Assessing Si-based anodes for Ca-ion batteries: Electrochemical decalciation of CaSi2

Ponrouch, Alexandre; Tchitchekova, Deyana S.; Frontera, C.; Bardé, Fanny; Dompablo, M. Elena Arroyo-de; Palacín, M. Rosa

doi:10.1016/j.elecom.2016.03.004

Cited by 64 publications

(44 citation statements)

References 16 publications

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“…Attractive electrochemical capacities may also be possible using alloy‐based anode materials. Ponrouch et al investigated the feasibility of using Ca–Si intermetallic alloys as anodes for CIBs with an attractive maximum theoretical capacity of 991 mAh g −1 for the reaction of 1 mol fcc–Si with 2 mol of Ca ions. As a first step in the examination of the feasibility of Ca–Si alloy anodes they investigated the commercially available Ca–Si alloy CaSi 2 .…”

Section: Anodes For Nonaqueous Ca‐ion Batteriesmentioning

confidence: 99%

“…Nanostructuring and Temperature Elevation : Two further ways of improving the performance of multivalent ion insertion electrodes are the use of nanostructured materials to reduce the diffusion length from the electrode surface into the bulk[6b,41] and the elevation of the cell operating temperature. The use of elevated temperature cycling proved essential to the demonstration of reversible magnesium cycling in TiS 2 and thiospinels[23a] and also in the demonstration of reversible Ca plating in conventional electrolytes . However, the increased temperature of cell operation unfortunately also increases the kinetics of parasitic side reactions such as current collector corrosion and electrolyte breakdown …”

Section: Cathodes For Calcium‐ion Batteriesmentioning

confidence: 99%

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Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

et al. 2018

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Recent developments in rechargeable battery technology have seen a shift from the well-established Li-ion technology to new chemistries to achieve the high energy density required for extended range electric vehicles and other portable applications, as well as low-cost alternatives for stationary storage. These chemistries include Li-air, Li-S, and multivalent ion technologies including Mg , Zn , Ca , and Al . While Mg battery systems have been increasingly investigated in the last few years, Ca technology has only recently been recognized as a viable option. In this first comprehensive review of Ca ion technology, the use of Ca metal anodes, alternative alloy anodes, electrolytes suitable for this system, and cathode material development are discussed. The advantages and disadvantages of Ca ion batteries including prospective achievable energy density, cost reduction due to high natural abundance, low ion mobility, the effect of ion size, and the need for elevated temperature operation are reviewed. The use of density functional theory modeling to predict the properties of Ca-ion battery materials is discussed and the extent to which this approach is successful in directing research into areas of promise is evaluated. To conclude, a summary of recent achievements is presented and areas for future research efforts evaluated.

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Section: Anodes For Nonaqueous Ca‐ion Batteriesmentioning

confidence: 99%

Section: Cathodes For Calcium‐ion Batteriesmentioning

confidence: 99%

Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

et al. 2018

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“…Using a Sn anode and graphite cathode, Wang et al [14] recently reported a highvoltage (4.45 V) CIB cell with a reasonable capacity of 85 mAh g and a remarkable cyclability (95% capacity retention in 350 cycles). [13,14,30,31] All of them except Na have been reported to mix with Ca in wide composition ranges, forming various intermetallic compounds. [13,14,30,31] All of them except Na have been reported to mix with Ca in wide composition ranges, forming various intermetallic compounds.…”

Section: Introductionmentioning

confidence: 99%

“…Using a Sn anode and graphite cathode, Wang et al recently reported a high‐voltage (4.45 V) CIB cell with a reasonable capacity of 85 mAh g and a remarkable cyclability (95% capacity retention in 350 cycles). Besides Sn, several metals and metalloids including Zn, Al, Si, Li, and Na have also been investigated for the use of alloying‐type CIBs anodes with largely disparate capacities achieved . All of them except Na have been reported to mix with Ca in wide composition ranges, forming various intermetallic compounds .…”

