A Study of the Anode‐Electrolyte Interface in a Thermal Battery

Nissen, D. A.

doi:10.1149/1.2129001

Cited by 15 publications

(10 citation statements)

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“…14 Some attempts to modify the surface of the calcium metal anodes with acetic acid to yield CaCO 3 were reported, 15 despite the chemistry being shown to be extremely complex involving also corrosion with formation of both Ca 2 CrO 4 Cl and KCaCl 3 . 16 Efforts to replace the chlorides by nitrates, with lower melting points, as electrolytes were also reported. 17 A maximum exchange of one electron per mole of calcium was observed with the formation of a passivation film most likely consisting of CaO, hindering any fast kinetics.…”

Section: Historical Perspective (−2015): a Myriad Of Conceptsmentioning

confidence: 99%

“…This type of cell was used in military applications since World War II . Some attempts to modify the surface of the calcium metal anodes with acetic acid to yield CaCO 3 were reported, despite the chemistry being shown to be extremely complex involving also corrosion with formation of both Ca 2 CrO 4 Cl and KCaCl 3 . Efforts to replace the chlorides by nitrates, with lower melting points, as electrolytes were also reported .…”

Section: Introductionmentioning

confidence: 99%

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Achievements, Challenges, and Prospects of Calcium Batteries

et al. 2019

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This Review flows from past attempts to develop a (rechargeable) battery technology based on Ca via crucial breakthroughs to arrive at a comprehensive discussion of the current challenges at hand. The realization of a rechargeable Ca battery technology primarily requires identification and development of suitable electrodes and electrolytes, which is why we here cover the progress starting from the fundamental electrode/electrolyte requirements, concepts, materials, and compositions employed and finally a critical analysis of the state-of-theart, allowing us to conclude with the particular roadblocks still existing. As for crucial breakthroughs, reversible plating and stripping of calcium at the metal-anode interface was achieved only recently and for very specific electrolyte formulations. Therefore, while much of the current research aims at finding suitable cathodes to achieve proof-of-concept for a full Ca battery, the spectrum of electrolytes researched is also expanded. Compatibility of cell components is essential, and to ensure this, proper characterization is needed, which requires design of a multitude of reliable experimental setups and sometimes methodology development beyond that of other next generation battery technologies. Finally, we conclude with recommendations for future strategies to make best use of the current advances in materials science combined with computational design, electrochemistry, and battery engineering, all to propel the Ca battery technology to reality and ultimately reach its full potential for energy storage.

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Section: Historical Perspective (−2015): a Myriad Of Conceptsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Achievements, Challenges, and Prospects of Calcium Batteries

et al. 2019

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“…electrochemical cells, and it also often be used in many industrial process as an intermediate compound formed in the system of Ca-Cr-O [1][2][3] . The thermodynamic properties of CaCrO 4 , such as enthalpy, entropy, Gibbs free energy, heat capacity and so on have been investigated in detail for the wide application of CaCrO 4 [4][5][6][7][8] .…”

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confidence: 99%

Pressure-induced structural phase transition in CaCrO4: Evidence from Raman scattering studies

Long

Zhang

Yang

et al. 2005

Applied Physics Letters

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Raman spectroscopic studies have been carried out on CaCrO 4 under pressure up to 26GPa at ambient temperature. The Raman spectra showed CaCrO 4 experienced a continuous structural phase transition started at near 6GPa, and finished at about 10GPa. It is found that the high-pressure phase could be quenched to ambient conditions. Pressure dependence of the Raman peaks suggested there existed four pressure regions related to different structural characters. We discussed these characters and inferred that the nonreversible structural transition in CaCrO 4 , most likely was from a zircon-type (I4 1 /amd) ambient phase to a scheelite-type high pressure structure (I4 1 /a).

