Dawn of Calcium Batteries

Nielson, Kevin V.; Liu, Tianbiao

doi:10.1002/anie.201913465

Cited by 33 publications

(25 citation statements)

References 18 publications

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“…Calcium (ion) batteries have emerged as potential next-generation electrochemical energy storage systems. [1][2][3][4] As examples of their benefits, calcium is the most abundant alkaline earth element and the 5 th most abundant element in the Earth's crust. Ca sourcing is low-cost and of significant global production (e.g., crushed lime) to supply its future battery industry.…”

Section: Introductionmentioning

confidence: 99%

A Computational Study on the Ca2+ Solvation, Coordination Environment, and Mobility in Electrolytes for Calcium Ion Batteries

Biria

Pathreeker

Hosein

2021

Preprint

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Calcium (ion) batteries are promising next-generation energy storage systems, owing to their numerous benefits in terms of performance metrics, low-cost, mineral abundance, and economic sustainability. A central and critical area to the advancement of the technology is the development of suitable eletrolytes that allow for good salt solubility, ion mobility, electrochemical stability, and reversible redox activity. At this time, the study of different solvent-salt combinations is very limited. Here, we present a computational study on the coordination environment, solvation energetics, and diffusivity of calcium ions over a range of pertinent ionic liquids, cyclic and acylic alkyl carbonates, and specific alkyl nitriles and alkyl formamides, using the salts calcium bis(trifluoromethylsulfonyl)imide (Ca(TFSI)2) and calcium perchlorate (Ca(ClO4)2). Key findings are that several solvents from different solvent classes present comparable solvation environments and mobilities. Ca(TFSI)2 is prefered over Ca(ClO4)2 owing to the former’s mix coordination of Ca2+ to O and N atoms. Ionic liquids with alkyl sulfonate anions provide better coordation over TFSI, which leads to greater diffusivity. Binary organic mixtures (carbonates) provide the best solvation of Ca2+, however, single organic solvents also provide good solvation, such as EC, THF and DMF, as well as some acyclic carbonates. Ion pairing with the salt anion is always present, but can be mitigated through solvent selection, which also correlates to greater mobility; however, there are examples in which strong ion pairing is not significantly adverse to diffusivity. The solvent incorporate into the solvation structure with binary organic mixtures correlates well with the solvation capabilities of the individual solvents. Finally, we show that ionic liquids (specifically alkyl imidazole (cation) alkyl sulfonate (anion) ionic liquids) do not decompose when coordinating at a Ca metal interface, which indicates its promising stability. Overall, this study contributes further generalized understanding of the correlation between solvent and salt and the resultant Ca2+ complexes and Ca2+ mobility in a range of electrolytes, and reveals a range of possible solvents suitable for exploration in calcium (ion) batteries.

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Section: Introductionmentioning

confidence: 99%

A Computational Study on the Ca2+ Solvation, Coordination Environment, and Mobility in Electrolytes for Calcium Ion Batteries

Biria

Pathreeker

Hosein

2021

Preprint

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“…More recently, the group of Zhao-Karger and Fichtner, shortly followed by those of Nazar and Liu, proposed a new calcium alkoxyborate salt able to plate and strip calcium at room temperature. [47][48][49] This salt that can be considered as the initiator of a new generation of non-nucleophilic calcium electrolyte salts working at room temperature, 50 which are expected to be adapted to sulfur-based cathode systems, Indeed, a first example of rechargeable Ca/S has been published at the end of the review process of the current work. 51 In this work, first we confirm the electrochemical activity of Ca/S battery at room temperature using the above-mentioned alkoxyborate-based electrolyte and a composite positive electrode made from sulfur-impregnated activated carbon cloth (ACC), in agreement with the recent results of Li et al 51 Moreover, by using a combination of in situ and ex situ spectroscopic techniques such as X-ray absorption (XAS) and X-ray photoemission (XPS) spectroscopy we propose a clear view of the electrochemical mechanisms, which proceed through the formation of several calcium polysulfide species to calcium sulfide as end of discharge product.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Insights into the Electrochemical Mechanism of Rechargeable Calcium/Sulfur Batteries

