The Promise of Calcium Batteries: Open Perspectives and Fair Comparisons

Hosein, Ian D.

doi:10.1021/acsenergylett.1c00593

Cited by 61 publications

(65 citation statements)

References 50 publications

(96 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…Kinetically, owing to calcium's larger ionic radius (1.00 Å) than magnesium (0.72 Å), which is also similar to Na (1.02 Å), Ca 2+ may have faster diffusion in electrolytes due lower charge density and polarizing properties. There is particular interest in the development of calcium metal batteries, 1,[4][5][6] owing to its potential to achieve similar performance figure of merits as incumbent Li-ion technology. 7 A crucial bottleneck to developing rechargeable Ca metal batteries is the lack of suitable electrolytes, [8][9] as has been the case for many multivalent systems, 10 that can simultaneously satisfy conditions such as : i) exhibit high ionic conductivity and transference number, both of which depend upon the solubility of the salt in the solvent, ii) allow facile desolvation of solvated cations ions in a reversible manner, which is connected to the nature of the salt anion, extent of ion-pairing, and stability of the coordinated complexes, iii) possess a wide electrochemical stability window, and iv) must be stable against metallic calcium to minimize side reactions and decomposition.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Biria

Pathreeker

Hosein

2021

Preprint

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4] Among various metals, calcium exhibits a theoretical redox potential slightly above those of Li and K, and a large capacity of 1337 mAh g À1 and 2072 mAh cm À3 . [5][6][7][8] Ca-ion also offers a charge number doubled that of an alkaline metal ion and favorable polarization much lower than other multivalent metal ions (Mg 2þ , Al 3þ ), which contribute to fast and efficient charge transport. [7,9] In addition, the cost of Ca resource is merely one-eighth of that for Li owing to calcium as the third most abundant metal element in the Earth's crust.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7][8] Ca-ion also offers a charge number doubled that of an alkaline metal ion and favorable polarization much lower than other multivalent metal ions (Mg 2þ , Al 3þ ), which contribute to fast and efficient charge transport. [7,9] In addition, the cost of Ca resource is merely one-eighth of that for Li owing to calcium as the third most abundant metal element in the Earth's crust. [9] However, only recent years witnessed the fast development of Ca-metal batteries (CMBs), benefiting from the introduction and demonstration of a few calcium salts, which afford continuously plating and stripping of calcium in nonaqueous electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Current Status and Challenges of Calcium Metal Batteries

Song

Wang

2022

Adv Energy and Sustain Res

View full text Add to dashboard Cite

Ca‐metal batteries, one of the promising advanced energy storage devices, have received significant development in the last few years. However, challenges still exist in efficient and cost‐effective Ca‐metal utilization, fast Ca‐ion transport and diffusion, and high energy density and stable‐cycling Ca‐storage. Herein, by cross‐checking most relevant literature reported previously, an intuitive depiction for state‐of‐the‐art Ca‐metal batteries, including collectors, electrolytes, and cathode materials, is presented from a voltage‐capacity‐efficiency's view, which facilitates reasonable comparisons from related fields. The performance of most cathode materials and calcium‐metal electrodes in various electrolytes reported previously is comprehensively reviewed, as well as interphases and collectors. The strong and weak points of various electrolytes are discussed, and relevant challenges are pointed out. Recent breakthroughs in electrolyte and interphase engineering are emphasized. Finally, potential development directions for Ca‐metal and electrolytes, as well as some future prospects for cathode materials, are rationally predicted.

show abstract

“…Calcium batteries have emerged as a promising post-Li energy storage technology owing to its numerous benefits such as high energy density, competitive capacities and C-rates, vast and sustainable resource supply, low cost, and earth abundance. 1 However, one of the challenges with their development is the discovery of suitable electrolytes. The strong reducing nature of calcium metal renders many solvents unstable, and likewise many electrolyte systems can decompose into products that passivate the metal surface, thereby shutting down Ca redox kinetics.…”

Section: Introductionmentioning

confidence: 99%

Why Is Tetrahydrofuran a Good Solvent for Calcium Batteries? Insights From Ab Initio Molecular Dynamics Simulations

Pathreeker

Hosein

2021

Preprint

View full text Add to dashboard Cite

Calcium batteries are rapidly emerging as a potential, future energy storage technology; however, their advancement relies heavily on understanding of the liquid electrolyte component in terms of stability and interactions with a calcium metal anode. Tetrahydrofuran, a cyclic ether, is an experimentally common and promising solvent for the preparation of stable and efficient calcium electrolytes. However, insights into the reasons why are lacking, which could unveil key principles to electrolyte design. In this report, we provide a theoretical study employing ab initio molecular dynamics (AIMD) simulations of the interactions of Ca metal with the cyclic ether tetrahydrofuran (THF). The results show that the electrochemical breakdown and decomposition of THF at the Ca surface is highly orientation- and surface-site dependent, thereby significantly reducing the likelihood of its instability in a randomly organized bulk solvent. Likewise, in bulk electrolytes, its likelihood for breakdown is further diminished, in preference for coordination Ca2+ to form solvated structure. Hence, the finding that molecules require such strict conditions for their decomposition is an important selection and design principle for any solvent to prepare suitable calcium electrolytes. These findings are critical to the advancement of the calcium batteries.

show abstract

The Promise of Calcium Batteries: Open Perspectives and Fair Comparisons

Cited by 61 publications

References 50 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

Current Status and Challenges of Calcium Metal Batteries

Why Is Tetrahydrofuran a Good Solvent for Calcium Batteries? Insights From Ab Initio Molecular Dynamics Simulations

Contact Info

Product

Resources

About