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“…For the Ca/LiC104 cell reaction Cacs~ + LiC104r -~ CaO(s~ + LiClO3(i) [2] at 350~ an even higher cell potential of about 3.2V is calculated that yields a theoretical energy density of 1170 W-hr/kg. Open-circuit cell potentials close to these calculated values have been observed at 350~ in the presence of chloride ions that attack the passivating film on the anode (8,9).…”

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confidence: 99%

“…Eutectic mixtures of these oxidizing molten salts generally have much lower melting points than the conventional LiC1-KC1 mixtures used in thermal battery cells (1)(2)(3). For example, LiNO3-KNO8 mixtures melt at temperatures as low as 132~ (4) while an equimolar LiC104-LiNO3 mixture melts at about 150~ (5).…”

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High Rate Discharge of Ca / LiClO4 ‐ LiNO3 Thermal Battery Cells

Miles

Fletcher

1981

J. Electrochem. Soc.

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The high rate discharge of the Ca/LiCIO4-LiNOJNi thermal battery cell is limited by the reduction of the oxidizing molten salts on the nickel current collector. With the addition of AgNQ to improve the cathodic reaction, this cell can sustain current densities of 100 mA/cm 2 at 350~ to give cell voltages in excess of 2V for several minutes. In cells containing added AgNOs, the source of eventual polarization is the anode rather than the cathode. Based upon the weight of the calcium and electrolyte, cell discharge at 100 mA/cm 2 gives a power density of 740 W/kg and an energy density of 120 W-hr/kg. At a lower rate of discharge (10 mA/cm2), these cells give very stable potentials of about 2.5V for time periods exceeding 60 min. These cells, therefore, show promise for both high and low rate applications of thermal batteries.Nitrate and perchlorate salts are attractive for use in thermal batteries since these molten salts have relatively low melting points and can function as both the electrolyte and oxidizer. Eutectic mixtures of these oxidizing molten salts generally have much lower melting points than the conventional LiC1-KC1 mixtures used in thermal battery cells (1-3). For example, LiNO3-KNO8 mixtures melt at temperatures as low as 132~ (4) while an equimolar LiC104-LiNO3 mixture melts at about 150~ (5). For thermal battery cells using molten salt mixtures containing LiC104, the operating temperature range is expected to be about 250~176(5). The nature of the molten salt cation plays an important role in the reactions of both nitrates (6, 7) and perchlorates (5). The small lithium ion is more effective than the larger alkali metal cations in catalyzing the electrochemical reduction of molten nitrates.Thermochemical caIculations for the cell reactionat 350~ indicate a cell potential of about 2.8V and a theoretical energy density of 1380 W-hr/kg. For the Ca/LiC104 cell reactionat 350~ an even higher cell potential of about 3.2V is calculated that yields a theoretical energy density of 1170 W-hr/kg. Open-circuit cell potentials close to these calculated values have been observed at 350~ in the presence of chloride ions that attack the passivating film on the anode (8,9). Previous studies showed that Ca/LiNQ-LiC1-KC1 [50-25-25 mole percent (m/o)] thermal battery cells gave promising results when discharged at 10 mA/cm 2 over a temperature range of 250~176 (9). At current densities above 20-30 mA/cm~, however, the cell performance deteriorates due to polarization at the anode. The rate of the calcium anode reaction in molten nitrates is determined largely by the passivating film that hinders the passage of calcium ions across the oxide layer (8). Comparisons of measured and calculated cell resistances suggest that the anodic oxide film makes a sizeable contribution to the total cell resistance (9). This study shows that the presence of LiCIO4 improves the performance of the anode during high rate discharge. 9 Electrochemical Society Active Member. ExperimentalThe electrochemical cells were fabricated from calcium ...

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A Study of the Anode‐Electrolyte Interface in a Thermal Battery

Cited by 15 publications

References 1 publication

Achievements, Challenges, and Prospects of Calcium Batteries

Achievements, Challenges, and Prospects of Calcium Batteries

Pressure-induced structural phase transition in CaCrO4: Evidence from Raman scattering studies

High Rate Discharge of Ca / LiClO4 ‐ LiNO3 Thermal Battery Cells

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