A new aspect of Chevrel compounds as positive electrodes for magnesium batteries

Ichitsubo, Tetsu; Yagi, Shunsuke; Nakamura, Ryosuke; Ichikawa, Y.; Okamoto, Shinya; Sugimura, Kazuki; Kawaguchi, Tomoya; Kitada, Atsushi; Oishi, Masatsugu; Doi, Takayuki; Matsubara, Eiichiro

doi:10.1039/c4ta03063j

Cited by 34 publications

(29 citation statements)

References 29 publications

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“…The potential profiles are sloping curves with a final discharge capacity of 149 mA h g −1 when cycled at 500 mA g −1 with negligible polarization. The rate performance was quite commendable where reversible capacities of 265,187,149,125,114, and 102 mA h g −1 were delivered at 50, 200, 500, 1500, 3000, and 6000 mA g −1 , respectively. Additionally, reversible capacity of 120 mA h g −1 can be maintained for more than 4300 cycles at a current rate of 500 mA g −1 , clearly attesting to the superior long-term cyclability of the hybrid material.…”

Section: Science China Materialsmentioning

confidence: 95%

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Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

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to develop and install renewable energy harvesting technologies [3]. However, their successful implementation will be dependent on reliable and robust storage devices since harvesting solar and wind energy is inherently intermittent and the majority of consumption targets cannot be readily tethered to the grid.As energy storage devices, batteries possess high portability, high energy density, high Coulombic efficiency, and long cycle life. They are ideal power sources for portable devices, automobiles, and backup power supplies; accordingly, batteries power nearly all of our mobile electronics and are used to improve the efficiency of hybrid electric vehicles [4,5]. Unfortunately, considerable improvements in performance are still required in order to meet the demands of advanced portable devices and achieve energy sustainability (e.g., through smart grid and electric vehicle technologies) [6]. These enduring needs have driven intensive research investments. While efforts have been successful, there is still significant room for improvement regarding the development and understanding of electrode materials [7]. The overall capacity and potential cycling window of many electrode materials are limited to prevent degradation over long term cycling. In addition to exploring new electrode materials, there have been strong efforts to improve those that are already utilized. Expense reduction is a priority as approximately 23% and 8% of the overall battery pack costs stem from the respective cathode and anode active materials alone [8].An alkali-ion battery consists of several electrochemical cells connected in parallel and/or in series to provide a designated current or voltage. Each electrochemical cell has two electrodes separated by an electrolyte that is electrically insulating but ionically conductive. During discharge, when the alkali-ion battery operates as a galvanic cell, alkali ions exit the negative electrode (typically carbon) and insert themselves into the positive electrode while electronsThe need for economical and sustainable energy storage drives battery research today. While Li-ion batteries are the most mature technology, scalable electrochemical energy storage applications benefit from reductions in cost and improved safety. Sodium-and magnesium-ion batteries are two technologies that may prove to be viable alternatives. Both metals are cheaper and more abundant than Li, and have better safety characteristics, while divalent magnesium has the added bonus of passing twice as much charge per atom. On the other hand, both are still emerging fields of research with challenges to overcome. For example, electrodes incorporating Na + are often pulverized under the repeated strain of shuttling the relatively large ion, while insertion and transport of Mg 2+ is often kinetically slow, which stems from larger electrostatic forces. This review provides an overview of cathode and anode materials for sodium-ion batteries, and a comprehensive summary of research on cathodes for magnesium-ion batteries. In additi...

