…In fact, recent reports demonstrated the formation of a solid electrolyte interphase (SEI) on the particle surface and eventually may lead to the structural degradation of the electrode at low cutoff potentials. 66,[72][73][74] Interestingly, the electrochemical profiles obtained in the 50 th cycle for all the prepared electrodes (Fig. 5b) reveals a new behavior at the charging potential of 2.8 V and becomes more pronounced on prolonged cycling (not shown here).…”

Section: Resultsmentioning

confidence: 76%

“…The pronounced sloping profile leading to higher specific capacities in nanostructured materials is generally caused by pseudo-capacitive reaction with lithium. [64][65][66]69,71 Furthermore, the over-potential observed at the onset of the charge plateau is specific to the 600…”

Section: Resultsmentioning

confidence: 98%

A Porous TiO₂Electrode Prepared by an Energy Efficient Pyro-Synthesis for Advanced Lithium-Ion Batteries

Mathew

Gim

Alfaruqi

et al. 2015

J. Electrochem. Soc.

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Anatase-type titanium dioxide (TiO 2 ) anodes were prepared by a polyol-assisted pyro-synthetic process followed by mild annealing at temperatures in the range of 300 to 600 • C for 3 h. The XRD studies clearly revealed the formation of anatase-type TiO 2 for all of the prepared samples. The average crystallite size, calculated using the Scherrer formula, was determined to be less than 50 nm in all samples. Electron microscopy studies revealed that the particle-size in all samples ranged from 5 to 50 nm. N 2 adsorption studies confirmed that the samples show mesoporous characteristics and in particular the TiO 2 anode prepared at 500 • C demonstrated a unique tri-porous feature that appears to benefit its electrochemical performances vs. lithium. Although there is no order of variation in the particle-size of the samples prepared at temperatures under 600 • C, the tri-porous feature in combination with the sufficiently high particle crystallinity in the TiO 2 anode prepared at 500 • C appears to contribute to its impressive electrochemical lithium storage properties among the prepared electrodes. The pyro-synthetic strategy aids in developing nanostructured battery electrodes with porous morphologies and appears to offer promise for being developed as an energy saving process for large-scale applications. Rechargeable Li-ion batteries (LIBs) are state-of-the-art devices in the field of electrochemical energy storage due to their high energy densities and extensive usage for a wide range of applications, including portable electronics, electric vehicles, stationary storage, and medical devices.1-5 However, their short cycle-life and safety issues due to rapid charging, charging at low temperatures, and lithium plating on graphite remain as obstacles to the realization of next generation LIBs. 6,7 In particular, the use of graphite anodes limits the performance and increases the safety risks of the current LIBs. Since their electrochemical properties and safety issues are critically dependent on the electrode materials, much effort has been made to develop alternative anodes based on transition metal oxides in an attempt to produce safer LIBs exhibiting higher performance. [8][9][10][11][12][13][14][15][16][17][18] In this regard, anatase-type TiO 2 anodes with a relatively high voltage potential (∼1.7 V) vs. Li/Li + , high capability, thermodynamic stability, low safety risks, and costs have been widely investigated.15-21 Despite these advantages, the low electronic conductivity and lithium diffusivity within the lattice restricts the application of TiO 2 as a high-power anode.22-24 For instance, the theoretical specific capacity of TiO 2 is high (335 mAh g −1 ); however, in reality, only 0.5 mol lithium (equivalent to a specific capacity of 168 mAh g −1 ) is reversibly inserted per formula unit of TiO 2 consisting of micro-sized particles. The established strategy to overcome this drawback is to develop composite/coating with metals (Cu, Sn, Ag, Au), metal oxides (SnO, SnO 2 , RuO 2 ) and carbonaceous materials ...

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Percolating networks of TiO2 nanorods and carbon for high power lithium insertion electrodes

Cited by 86 publications

References 52 publications

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Improving Reversible Capacities of High-Surface Lithium Insertion Materials â€“ The Case of Amorphous TiO2

A Porous TiO₂Electrode Prepared by an Energy Efficient Pyro-Synthesis for Advanced Lithium-Ion Batteries

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Percolating networks of TiO2 nanorods and carbon for high power lithium insertion electrodes

Cited by 86 publications

References 52 publications

Nanocrystalline TiO2(B) as Anode Material for Sodium-Ion Batteries

Nanocrystalline TiO2(B) as Anode Material for Sodium-Ion Batteries

Improving Reversible Capacities of High-Surface Lithium Insertion Materials â€“ The Case of Amorphous TiO2

A Porous TiO2Electrode Prepared by an Energy Efficient Pyro-Synthesis for Advanced Lithium-Ion Batteries

Contact Info

Product

Resources

About

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

A Porous TiO₂Electrode Prepared by an Energy Efficient Pyro-Synthesis for Advanced Lithium-Ion Batteries