Na2Ti6O13: a potential anode for grid-storage sodium-ion batteries

Rudola, Ashish; Kuppan, Saravanan; Devaraj, S.; Gong, Hao; Balaya, Palani

doi:10.1039/c3cc44381g

Cited by 195 publications

(199 citation statements)

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“…The main issues encountered with anode materials are (a) low capacity in case of insertion-type compounds, (b) large volume changes in case of both insertion as well as alloying reactions, (c) poor cycling performance of conversion-type materials, and (d) sodium plating at low voltages. In the literature, sodium storage in the conversion reaction-based systems involving binary [3][4][5] and ternary oxides [6] were explored as alternative to the insertion [7,8] and alloying [9,10] based compounds. We embarked on a comprehensive program on search for new anode materials in the ternary oxide regime containing sodium in the lattice via conversion reactions.…”

Section: Introductionmentioning

confidence: 99%

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Verma

Raman

Varadaraju

2016

J Solid State Electrochem

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Na 2 Mo 2 O 7 was synthesized by solid-state reaction route and explored as possible anode material for sodium ion battery for the first time. The electrochemical reaction with sodium involves an initial insertion of 0.33 Na/f.u into the lattice followed by conversion reaction. The material shows good reversibility and high rate capability. A reversible capacity of ∼200 mAh g −1 is obtained after 50 cycles. The presence of lattice sodium facilitates reversible sodiation/de-sodiation.

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Section: Introductionmentioning

confidence: 99%

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Verma

Raman

Varadaraju

2016

J Solid State Electrochem

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“…Despite such harsh demands, there have been a few promising NIB electrode materials reported which meet most of the above requirements for grid-storage batteries. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Among them, there is a class of cathodes belonging to the Prussian Blue Analogue (PBA) family which is very appealing due to its reliance on Fe and/or Mn as the redox active centers and possession of high sodium storage capacities (theoretical capacity limit as high as 170.8 mAh g −1 assuming two mole sodium storage per mole of material) at relatively high voltages. 23 The general formula for PBAs relevant for NIBs is Na x M 1 [M 2 (CN) 6 ] 1-y y .nH 2 O with 0 ≤ x ≤ 2 and 0 ≤ y < 1.…”

mentioning

confidence: 99%

Monoclinic Sodium Iron Hexacyanoferrate Cathode and Non-Flammable Glyme-Based Electrolyte for Inexpensive Sodium-Ion Batteries

Rudola

Balaya

2017

J. Electrochem. Soc.

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103

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One of the key requirements of large-scale grid-storage systems is development of inexpensive and safe batteries. Sodium-ion batteries using earth-abundant Fe or Ti based cathodes and anodes would be ideal candidates for such storage systems. Herein, a new phase of Na-rich and all Fe Prussian Blue Analogue, monoclinic Na2Fe2(CN)6.2H2O, is reported as a potential cathode for such grid-storage sodium-ion batteries. This water-insoluble and air-stable cathode can deliver 85 mAh g−1 at an average discharge voltage of 3 V vs Na/Na+ with excellent cycle life (3,000 cycles). Many facets about its sodium storage characteristics are discussed with particular emphasis on the role of interstitial water on the sodium storage performance and its conversion to the dehydrated rhombohedral phase. Its compatibility with a newly developed non-flammable glyme-based liquid electrolyte, 1M NaBF4 in tetraglyme, is also disclosed along with general electrochemical and thermal characterization of this electrolyte for sodium-ion battery application. Finally, three different types of full cells are revealed with either monoclinic or rhombohedral phase as cathode and graphite or the recently reported Na2Ti3O7 ⇋ Na3-xTi3O7 pathway of Na2Ti3O7 as anode. Full cell energy densities of 70–90 Wh kg−1 (using cumulative cathode and anode weights) could be obtained without any pre-cycling steps. This new cathode and safe electrolyte may hold great promise toward development of inexpensive, non-flammable and highly stable grid-storage sodium-ion batteries.

