In Situ FT-IR/ATR Spectroelectrochemistry of Prussian Blue in the Solid State

Kulesza, Paweł J.; Malik, Marcin A.; Deńca, Andrzej; Strojek, Jerzy W.

doi:10.1021/ac950380k

Cited by 145 publications

(109 citation statements)

References 32 publications

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“…41 To ascertain which Fe partakes in the low (3.0-3.3 V) and high (4.0 V) voltage plateaus witnessed during galvanostatic cycling, ex-situ FTIR measurements were conducted at relevant states of charge and discharge to follow the cyanide stretching vibration band as it is a sensitive indicator of the Fe oxidation state in such PBAs. 25,[45][46][47] Within the 3.9-2.0 V window, the cyanide stretching bands shift from 2072 cm −1 for the pristine state to 2078 cm −1 for the cathode charged to 3.9 V and then it shifts back to 2072 cm −1 when discharged to 2.0 V (see Figure 3d). The stretching band at 2078 cm −1 agrees well with the band at 2076 cm −1 reported for Na 0.75 Fe 2.08 (CN) 6 , indicating that one of the Fe 2+ has been oxidized to Fe 3+ .…”

Section: Redoxmentioning

confidence: 96%

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: 96%

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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“…The sandwich geometries and the interdigitated array (IDA) electrode systems [9,11,13,38,44,66,70,71] often have been used to inspect the dynamics of charge propagation in mixed-valence electron-hopping materials. The simplest sandwich design is constructed from two opposing plane parallel electrodes (Fig.…”

Section: Electrochemical Cellsmentioning

confidence: 99%

Solid-State Voltammetry — Analytical Prospects

Kulesza¹,

Cox

1998

Electroanalysis

Self Cite

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The present review discusses some current issues related to the principles and analytical aspects of electrochemical studies (typically done at room temperature) of solid, rigid or semirigid (nonfluid) systems in the absence of a liquid solution phase. Representative examples include redox and conducting organic polymers, melts and solid solutions of redox centers in solid ionic conductors, mixed-valence polynuclear inorganic materials, transition metal salts, oxides, and zeolites. The emphasis is on the elements of dynamics for the efficient delivery of charge and on reactivity of the 'redox conducting' materials. The effective (apparent) diffusional mechanism is critical to the success of most analytical measurements in solidstate. Also described are typical electrochemical cells and experimental tactics to overcome the relatively slow dynamics of transport in solid (nonfluid) systems. Application of microdimensional electrodes leads to an improvement in the quality of solid-state electrochemical data and provides new diagnostic and analytical possibilities. Results of mechanistic studies, which are relevant to the development of novel analytical methods, together with trends towards possible future applications also are discussed.

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“…For both samples, a similar peak near 2090 cm -1 was observed. This band belongs to the characteristic of stretching vibration of Fe-CN-Ni [87]. Therefore, the PXRD and FT-IR investigations confirm that both 1 cube and 1 frame present the same crystal structure and composition, allowing us to explore the mesostructural property.…”

Section: Resultsmentioning

confidence: 58%

Prussian Blue Analogue Mesoframes for Enhanced Aqueous Sodium-ion Storage

Sun

Zhang

2018

Crystals

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Mesostructure engineering is a potential avenue towards the property control of coordination polymers in addition to the traditional structure design on an atomic/molecular scale. Mesoframes, as a class of mesostructures, have short diffusion pathways for guest species and thus can be an ideal platform for fast storage of guest ions. We report a synthesis of Prussian Blue analogue mesoframes by top-down etching of cubic crystals. Scanning and transmission electron microscopy revealed that the surfaces of the cubic crystals were selectively removed by HCl, leaving the corners, edges, and the cores connected together. The mesoframes were used as a host for the reversible insertion of sodium ions with the help of electrochemistry. The electrochemical intercalation/de-intercalation of Na + ions in the mesoframes was highly reversible even at a high rate (166.7 C), suggesting that the mesoframes could be a promising cathode material for aqueous sodium ion batteries with excellent rate performance and cycling stability.

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In Situ FT-IR/ATR Spectroelectrochemistry of Prussian Blue in the Solid State

Cited by 145 publications

References 32 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

Solid-State Voltammetry — Analytical Prospects

Prussian Blue Analogue Mesoframes for Enhanced Aqueous Sodium-ion Storage

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