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Section: Science China Materialsmentioning

confidence: 95%

“…Another novel approach to increasing the energy density of MIBs has recently been proposed by Ichitsubo et al [149]. They note the discrepancy between the potentials for Cu extraction from Cu x CP (~1.2 V) and Cu metal dissolution (~1.7 V) in Mg-compatible electrolytes.…”

Section: Science China Materialsmentioning

confidence: 99%

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

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“…In the case of Mg ion intercalation, spectroscopic tools such as 25 Mg nuclear magnetic resonance (NMR) 7,9 have been developed, in combination with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and energy dispersive spectroscopy (EDS), to provide strong evidence of magnesium ion intercalation, and in some cases, identify cases of solvent co-intercalation, the presence of structural protons, or nanoscale decomposition. 10,11 Whereas magnesium (Mg 2+ ) and aluminum (Al 3+ ) cations have received the most attention as multivalent alternatives to lithium (Li + ), calcium cations (Ca 2+ ) have been identified as a promising candidate ion for transport of multiple electrons due to the high theoretical volumetric capacity of a calcium metal anode. 12 Calcium may also provide advantages as compared to magnesium due to its more negative reduction potential and larger ionic radius, which may allow for faster diffusion.…”

mentioning

confidence: 99%

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Proffit

Fister

Kim

et al. 2016

J. Electrochem. Soc.

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Multivalent-ion batteries have been under investigation as a technology that can provide energy densities beyond that provided by lithium ion batteries. An emerging cation of interest is calcium, as it has similar electrochemical properties and size to sodium, and systems incorporating it have high theoretical density. Common techniques used to investigate intercalation, such as NMR, are currently unable to distinguish calcium's role in energy storage materials. In this work, we investigated the ability of calcium XANES to provide fingerprint identification of intercalated species using Ca ion exchanged Na x CoO 2 and a Ca(PF 6 ) 2 -based electrolyte as a case study. Ca XANES was able to detect intercalation down to concentrations of ∼1 Ca per 950 Å 3 , even with residual electrolyte on the surface. The ability to observe the structure of the intercalated ion will enable the discovery of new electrolytes and intercalation cathodes by helping to confirm theoretical predictions, allowing multivalent batteries to become a viable high energy density storage 8 but understanding and improving upon multivalent intercalation requires experimental observation of the intercalated species and correlating it with the resulting structural changes, in combination with the electrochemistry of interest. In the case of Mg ion intercalation, spectroscopic tools such as 25 Mg nuclear magnetic resonance (NMR) 7,9 have been developed, in combination with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and energy dispersive spectroscopy (EDS), to provide strong evidence of magnesium ion intercalation, and in some cases, identify cases of solvent co-intercalation, the presence of structural protons, or nanoscale decomposition.10,11 Whereas magnesium (Mg 2+ ) and aluminum (Al 3+ ) cations have received the most attention as multivalent alternatives to lithium (Li + ), calcium cations (Ca 2+ ) have been identified as a promising candidate ion for transport of multiple electrons due to the high theoretical volumetric capacity of a calcium metal anode.12 Calcium may also provide advantages as compared to magnesium due to its more negative reduction potential and larger ionic radius, which may allow for faster diffusion. Unlike for magnesium and yttrium ions, however, NMR is not currently a practical diagnostic tool for determining the local structure of the calcium ion to confirm intercalation because of the low abundance and poor sensitivity of 43 Ca, the most active calcium isotope. Therefore, different approaches need to be developed to validate the alternative design paradigm, notably using the Materials Project, 3 which hypothesizes that cations in undesirable coordination environments are more likely to have high diffusivity than ones in stable coordination environment. By providing data for such models, the process of screening potential intercalation cathodes can be narrowed. In addition, this * Electrochemical Society Member.c Present Address: Spectrum Brands -Rayovac, Madison...

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“…[42][43][44][45] In this case, Mg metal was used as the counter electrode, and Li metal immersed in 0. Fig.…”

Section: N M'mentioning

confidence: 99%

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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A new aspect of Chevrel compounds as positive electrodes for magnesium batteries

Abstract: Chevrel compounds have been reexamined as potential positive electrodes for magnesium rechargeable batteries; their redox potential can be as high as about 2–3 V vs. Mg/Mg2+.

Cited by 34 publications

References 29 publications

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

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

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