Reversible Calcium Ion Batteries Using a Dehydrated Prussian Blue Analogue Cathode

Tojo, Tomohiro; Sugiura, Yosuke; Inada, Ryoji; Sakurai, Yasuhisa

doi:10.1016/j.electacta.2016.04.159

Cited by 134 publications

(88 citation statements)

References 39 publications

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“…Initially, BaHCF does not show any peak of Ca‐ion, as expected. However, after the first discharge (Ca 2+ insertion) (Figure a), Ca 2 p peaks were observed at 346.7 eV and 350.4 eV . which confirms the presence of Ca‐ion in BaHCF lattice.…”

Section: Resultsmentioning

confidence: 99%

“…Prussian blue analogues are one of the foremost material due to its rapid kinetics providing prolonged durability. Interestingly, most of the reports are based on the flooded 3‐electrode cell. Hence, an initial development merging current collector selection, inexpensive non‐corrosive low‐cost electrolyte and the simple procurable electro‐active material is imperative to render the capability of Ca electrochemistry.…”

Section: Introductionmentioning

confidence: 98%

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An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

2018

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The capability of high‐rate cycling and environmental benignity at less expensive defines the ingress of upcoming energy storage system. The urge of such system comes into the picture because today, the state‐of‐the‐art lithium technology is ineffectual to improve its rapid‐charging ability beyond a certain limit, in commercial scale. Here, we introduce reversible electrochemistry of Ca‐ion full cell in conjunction with inexpensive aqueous electrolyte, 1M aq. Ca(ClO4)2. In the full cell, carbon cloth, barium hexacyanoferrate (BaHCF) and meso‐carbon microbeads (MCMB) have been explored as the current collector, cathode and anode material, respectively. The full cell provides 40 mAh g‐1 capacity at 5C rate till 100 cycles. We believe, the investigation of this simple full cell at the early stage of Ca‐ion battery will pave a fast transition in the forthcoming energy storage systems.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

2018

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“…For the Mg battery technology, proof-of-concept was achieved as late as in 2000, 6 although its practical development has been hampered by some fundamental challenges that are gradually being overcome. [7][8][9] For Ca, the viability of metal electrodeposition has only recently been achieved 10 and a few studies on possible cathode materials have started to appear in 2015-2016 [11][12][13][14][15][16][17][18][19] being to the best of our knowledge the exhaustive list. Since the Mg and Ca cations are divalent, the amount of ions that must react in order to achieve a certain electrochemical capacity is half compared to the monovalent Li + and Na + .…”

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confidence: 99%

On the Reliability of Half-Cell Tests for Monovalent (Li⁺, Na⁺) and Divalent (Mg²⁺, Ca²⁺) Cation Based Batteries

Tchitchekova

Monti

Johansson

et al. 2017

J. Electrochem. Soc.

114

141

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A comprehensive study is reported entailing a comparison of Li, Na, K, Mg, and Ca based electrolytes and an investigation of the reliability of electrochemical tests using half-cells. Ionic conductivity, viscosity, and Raman spectroscopy results point to the cationsolvent interaction to follow the polarizing power of the cations, i.e. Mg 2+ > Ca 2+ > Li + > Na + > K + and to divalent cation based electrolytes having stronger tendency to form ion pairs -lowering the cation accessibility and mobility. Both increased temperature and the use of anions with delocalized negative charge, such as TFSI, are effective in mitigating this issue. Another factor impeding the divalent cations mobility is the larger solvation shells, as compared to those of monovalent cations, that in conjunction with stronger solvent -cation interactions contribute to slower charge transfer and ultimately a large impedance of Mg and Ca electrodes. An important consequence is the non-reliability of the pseudo-reference electrodes as these present both significant potential shifts as well as unstable behaviors. Finally, experimental protocols in order to achieve consistent results when using half-cell set-ups are Although the lithium-ion battery is currently being considered as the most promising technology for electric vehicle propulsion, the development of alternative and complementary battery chemistries and technologies is of great importance, especially aiming at large-scale applications, i.e. the grid for which the cost in $/kWh and sustainability are crucial indicators. Indeed, the implementation of lithium based technology at large scale faces a significant challenge, since the controversial debates on lithium availability and cost cannot be overlooked. Amongst several chemistries possible the most appealing alternatives involve the use of sodium (Na), magnesium (Mg) or calcium (Ca) for mainly two reasons. The prime is the abundance of the raw materials, i.e. Na, Mg, and Ca being the 6 th , 8 th , and 5 th most abundant elements in the Earth's crust, vs. 25 th for Li, making them 20 to 50 times cheaper than Li, e.g. $5000/ton, $135-165/ton, $265/ton, and $100/ton for Li 2 CO 3 , Na 2 CO 3 , MgO 2 , and CaCO 3 , 1 respectively. Performance wise, the low cost alternatives of Na, Mg, and Ca technologies would also benefit from high standard reduction potentials, ca. −2.71, −2.37, and −2.87 V vs. SHE for Na, Mg, and Ca, respectively, as compared to −3.04 V for Li, and large theoretical electrochemical capacities, both gravimetric and volumetric, for the metal electrodes (Fig. 1).Sodium metal anodes are already used in the liquid state (m.p. ∼97• C) in the Na/S technology 2 and room-temperature Na-ion technology is currently intensively investigated with hundreds of papers appearing per year, with progress being summarized in several review papers amongst which 3-5 are the most recent. For Mg and Ca metal anodes, the situation is radically different. For the Mg battery technology, proof-of-concept was achieved as late as in 2000, 6 although i...

