Na2Ti3O7: an intercalation based anode for sodium-ion battery applications

Rudola, Ashish; Kuppan, Saravanan; Mason, C. W.; Balaya, Palani

doi:10.1039/c2ta01057g

Cited by 397 publications

(331 citation statements)

References 39 publications

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“…6 Several layered titanates have recently been shown to undergo reversible reductive intercalation of both lithium and sodium ions. 7,8,9,10,11 Some of these electrode materials, which have theoretical capacities in excess of 200 mAh/g, insert alkali metal cations at unusually low potentials (below 0.5V in some cases). These characteristics have important implications for the design of high-energy dual intercalation batteries, particularly when the intercalant is sodium.…”

Section: Introductionmentioning

confidence: 99%

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

2014

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The electrochemical characteristics of lepidocrocite-type titanates derived from K 0.8 Ti 1.73 Li 0.27 O 4 are presented for the first time. By exchanging sodium ions for potassium, the practical specific capacity of the titanate in both sodium and lithium half cells is considerably enhanced. Although the gross structural features of the titanate framework are maintained during the ion exchange process, the symmetry changes because sodium occupies different sites from potassium. The smaller size of the sodium ion compared to potassium and the change in site symmetry allow more alkali metal cations to be inserted reversibly into the structure during discharge in sodium and lithium cells than in the parent compound. Insertion of lithium cations takes place at an average of about 0.8V vs. Li + /Li while sodium intercalation occurs at 0.5V vs. Na + /Na, with sloping voltage profiles exhibited for both cell configurations, implying singlephase processes. Ex situ synchrotron X-ray diffraction measurements show that a lithiated 2 lepidocrocite is formed during discharge in lithium cells, which undergoes further lithium insertion with almost no volume change. In sodium cells, insertion of sodium initially causes an overall expansion of about 12% in the b lattice parameter but reversible uptake of solvent minimizes changes upon further cycling. In the case of the sodium cells, both the practical capacity and the cyclability are improved when a more compliant binder (polyacrylic acid) that can accommodate volume changes associated with insertion processes is used in place of the more common polyvinylidene fluoride. The ability to tune the electrochemical properties of lepidocrocite titanate structures by varying compositions and utilizing ion exchange processes make them especially versatile anode materials for both lithium and sodium ion battery configurations.

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Section: Introductionmentioning

confidence: 99%

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

2014

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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.…”

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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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“…[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 So far, research activities basically focused on hard carbons, [8][9][10][11][12][13][14] organic compounds like sodium terephthalate or carboxylates, [15][16][17][18] alloying materials such as Sn, [19][20][21][22][23][24][25][26][27] Sb, 28,29 or Ge, 30 conversion materials, [31][32][33][34] or titanium-based insertion materials like Na 2 Ti 3 O 7 [35][36][37] or Li 4 Ti 5 O 12. 38 Generally, insertion materials offer substantial advantages compared to alloying or conversion materials with respect to safety issues, long-term cycling stability, and frequently also environmental friendliness as well as natural abundance.…”

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confidence: 99%

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

Wu¹,

Bresser²,

Buchholz³

et al. 2014

J. Electrochem. Soc.

111

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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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Na2Ti3O7: an intercalation based anode for sodium-ion battery applications

Cited by 397 publications

References 39 publications

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

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

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

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Na2Ti3O7: an intercalation based anode for sodium-ion battery applications

Cited by 397 publications

References 39 publications

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

Lepidocrocite-type Layered Titanate Structures: New Lithium and Sodium Ion Intercalation Anode Materials

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

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

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