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

See, Kimberly A.; Gerbec, Jeffrey A.; Jun, Young‐Si; Wudl, Fred; Stucky, Galen D.; Seshadri, Ram

doi:10.1002/aenm.201300160

Cited by 98 publications

(127 citation statements)

References 32 publications

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“…This indicates that Li as well as Ca deposition on Ca in TFA‐TEGDME is unlikely. The initial plateau for discharge occurs at 1.5 V versus Ca, which is in agreement with the previous observation that Ca dissolution in most of the organic solvents requires an SEI breakdown potential of approximately 1 V . We also observed a similar degrading trend in CaLi 2 –sulfur cells using elemental sulfur, Super P, and LiTFA‐TEGDME; the passivation of polysulfides on a CaLi 2 anode quickly quenched the cells after the first cycle (Figure S5 in the Supporting Information) …”

Section: Resultssupporting

confidence: 90%

“…[1,24] We also observed as imilard egrading trend in CaLi 2 -sulfur cells using elemental sulfur,S uper P, and LiTFA-TEGDME;t he passivation of polysulfides on aC aLi 2 anode quicklyq uenched the cells after the first cycle ( Figure S5 in the Supporting Information). [24] CaLi 2 greatly affects the morphologye volution of the dischargep roducts.T ypical Li 2 O 2 flat toroidsw ith surface crystalline nanoparticlesw ere observed in Li-O 2 cells when using LiTFA-TEGDME (Figure 3a-c). [25] Using the CaLi 2 anode leads to the formation of spherical (2-4 mm) and layered microparticles ( % 10 mm) in LiTFA-and Ca(TFA) 2 -TEGDME,r espectively,a tt he full discharge condition (Figure 3d-i and Figure S6 in the Sup- ChemSusChem 2020, 13,574 -581 www.chemsuschem.org porting Information).…”

Section: Super Pmentioning

confidence: 54%

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Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries

Kim

Kang

et al. 2019

ChemSusChem

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The growing demand for rechargeable batteries with high energy density has triggered research on batteries based on polyvalent cations such as Ca2+, Mg2+, Al3+, and Y3+. Ca is, in particular, a promising anode material as an alternative to Li because of its mechanical strength (ρ=1.55 g cm−3), safety in terms of thermal runaway (m.p.=839 °C), earth‐abundance (world production of 150 million tons of gypsum in 2012), high specific charge capacity (1.340 mAh g−1 or 2.077 mAh cm−3), and standard reduction potential (−2.87 V vs. normal hydrogen electrode, NHE) comparable to that of Li. As with Mg, the practical application of Ca in rechargeable batteries with organic liquid electrolytes has been hindered by the passivation layer resulting from undesirable reactions between metallic Ca and electrolytes, which precludes the possibility of reversible plating of any metal cations on Ca electrodes. Here, a battery system based on intermetallic CaLi2 anodes was developed. Li was used as a host for Ca through the formation of an intermetallic compound, which simultaneously enabled 1) the assembly of a rechargeable battery system with Ca anodes and liquid organic electrolytes and 2) coupling these with an earth‐abundant, high‐energy‐density air cathode without special passivation agents. This strategy is simple and broadly applicable to the other polyvalent cations listed above, opening a new avenue to further engineer the electrode materials required for practical, efficient electrochemical energy‐storage systems.

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Section: Resultssupporting

confidence: 90%

Section: Super Pmentioning

confidence: 54%

Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries

Kim

Kang

et al. 2019

ChemSusChem

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“…However, to date, there has been only one study on calcium-sulfur (Ca-S) batteries, and the Ca-S cells demonstrated in that study were not reversible. [15] Furthermore, the Ca-S cell showed a low discharge voltage due to lack of an effective electrolyte.Herein, we present, for the first time, a reversible Ca-S battery enabled by a lithium-ion mediation strategy. The Ca-S battery is developed with a hybrid electrolyte comprised of a mixture of lithium and calcium ions.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach

Boyer

Hwang

et al. 2019

Advanced Energy Materials

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attract increasing attention. [2] However, the progress in Ca 2+ -ion batteries is very sluggish due to multiple difficulties. One major challenge is the lack of applicable electrolytes that can provide a proper function for the stripping and plating of calcium metal. [3] Another challenge is the difficulty in realizing proper cathode host materials. As a matter of fact, there are substantial differences in the interaction behavior between the divalent Ca 2+ -ion and that of the monovalent Li + -ion. [4] Therefore, neither theoretical guidance nor practical experience with Li + -ion intercalation cathode materials may be straightforwardly adopted for the development of Ca 2+ -ion batteries.In an early stage, V 2 O 5 has been explored as an intercalation-type cathode for Ca 2+ -ion batteries, but the utilization of Ca is very low. [5] Ca-SOCl 2 battery systems have also been exploited, but the utilization of the SOCl 2 electrode is very low due to the passivation of the electrode. [6] In recent years, an intercalation cathode CaCo 2 O 4[7] and various conversion-type hexacyanoferratebased cathodes [8] have been investigated. The Ca 2+ -ion cells demonstrated with these cathode materials have shown interesting performances. However, the capacity of these materials is intrinsically low. Nonaqueous metal-sulfur batteries based on a sulfur cathode chemistry have recently been considered as a promising solution for the development of nextgeneration electrochemical energy storage technologies. [9] Sulfur can facilitate a 2-electron charge transfer and theoretically deliver a high gravimetric capacity of 1672 mA h g −1 . In addition to the primary emphasis on lithium-sulfur (Li-S) batteries, [10] sodiumsulfur batteries, [11] magnesium-sulfur (Mg-S) batteries, [12] potassium-sulfur batteries, [13] and aluminum-sulfur (Al-S) batteries [14] have also received significant attention. However, to date, there has been only one study on calcium-sulfur (Ca-S) batteries, and the Ca-S cells demonstrated in that study were not reversible. [15] Furthermore, the Ca-S cell showed a low discharge voltage due to lack of an effective electrolyte.Herein, we present, for the first time, a reversible Ca-S battery enabled by a lithium-ion mediation strategy. The Ca-S battery is developed with a hybrid electrolyte comprised of a mixture of lithium and calcium ions. In addition to enabling the reversibility of Ca-S chemistry, the use of Li + -ion mediated electrolyte enhances the ionic charge transfer, thus both utilization of the active sulfur cathode and the discharge voltage of the Ca-S batteries are significantly improved.Calcium represents a promising anode for the development of high-energydensity, low-cost batteries. However, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calciumsulfur (Ca-S) battery has not yet been reported. Herein,...

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

Cited by 98 publications

References 32 publications

Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries

Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries

Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach

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

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

Cited by 98 publications

References 32 publications

Rechargeable Intermetallic Calcium–Lithium–O2 Batteries

Rechargeable Intermetallic Calcium–Lithium–O2 Batteries

Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach

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

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Product

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Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries

Rechargeable Intermetallic Calcium–Lithium–O₂ Batteries