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“…For example, it is reported that the removal or existence of interstitial water plays an essential role in the structure of PBA . These studies showed alkaline cations (A), transition metal (M), and H 2 O have an effect on determining the structure and stability of the material …”

Section: Introductionmentioning

confidence: 99%

Interpretation of the Role of Composition on the Inclusion Efficiency of Monovalent Cations into Cobalt Hexacyanoferrate

Zhang

Kawamoto

Jiang

et al. 2019

Chemistry A European J

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Cobalt hexacyanoferrate of various compositions was prepared in flow mode and the role of the vacancy on the structure, thermogravimetric (TG) properties, and the adsorption efficiency was studied. The material, NayCo[Fe(CN)6]1−x⋅z H2O, with a minimum vacancy of x=0.014 to the highest x=0.47, was obtained. The TG‐differential scanning calorimetry (DSC) profile showed a distinct influence of the vacancy on the water release temperature. Materials with x>0.35 showed a smooth release of water at a relatively lower temperature. However, for the materials with x<0.35, water release took place in multiple steps, suggesting the existence of various forms of water. The FTIR profiles supported the existence of free and bonded water molecules. However, the materials with multiple water peaks in the FTIR spectra showed a shift of the major XRD peaks when heated at 285 °C in N2 atmosphere. Regarding the effect of the vacancy on the adsorption behavior, for NH4, the adsorption was found to be proportional to the number of Na atoms in the material, confirming the ion‐exchange process. On the contrary, the materials with low vacancy and high Na content showed nominal Cs adsorption capacity. Interestingly, the K adsorption capacity was found to be in between that of the other two ions. This means the ionic size decides the rate of placement into the interstitial sites. For larger ions like Cs, the ease of percolation via the vacancy decides the overall adsorption efficiency.

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Reversible Calcium Ion Batteries Using a Dehydrated Prussian Blue Analogue Cathode

Cited by 134 publications

References 39 publications

An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

On the Reliability of Half-Cell Tests for Monovalent (Li⁺, Na⁺) and Divalent (Mg²⁺, Ca²⁺) Cation Based Batteries

Interpretation of the Role of Composition on the Inclusion Efficiency of Monovalent Cations into Cobalt Hexacyanoferrate

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Reversible Calcium Ion Batteries Using a Dehydrated Prussian Blue Analogue Cathode

Cited by 134 publications

References 39 publications

An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

An Aqueous Ca‐ion Full Cell Comprising BaHCF Cathode and MCMB Anode

On the Reliability of Half-Cell Tests for Monovalent (Li+, Na+) and Divalent (Mg2+, Ca2+) Cation Based Batteries

Interpretation of the Role of Composition on the Inclusion Efficiency of Monovalent Cations into Cobalt Hexacyanoferrate

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On the Reliability of Half-Cell Tests for Monovalent (Li⁺, Na⁺) and Divalent (Mg²⁺, Ca²⁺) Cation Based Batteries