Microgravimetric monitoring of transport of cations during redox reactions of indium(III) hexacyanoferrate(III,II)

Malik, Marcin A.; Horányi, G.; Kulesza, Paweł J.; Inzelt, György; Kertész, Vilmos; Schmidt, Rupert; Czirók, E.

doi:10.1016/s0022-0728(98)00095-3

Cited by 49 publications

(31 citation statements)

References 34 publications

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“…3c, the fraction of Mg 2+ ions is approximately 85% below 0.9 V and approximately 75% above 0.9 V during the anodic sweep, indicating that the contribution of SO 2− 4 ions increases above 0.9 V. During the cathodic sweep, the fraction is nearly constant although a flexion point is seen at approximately 0.82 V. The contribution of anionic species was postulated by Itaya et al, 14 and was experimentally verified by Malik et al using the radiotracer method. 15 Also in the present study, the contribution of anionic species was substantiated by EQCM measurement. It should be noted that the fraction of Mg 2+ ions would be smaller when considering hydrated or partially dehydrated Mg 2+ ions as carrier ions.…”

Section: Resultssupporting

confidence: 65%

“…In fact, monovalent K + ions with a larger ionic radius are reversibly inserted/extracted through an almost complete dehydration in PB without an obvious peak splitting in a KCl aqueous electrolyte. 15,27 However, mixed charge compensation with cations and anions is also seen for CuFe-PBA in a K 2 SO 4 aqueous electrolyte as shown in Fig. 6, although peak splitting is significantly suppressed.…”

Section: Resultsmentioning

confidence: 75%

“…6, although peak splitting is significantly suppressed. Therefore, the peak splitting and the mixed charge compensation depend on all of the following factors: the size and defectiveness of the framework structure (insoluble or soluble form 15 ), the number of valence electrons of carrier ions, and the sizes of solvated or desolvated carrier ions. It should be noted that peak splitting can also be caused by the mixture of PBAs with different stoichiometries, for example, K 2 Figure 7 shows the charge-discharge curves and changes in capacities with cycles for CuFe-PBA mesured in a 1.0 M MgSO 4 aqueous electrolyte at 1 C rate.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, since Neff first reported the redox behavior of a Prussian blue (PB)-modified electrode with rapid color change, 13 the structures, electronic and optical properties, and redox behaviors of PB and its analogs (PBAs) have been thoroughly investigated. [14][15][16][17][18][19][20][21][22][23][24][25] As shown in Fig. 1, PB and PBAs possess a large space in the crystal structure, where fast diffusion 17 and reversible insertion/extraction of cations such as K + , Li + , Na + , and NH + 4 are possible.…”

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confidence: 99%

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EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Yagi

Fukuda

Ichitsubo

et al. 2015

J. Electrochem. Soc.

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A wide variety of ions and molecules can be accommodated in the framework structure of Prussian blue (PB) and its analogs (PBAs). Mono-and polyvalent ions accommodated in the PB framework structure and PBAs can be extracted or re-inserted by redox reactions of transition metal ions composing the framework for charge compensation. In the present work, we report the detailed mechanism of the electrochemical inseration/extraction of Mg 2+ ions and the effect of anions on the redox chemistry of a PBA composed of Cu and Fe ions by electrochemical quartz crystal microbalance and X-ray absorption spectroscopy. Furthermore, we evaluated the PBA as an active material using aqueous and organic electrolytes for Mg battery systems, and clarified that the redox potential of CuFe-PBA is approximately 3 V vs. Mg/Mg 2+ in both aqueous and organic electrolytes. Rechargeable Mg batteries have received intensive attention as affordable rechargeable batteries with high electromotive force, high energy density, and high safety because of the following superb properties of Mg; Mg possesses two valence electrons and has the lowest standard electrode potential (ca. −2.36 V vs. SHE) among the airstable metals; 1,2 Mg metal can be used as an active material because Mg metal hardly forms dendrites; 3-6 and Mg is a lightweight and abundant element widely spread in the world. However, the slow diffusion of Mg 2+ ions in solid crystals prevents the realization of active materials for Mg rechargeable batteries at room temperature. Although some complex oxides have been reported to work as active materials at higher temperatures, [7][8][9][10] Chevrel compounds are still the gold standards, which work at room temperature.11,12 However, the working voltage of the magnesium battery using a Chevrel compound for the positive electrode is only ca. 1.2 V, which is far below that of lithium ion batteries (3-5 V). Nevertheless, Chevrel compounds have the significant advantage that a relatively large space exists in the crystal structure, which allows for fast Mg 2+ ion diffusion. On the other hand, since Neff first reported the redox behavior of a Prussian blue (PB)-modified electrode with rapid color change, 13 the structures, electronic and optical properties, and redox behaviors of PB and its analogs (PBAs) have been thoroughly investigated. [14][15][16][17][18][19][20][21][22][23][24][25] As shown in Fig. 1 2+ ions? Why do several peaks appear in voltammograms of these compounds? In the present study, to answer these questions, we investigated the insertion and extraction behavior of Mg 2+ ions in a CuFe-PBA using electrochemical quartz crystal microbalance (EQCM) and X-ray absorption spectroscopy (XAS). This work is expected to provide guidance for choosing framework compounds as active materials for Mg 2+ batteries. * Electrochemical Society Active Member. z E-mail: s-yagi@21c.osakafu-u.ac.jp ExperimentalSynthesis of a Prussian blue analog CuFe-PBA.-All chemicals for the synthesis of CuFe-PBA and electrochemical tests in aqueous electrolytes wer...

