Calcium Thionyl Chloride High‐Rate Reserve Cell

Peled, E.; Meitav, A.; Brand, Moshe

doi:10.1149/1.2127768

Cited by 33 publications

(40 citation statements)

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“…[ 6 ] Ca has also been used as an anode in Ca/SOCl 2 catholyte systems in which the cathode material is underutilized due to passivation by the insulating CaCl 2 discharge product. [8][9][10][11] Thermal cells have also used Ca anodes in conjunction with molten Li salt electrolytes such as LiCl, LiNO 3 . [ 12 , 13 ] Secondary battery behavior has been demonstrated in these cells but only at temperatures greater than 400 ° C [ 12 ] and with the use of alloyed anodes such as CaSi.…”

Section: Full Papermentioning

confidence: 99%

A High Capacity Calcium Primary Cell Based on the Ca–S System

See

Gerbec

Jun

et al. 2013

Advanced Energy Materials

104

118

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Conversion reaction cells afford the ability to explore new energy storage paradigms that transcend the dogma of small, low‐charge cations essential to intercalative processes. Here we report the use of earth‐abundant and green calcium and sulfur in unprecedented conversion reaction Ca–S primary cells. Using S‐infiltrated mesoporous carbon (abbreviated S@meso‐C) cathodes, we achieve discharge capacities as high as 600 mAh g−1 (S basis) within the geometry Ca|Ca(ClO4)2/CH3CN|S@meso‐C, at a discharge rate of C/3.5. The electrolyte system in the Ca–S battery is of paramount importance as the solid electrolyte interface (SEI) formed on the Ca anode limits the capacity and stability of the cell. We determine that 0.5 M Ca(ClO4)2 in CH3CN forms an SEI that advantageously breaks down under anodic bias to allow oxidation of the anode. This same SEI, however, exhibits high impedance which increases over time at open circuit limiting the shelf life of the cell.

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Section: Full Papermentioning

confidence: 99%

A High Capacity Calcium Primary Cell Based on the Ca–S System

See

Gerbec

Jun

et al. 2013

Advanced Energy Materials

104

118

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“…Previous work on calcium primary batteries include the Ca-S system, 16 the Ca/Ca(AlCl 4 ) 2 /SOCl 2 system, [17][18][19][20] as well as thermal cells using lithium-based molten salts; 21,22 reversible behavior has not yet been demonstrated in these systems except for the molten salt batteries when heated above 400…”

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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“…The [MX~] chains are weakly bonded with each other. Lithium ions were assumed to be intercalated in the interchain space (2). The overall reaction of lithium intercalation was represented by the following equations (3,4) 2Li + + 2e-+ M4+X2-X~ 2 ~ (Li+)2M 4+ (X2-)3 [1] Li + + e-+ (Li+)2M 4 § (X2-)3 ~ (Li+)3M3+(X2-)3 [2] The X-X dimer is reduced in the first reaction and the transition metal in the second.…”

Section: T Yamamoto *'L S Kikkawa and M Koizumimentioning

confidence: 99%

“…The calcium-thionyl chloride battery system has been attracting considerable attention (1)(2)(3)(4)(5)(6) for its high opencircuit potentials (->3.2V), high theoretical energy density (1100 Wh/kg), broad operating temperature range~ and projected high degree of system safety. This increased safety is due to the high melting point of calcium metal (839 ~ vs. 180~ for lithium) which precludes the likelihood of difficulties traceable to a molten anode.…”

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Cathode Performance Improvement in Calcium‐Thionyl Chloride Cells

Walker

Wade

Binder

et al. 1986

J. Electrochem. Soc.

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Carbon cathode performance in ealcium-thionyl chloride cells was markedly improved with a cathode comprised of a mixture of high and low surface area carbon blacks. Addition of sulfur dioxide gas to the electrolyte further enhanced cathode performance and electrolyte conductivity. Load potentials and cathode life were nearly equal to that of the analogous lithium based system. The advantage of the calcium based system is its potential for greater safety.The calcium-thionyl chloride battery system has been attracting considerable attention (1-6) for its high opencircuit potentials (->3.2V), high theoretical energy density (1100 Wh/kg), broad operating temperature range~ and projected high degree of system safety. This increased safety is due to the high melting point of calcium metal (839 ~ vs. 180~ for lithium) which precludes the likelihood of difficulties traceable to a molten anode.

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Calcium Thionyl Chloride High‐Rate Reserve Cell

Abstract: not Available.

Cited by 33 publications

References 0 publications

A High Capacity Calcium Primary Cell Based on the Ca–S System

A High Capacity Calcium Primary Cell Based on the Ca–S System

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

Cathode Performance Improvement in Calcium‐Thionyl Chloride Cells

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