Introducing a 0.2 V sodium-ion battery anode: The Na2Ti3O7 to Na3−xTi3O7 pathway

Rudola, Ashish; Sharma, Neeraj; Balaya, Palani

doi:10.1016/j.elecom.2015.09.016

Cited by 65 publications

(61 citation statements)

References 20 publications

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“…For the CV curves of S‐NTO shown in Figure a, the broad peak at around 0.5 V in cathodic process of the initial cycle is ascribed to electrolyte decomposition to form the solid electrolyte interphase (SEI) layer, and these peaks disappear in the following cycles due to the irreversible reaction . The peak centred at 0.8 V is due to the sodium‐ion insertion into Na 2 Ti 3 O 7 along with the reduction of Ti 4+ to Ti 3+ . This peak shifts to 0.85 V in the subsequent cycles, probably stemmed from reduced overpotential for the reversible sodium storage .…”

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confidence: 98%

“…The S‐NTO electrode delivers a discharge capacity of 457 mAh g −1 and charge capacity of 250 mAh g −1 at 1 C (1 C = 177 mA g −1 , referring to 2 sodium ions inserted into NTO in 1 h) in the first cycle, corresponding to a coulombic efficiency of 54.7%, which is higher than that of C‐NTO (50.2%) and NTO (43.0%). Their low first cycle coulombic efficiencies are attributed to the irreversible formation of the SEI layer …”

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Boosting Sodium Storage of Double‐Shell Sodium Titanate Microspheres Constructed from 2D Ultrathin Nanosheets via Sulfur Doping

Wang

Liao

et al. 2018

Advanced Materials

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with abundant natural resources, much lower cost, and ubiquitous presence around the globe. Therefore, sodiumion batteries (SIBs) are expected to be the most promising candidates as nextgeneration batteries. [1,2] The commercial LIB anode (graphite), however, exhibits extremely poor sodium storage (capacity of only 31 mAh g −1 ) in ester-based electrolytes, and has a low insertion voltage (close to 0 V, which easily causes sodium plating and arouses safety concerns), which largely restricts it in practical use in SIBs. [2][3][4] Alloying and conversion-type materials also suffer from huge volume changes during cycling that will lead to electrode pulverization and thus capacity fading. [5][6][7] Therefore, searching for suitable anodes with high capacity, long cycling stability, and high rate capability is the critical issue for bringing SIBs into practical application.As a typical Ti-based compound, sodium titanate (Na 2 Ti 3 O 7 ) comprises zigzag layers of titanium and oxygen octahedral, where 3.5 Na ions per formula unit can be easily inserted into the interlayer space, resulting in a capacity of 310 mAh g −1 . [8] In addition, Na 2 Ti 3 O 7 displays the lowest average Na intercalation potential (0.3 V for Na + insertion, but above the voltage for the formation of Na dendrites) compared to the reported insertion-type oxides, which is beneficial for achieving high operating voltage and energy density in full batteries. [9,10] In particular, the large interlayered spacing of ≈0.83 nm is favorable for the charge storage properties and the diffusion of electrolyte ions. [11][12][13][14] Notwithstanding, there are still some shortcomings of Na 2 Ti 3 O 7 anode [15][16][17][18][19] : i) the low electronic conductivity caused by the large bandgap (3.7 eV) results in ineffective charge transport and thus limits the rate performance of SIBs; [8][9][10][11] ii) the aggregation and overlapping of Na 2 Ti 3 O 7 layers due to the large surface energy leads to fast capacity decay during Na + insertion/extraction; [15] and iii) the stability and lifetime concerns aroused by the volume expansion upon Na uptake are still an obstacle to the use of Na 2 Ti 3 O 7 in large-scale SIB application. [8] To address these issues, a series of effective strategies have been developed, including widening the interlayer spacing of Na 2 Ti 3 O 7 , [16] regulating the morphology on the nanoscale, [8,10,12] and using carbonaceous materials as a conductive matrix. [14,17] Sodium-ion batteries (SIBs) have drawn remarkable attention due to their low cost and the practically inexhaustible sodium sources. The major obstacle for the practical application of SIBs is the absence of suitable negative electrode materials with long cycling stability and high rate performance. Here, sulfur-doped double-shell sodium titanate (Na 2 Ti 3 O 7 ) microspheres constructed from 2D ultrathin nanosheets are synthesized via a templating route combined with a low-temperature sulfurization process. The resulting double-shell microspheres deliver a high specific capaci...

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confidence: 98%

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confidence: 99%

Boosting Sodium Storage of Double‐Shell Sodium Titanate Microspheres Constructed from 2D Ultrathin Nanosheets via Sulfur Doping

Wang

Liao

et al. 2018

Advanced Materials

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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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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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“…The exceptionally low sodium storage potential was due to the structural instability of the Na intercalated compound from the calculation of the electrostatic interaction in the structure [278]. And the charge/discharge profile was notably changed depending on the discharge cutoff voltage of the electrode, which was associated with the appearance of an intermediate phase [279]. Casas-Cabanas and co-workers discovered that the SEI formed upon discharge was unstable during electrochemical cycling, resulting in poor cycling stability [280].…”

Section: Ti-based Materialsmentioning

confidence: 99%

Recent Advances in Sodium-Ion Battery Materials

Fang

Xiao

Chen

et al. 2018

Electrochem. Energ. Rev.

255

142

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Grid-scale energy storage systems with low-cost and high-performance electrodes are needed to meet the requirements of sustainable energy systems. Due to the wide abundance and low cost of sodium resources and their similar electrochemistry to the established lithium-ion batteries, sodium-ion batteries (SIBs) have attracted considerable interest as ideal candidates for grid-scale energy storage systems. In the past decade, though tremendous efforts have been made to promote the development of SIBs, and significant advances have been achieved, further improvements are still required in terms of energy/ power density and long cyclic stability for commercialization. In this review, the latest progress in electrode materials for SIBs, including a variety of promising cathodes and anodes, is briefly summarized. Besides, the sodium storage mechanisms, endeavors on electrochemical property enhancements, structural and compositional optimizations, challenges and perspectives of the electrode materials for SIBs are discussed. Though enormous challenges may lie ahead, we believe that through intensive research efforts, sodium-ion batteries with low operation cost and longevity will be commercialized for large-scale energy storage application in the near future.

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Introducing a 0.2 V sodium-ion battery anode: The Na2Ti3O7 to Na3−xTi3O7 pathway

Cited by 65 publications

References 20 publications

Boosting Sodium Storage of Double‐Shell Sodium Titanate Microspheres Constructed from 2D Ultrathin Nanosheets via Sulfur Doping

Boosting Sodium Storage of Double‐Shell Sodium Titanate Microspheres Constructed from 2D Ultrathin Nanosheets via Sulfur Doping

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

Recent Advances in Sodium-Ion Battery Materials

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