Prussian blue without coordinated water as a superior cathode for sodium-ion batteries

Yang, Dezhi; Xu, Jun; Liao, Xiao‐Zhen; Wang, Hong; He, Yu‐Shi; Ma, Zi-Feng

doi:10.1039/c5cc01180a

Cited by 154 publications

(123 citation statements)

References 31 publications

(37 reference statements)

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“…[28][29][30][31][32] However, more detailed investigation into this phase was not attempted and is left for future studies. These XRD results indicate that M-Na 2 Fe 2 (CN) 6 .2H 2 O is a metastable phase in ambient air.…”

Section: Redoxmentioning

confidence: 99%

“…[24][25][26][27] Most of the PBAs which have been reported to store sodium have less Na content in the as-synthesized compounds (0 ≤ x ≤ 1) demonstrating a cubic structure with a space group Fm-3m. [28][29][30][31][32][33] This may become a disadvantage in a full cell formulation against a suitable anode as a full cell relies on the cathode supplying Na during the first charging (sodium extraction from cathode and insertion into the anode). An x = 1 value would mean that the practically achieved capacity of such a cathode would be half of its theoretical capacity (corresponding to the capacity for an analogous cathode with x = 2) in a practical full cell assuming no loss of Na due to surface passivation and 100% coulombic efficiency for both cathode and anode.…”

mentioning

confidence: 99%

“…[28][29][30][31][32][33][34][35][36][37][38] Goodenough et al synthesized Na rich PBAs with x ≈ 2 at an elevated temperature of 140…”

mentioning

confidence: 99%

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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.

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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Section: Redoxmentioning

confidence: 99%

mentioning

confidence: 99%

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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.

103

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“…[ 212,213,[229][230][231][232] The general formula of PBAs can be described as A x P[R(CN) 6 ] 1-y ·ٗ y ·mH 2 O (A: alkali metal ion; P: N-coordinated transition metal ion; R: C-coordinated transition metal ion; ٗ: [R(CN) 6 ] vacancy; 0 ≤ x ≤ 2; 0 ≤ y ≤ 1). PBAs generally adopt a face-centered cubic structure with a space group of Fm3m , where transition metal ions are connected by (CN) ligands forming large cage-like interstitial A sites (see Figure 9 d).…”

Section: Prussian Blue Analoguesmentioning

confidence: 99%

Recent Progress in Electrode Materials for Sodium‐Ion Batteries

Kim

Zhang

et al. 2016

Advanced Energy Materials

850

592

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Grid‐scale energy storage systems (ESSs) that can connect to sustainable energy resources have received great attention in an effort to satisfy ever‐growing energy demands. Although recent advances in Li‐ion battery (LIB) technology have increased the energy density to a level applicable to grid‐scale ESSs, the high cost of Li and transition metals have led to a search for lower‐cost battery system alternatives. Based on the abundance and accessibility of Na and its similar electrochemistry to the well‐established LIB technology, Na‐ion batteries (NIBs) have attracted significant attention as an ideal candidate for grid‐scale ESSs. Since research on NIB chemistry resurged in 2010, various positive and negative electrode materials have been synthesized and evaluated for NIBs. Nonetheless, studies on NIB chemistry are still in their infancy compared with LIB technology, and further improvements are required in terms of energy, power density, and electrochemical stability for commercialization. Most recent progress on electrode materials for NIBs, including the discovery of new electrode materials and their Na storage mechanisms, is briefly reviewed. In addition, efforts to enhance the electrochemical properties of NIB electrode materials as well as the challenges and perspectives involving these materials are discussed.

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“…Yang et al employed an effective heat-treatment method to remove such coordinated water from the PBA framework via charge transfer between the PBA particles and graphene oxide, which can show a high specific capacity of 163.3 mA h g −1 at 30 mA g −1 , and high cycling stability (91.9% retention at 200 mA h g −1 over 500 cycles) and rate performance (112 mA h g −1 at 800 mA h g −1 ). [190] Alkali-rich Prussian White (Na 2 M[M(CN)] 6 ), developed by the Sharp Lab of America, is regarded as a promising alternative for SIB cathodes, which, unlike PBAs, has Na + occupied in all cubic cavities, which hence increases the first-cycle Coulombic efficiency. [191,192] To date, a range of Prussian White variants with different phases have been developed for low-cost SIB cathodes.…”

Section: Metal-organic Compoundsmentioning

confidence: 99%

Advanced Cathode Materials for Sodium‐Ion Batteries: What Determines Our Choices?

et al. 2017

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lithium with cheaper alternatives might make future batteries less susceptible to price fluctuations when the market expands. [5] This concern has in turn spawned a flurry of research activity to look beyond LIB technology. In view of the various rechargeable batteries, sodiumion batteries (SIBs) that consist of a main element of seawater made their presence felt in the battery industry due to their chemical similarity (e.g., only 0.3 V more positive than lithium) but higher abundance compared to lithium, [6] as illustrated in Table 1. SIBs work in the same way as LIBs in that they involve the reversible migration of cations/anions across a separator toward the electrodes to realize voltage-driven electrochemical reactions. [7] The upward trend for sodium-ion battery research is driven by the concern over the scarcity and price rise of lithium. Hence, these major merits, as well as the suitable redox potential (E = 0.3 V vs Li) make the SIB an appropriate choice as a rechargeable battery system.In fact, SIBs started almost in parallel with LIBs in the 1980s but the development of LIBs eventually eclipsed SIBs due to the electrochemical performances of SIBs. [8,9] A major obstacle is that it is difficult to get a sodium host material with comparable operating voltage and capacity as the LIB analogs. Firstly, the larger Na + radius (0.98 Å) than that of Li + (0.69 Å) leads to the kinetically sluggish Na + insertion/extraction and transport cross the host-material framework, which will always make the specific capacity and rate capacity largely degraded. [10] Secondly, the larger volume expansion caused by Na + insertion will also bring a change in the phase and lattice of the host materials, making it difficult to achieve a favorable electrochemical stability compared with the LIB counterparts. [11] In addition, they also suffer from a lower specific energy than LIBs, due to the lower potential and larger atomic weight of sodium. It is still a challenge to build an affordable Na-host materials endowed with a high specific energy (e.g., 500 W h kg −1 in LIBs). [12] Recently, the topic of SIBs was revisited in the hope of exploring possible ways to overcome the concerns about the low energy density and poor cycling life of SIBs.In spite of the above distinct drawbacks, SIBs can actually behave slightly differently in some chemical aspects. For instance, sodium does not react with aluminum, which is contrary to the alloying tendency of lithium. In the commercial market, manufacturers could appreciate this "inertness" to reduce the production cost of batteries by substituting the Among the various energy solutions, lithium-ion batteries (LIBs) play an important role in the process of the transition from fossil fuels to renewables. However, the necessity to replace lithium with cheaper alternatives due to its scarcity has recently attracted great interest to developing sodium-ion batteries (SIBs). Hence, the discovery and development of suitable cathode materials that exhibit high specific capacity, good cycling stabil...

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Prussian blue without coordinated water as a superior cathode for sodium-ion batteries

Cited by 154 publications

References 31 publications

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

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

Recent Progress in Electrode Materials for Sodium‐Ion Batteries

Advanced Cathode Materials for Sodium‐Ion Batteries: What Determines Our Choices?

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