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Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Yagi

Fukuda

Ichitsubo

et al. 2015

J. Electrochem. Soc.

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“…It is well known that CuHCF films are potentially permeable membranes for cations such as K + , NH 4 + , Li + , and Na + [15,16]. The electrochemical behaviors of the CuHCF-modified GCE prepared via 15 continuous cycles in LiNO 3 , NaNO 3 , KNO 3 , and NH 4 NO 3 solution were explored.…”

Section: Electrochemical Behavior Of the Cuhcf-modified Gcementioning

confidence: 99%

Cubic Copper Hexacyanoferrates Nanoparticles: Facile Template-Free Deposition and Electrocatalytic Sensing Towards Hydrazine

Wang

Zhang

Jiang

et al. 2011

International Journal of Electrochemistry

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Cubic copper hexacyanoferrate (CuHCF) nanoparticles prepared via electrolytic deposition are presented with their morphology and crystalline structure characterized with SEM and XRD. The advantage of this methodology is that it allows the fabrication of uniform cubic nanoparticles with permeable structures onto the desired underlying electrode substrate. It was observed that the CuHCF film acts as a permeable membrane for cations such as K + , Na + , Li + , and NH 4 + with a selection order of K + > Li + > NH 4 + > Na + . Furthermore, the analytical utility of these cubic-like CuHCF morphologies supported on a glassy carbon electrode was evaluated towards the electrochemical oxidation of hydrazine which was found to exhibit a linear response over the range 66 μM to 17 mM with a detection limit corresponding to 16.5 μM.

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Amperometric Detection of Cysteine at an In³⁺ Stabilized Indium Hexacyanoferrate Modified Electrode

Tseng

Chen

2006

Electroanalysis

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This research focuses on the stabilization of indium hexacyanoferrate (InHCF) modified electrode in aqueous solution and the amperometric detection of cysteine (Cys). It was found that the stability of the InHCF modified electrode in the aqueous solution could be improved upon adding In 3þ in the solution. EQCM experiments verified that such an In 3þ addition greatly inhibited an oxidized InHCF thin films dissociation and thus considerably stabilizes the InHCF modified electrode. The amperometric detection was performed by the application of a static potential at 1.2 V, with the sampling time at 30 s. The sampled current was linearly dependent on [Cys] when [Cys] was ranged from 100 mM to 1 mM. The sampled current approached a plateau gradually with the increase in the concentration of cysteine. The trend of calibration curve at the InHCF modified electrode generally follows the Michaelis -Menten type kinetics, and K m and v max were calculated to be 3.86 mM and 30.2 mA, respectively, from the Lineweaver -Burke plot. In addition, the amperometric detection was reversible and reproducible with relative standard deviations of 2.79%.

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Microgravimetric monitoring of transport of cations during redox reactions of indium(III) hexacyanoferrate(III,II)

Cited by 49 publications

References 34 publications

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Cubic Copper Hexacyanoferrates Nanoparticles: Facile Template-Free Deposition and Electrocatalytic Sensing Towards Hydrazine

Amperometric Detection of Cysteine at an In³⁺ Stabilized Indium Hexacyanoferrate Modified Electrode

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Microgravimetric monitoring of transport of cations during redox reactions of indium(III) hexacyanoferrate(III,II)

Cited by 49 publications

References 34 publications

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Cubic Copper Hexacyanoferrates Nanoparticles: Facile Template-Free Deposition and Electrocatalytic Sensing Towards Hydrazine

Amperometric Detection of Cysteine at an In3+ Stabilized Indium Hexacyanoferrate Modified Electrode

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Amperometric Detection of Cysteine at an In³⁺ Stabilized Indium Hexacyanoferrate Modified Electrode