et al. 2020

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Calcium batteries represent a promising alternative to lithium metal batteries. The combination of the low redox potential and low-cost and energy-dense calcium anode (2073 mAh/cm 3 , similar to 2044 mAh/cm 3 for Li) with appropriate low-cost cathode materials such as sulfur, could produce a game-changing technology in several fields of applications. In this work, we present the reversible activity of a proof-of-concept Ca/S battery at room temperature, characterized by a surprising medium-term cycling stability with low polarization, promoted by the use of a simple positive electrode made of sulfur supported on an activated carbon cloth scaffold, and a state-of-the-art fluorinated alkoxyborate-based electrolyte. Insights on the electrochemical mechanism governing the chemistry of the Ca/S system were obtained for the first time by combining X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The mechanism implies the formation of different types of soluble polysulfides species during both charge and discharge at room temperature, and the formation of solid CaS at the end of discharge. The reversible electrochemical activity is proven by the reformation of elemental sulfur at the end of the following charge. These promising results open the way to the comprehension of emerging Ca/S systems which may represent a valid alternative to Mg/S and Li/S batteries.

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“…The Mg‐ FPB / G2 solution showed an outstanding electrochemical performance of 95 % CE calculated by CV method, low overpotential for reversible Mg deposition, and anodic stability up to 4.0 V on SS, Ti, Al, and GC. Based on these reports, [42] it is reasonable to expect that other boron‐based bulky and weakly coordinating anions‐based electrolytes hold promise in the development of Mg electrolytes [43] and Ca electrolytes [44] …”

Section: Electrolytes and Electrolyte‐dependent Interfacesmentioning

confidence: 99%

“…Based on these reports, [42] it is reasonable to expect that other boron-based bulky and weakly coordinating anions-based electrolytes hold promise in the development of Mg electrolytes [43] and Ca electrolytes. [44] Despite recent advances on divalent metal electrolytes (Figure 2b and Table 1), most electrolyte systems cannot meet all performance metrics (Figure 2c), i. e., high anodic stability at the cathode, high cathodic stability at the metallic divalent anode, high charge-transfer kinetics for both electrodes, and long-term cycling performance. To date, fluoroalkoxyboratebased Mg electrolytes show excellent anodic stability but insufficient cathodic stability due to a potential passivation film formed on Mg or Ca anodes.…”

Section: Fluorinated Alkoxy-based Electrolytesmentioning

confidence: 99%

Advancing Electrolyte Solution Chemistry and Interfacial Electrochemistry of Divalent Metal Batteries

et al. 2021

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Divalent metal (Mg, Ca, etc.) battery chemistries potentially provide a sustainable long‐term technical solution for large‐scale energy storage because of the high natural abundance of divalent metal elements in the earth crust. Good progress has been made on materials especially electrolyte development in the past years; however, significant challenges exist, particularly the very limited fundamental understanding of electrolyte solution chemistry and interfacial electrochemistry. In this perspective, we review and discuss key discoveries and understanding of divalent battery chemistry with a focus on electrolyte‐dependent interfacial electrochemistry of divalent metal anodes. A concise review of electrolyte development, operando studies of the electrified interfaces, and unique charge‐transfer process is provided; the knowledge gaps and future research directions are discussed.

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Dawn of Calcium Batteries

Abstract: Calcium batteries are a potentially sustainable, high‐energy‐density battery technology beyond Li ion batteries. Now the development of Ca batteries has become possible with a newly invented Ca electrolyte capable of reversible Ca deposition/stripping at room temperature.

Cited by 33 publications

References 18 publications

A Computational Study on the Ca2+ Solvation, Coordination Environment, and Mobility in Electrolytes for Calcium Ion Batteries

A Computational Study on the Ca2+ Solvation, Coordination Environment, and Mobility in Electrolytes for Calcium Ion Batteries

Spectroscopic Insights into the Electrochemical Mechanism of Rechargeable Calcium/Sulfur Batteries

Advancing Electrolyte Solution Chemistry and Interfacial Electrochemistry of Divalent Metal Batteries

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