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“…2a and c. framework is often not affected by such an exchange [31,32]. Thus, for a detailed analysis of the Li/Na ratio, the spectral region up to 350 cm Figure 4 shows the theoretical prediction of Raman modes for Na 2 Ti 6 O 13 (Figure 4a) and Li 2 Ti 6 O 13 (Figure 4b tions between theory and experiment are in the range observed for other compounds in a previous study on Na 8 [AlSiO 4 ] 6 (BH 4 ) 2 [27]. Small deviations could arise from the fact that a powder is measured and its surface is not perfectly plain.…”

Section: Resultsmentioning

confidence: 69%

“…Another topic is the change of the cation, i.e. turning to sodium [8]. For example, TiO 2 or Na 2 Ti 3 O 7 seem to be excellent candidates as Na hosts [9,10].…”

Section: Introductionmentioning

confidence: 99%

Lattice Vibrations to Identify the Li/Na Ratio in Li_xNa_2−xTi₆O₁₃ (x = 0…2)

Volgmann¹,

Schulz²,

Welsch³

et al. 2015

Zeitschrift Für Physikalische Chemie

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Li x Na 2−x Ti 6 O 13 has received attention as 3 -metal oxide based anode material for possible battery application. Generally, titanium oxides represent excellent Li hosts due to their zero-strain behavior, cycling stability and high operating voltage. New developments choose Na as charge carrier, but less effort is put in the investigation of mixed cation conductors. Owing to the synthesis route of Li x Na 2−x Ti 6 O 13 (0 ≤ ≤ 2) the coordination of Na and Li in the channels is different which had been investigated by means of X-ray and neutron diffraction. Up to now, no Raman spectroscopy has been applied. This oxide is highly Raman-active, thus the local structure can also be analyzed in terms of vibrational spectroscopy. Micro-Raman spectroscopy carried out at room temperature with different cation contents ( = 0, 0.33, 1, 2) shows the continuous change from Na to Li by a superposition of the modes for Na 2 Ti 6 O 13 and Li 2 Ti 6 O 13 . The only exceptions are two distinct modes. They appear either for Li (118 cm −1 ) or Na (135 cm −1 ). The results confirm the high-temperature phase stability of Na 2 Ti 6 O 13 as well as the anisotropic thermal expansion of the unit cell seen by in situ X-ray powder diffrac- tion under two different gas atmospheres. Combining these results, we suppose that the anisotropic thermal expansion of the lattice parameters is affected by the normal vectors of the corresponding bond vibrations in Na 2 Ti 6 O 13 and Li 2 Ti 6 O 13 . Crystalline-orbital calculations of the Raman shifts of Li x Na 2−x Ti 6 O 13 were carried out for the cation contents = 0, 1, 2 and Raman modes were assigned to specific bond vibrations supported by theory. Besides, this gives additionally information about the Li/Na ratio in a new and simple way.

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Na2Ti6O13: a potential anode for grid-storage sodium-ion batteries

Abstract: The ultra-fast (30C or 2 min) rate capability and impressive long cycle life (>5000 cycles) of Na2Ti6O13 are reported. A stable 2.5 V sodium-ion battery full cell is demonstrated. In addition, the sodium storage mechanism and thermal stability of Na2Ti6O13 are discussed.

Cited by 195 publications

References 19 publications

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Monoclinic Sodium Iron Hexacyanoferrate Cathode and Non-Flammable Glyme-Based Electrolyte for Inexpensive Sodium-Ion Batteries

Lattice Vibrations to Identify the Li/Na Ratio in Li_xNa_2−xTi₆O₁₃ (x = 0…2)

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Na2Ti6O13: a potential anode for grid-storage sodium-ion batteries

Abstract: The ultra-fast (30C or 2 min) rate capability and impressive long cycle life (>5000 cycles) of Na2Ti6O13 are reported. A stable 2.5 V sodium-ion battery full cell is demonstrated. In addition, the sodium storage mechanism and thermal stability of Na2Ti6O13 are discussed.

Cited by 195 publications

References 19 publications

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Disodium dimolybdate: a potential high-performance anode material for rechargeable sodium ion battery applications

Monoclinic Sodium Iron Hexacyanoferrate Cathode and Non-Flammable Glyme-Based Electrolyte for Inexpensive Sodium-Ion Batteries

Lattice Vibrations to Identify the Li/Na Ratio in Li x Na2−x Ti6O13 (x = 0…2)

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Lattice Vibrations to Identify the Li/Na Ratio in Li_xNa_2−xTi₆O₁₃ (x = 0…2)