Section: Introductionmentioning

confidence: 99%

Discovery of Calcium‐Metal Alloy Anodes for Reversible Ca‐Ion Batteries

Yao

Hegde

Aspuru‐Guzik

et al. 2019

Advanced Energy Materials

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techniques with high energy density and low cost. [1] Multivalent batteries, like Mg-ion, [2] Ca-ion, [3,4] and Al-ion batteries, [5,6] have the potential to realize significantly improved capacities, compared to monovalent batteries (e.g., Li-ion batteries), due to more electrons carried per ion. Among them, Ca-ion batteries (CIB) have drawn special attention with merits besides the capacity enhancement:(1) Ca/Ca 2+ has a reduction potential (−2.87 V) only slightly higher than Li/Li + (−3.04 V), yet much lower than Mg/Mg 2+ (−2.36 V) and Al/Al 3+ (−1.68 V), which provides CIB the prospect to function at voltages comparable with Li-ion batteries and much higher than the counterparts of Mg-ion and Al-ion batteries. [7,8] (2) Ca is the fifth most abundant element in the earth's crust with an extensive global resource distribution, in contrast to lithium. (3) The kinetics of Ca-ion in solid electrodes are faster than Mg-and Al-ions due to reduced charge density. [9][10][11] The development of CIBs was originally pioneered by the study of Ca-ion electrochemical intercalations into layered transition metal oxides and sulfides. [12] Subsequently, many efforts then were made to search for cathode materials which will tolerate a large amount of Ca-ions reversibly extracted/ re-accommodated upon charge/discharge. Material systems including Prussian blue compounds, [10,13,14] Chevrel phases, [15,16] spinels, [17][18][19] perovskites, [20] layered transition metal (TM) sulfides, [21] and iron phosphate, [22] were suggested to be effective Ca-ion electrodes with the spinels and perovskites attracting extra attention because of their predicted high voltage (>3.5 V) and large theoretical capacities (>240 mAh g −1 ) during discharge at room temperature. [17][18][19][20] Distinct from these TM-based electrodes, a graphite cathode has been reported which functions via the (de-)intercalation of electrolyte salt anions (A − = PF 6 − , ClO 4 − , and so on) upon charge/discharge at remarkably high voltages (4.5-5.6 V) [23,24] with a theoretical capacity as high as 372 mAh g −1 (corresponding to AC 6 ). [24,25] Yet, the practical capacity of batteries based on this material suffers from a large degradation (≈90 mAh g −1 ) as a result of the electrolyte decomposition under high voltage. [24] Unlike the continuous development of CIB cathode materials, studies focusing on anodes have been relatively scarce. Graphite-based CIB anodes have been shown to be problematic at room temperature due to difficulties related to the intercalation of calcium. [26] The pursuit of a calcium metal Ca-ion batteries (CIBs) show promise to achieve the high energy density required by emerging applications like electric vehicles because of their potentially improved capacities and high operating voltages. The development of CIBs is hindered by the failure of traditional graphite and calcium metal anodes due to the intercalation difficulty and the lack of efficient electrolytes. Recently, a high voltage (4.45 V) CIB cell using Sn as the anode has been reported...

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“…First principles calculations are a unique tool to accelerate the identification of materials which could sustain reversible intercalation reactions delivering high specific energy [9][10][11][12][13] . A recent computational investigation of spinel AM 2 as a potential electrode material for Ca ion batteries 14 .…”

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confidence: 99%

A Joint Computational and Experimental Evaluation of CaMn₂O₄ Polymorphs as Cathode Materials for Ca Ion Batteries

et al. 2016

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The identification of potential cathode materials is a must for the development of a new calcium-ion based battery technology. In this work, we have firstly explored the electrochemical behaviour of marokite-CaMn 2 O 4 but the experimental attempts to deinsert Ca ion from this compound failed. First principles calculations indicate that in terms of voltage and capacity, marokite-CaMn 2 O 4 could sustain reversible Ca deinsertion reactions; half decalciation is predicted at an average voltage of 3.7 V with a volume variation of 6%. However, the calculated barriers for Ca diffusion are too high (1 eV), in agreement with the observed difficulty to deinsert Ca ion from the marokite structure. We have extended the computational investigation to two other CaMn 2 O 4 polymorphs, the spinel and the CaFe 2 O 4 structural types. Full Ca extraction from these CaMn 2 O 4 polymorphs is predicted at an average voltage of 3.1 V, but with a large volume variation of around 20%. Structural factors limiting Ca diffusion in the three polymorphs are discussed and confronted with a previous computational investigation of the virtual-spinel [Ca] T [Mn 2 ] O O 4 . Regardless the potential interest of [Ca] T [Mn 2 ] O O 4 as cathode forCa ion batteries, calculations suggests that the synthesis of this compound would hardly be feasible. The present results unravel the bottlenecks associated to the design of feasible intercalation Ca electrode materials, and allow proposing guidelines for future research. IntroductionSecondary (i.e. rechargeable) batteries are a power source widely used in portable devices (such as personal computers, camcorders and cellular phones) and are also increasingly present in transport and stationary applications. While the current state-of-the-art technology is Li-ion, research efforts are intensified towards the development of alternative technologies to satisfy the ever increasing demands for enhanced energy density 1 . Indeed, the use of lithium metal anodes with high electrochemical capacities (3860 mAh/g) is only possible under certain specific conditions to avoid safety issues and the most used negative electrode material is graphite (372 mAh/g). Efforts to develop successful magnesium anodes (2210 mAh/g) have culminated in proof of concept of this technology. Yet, the high charge-to-radius ratio for magnesium ions has resulted only in very covalent hosts such as Mo 6 S 8-y Se y (y=1,2) Chevrel phases fulfilling the requirements to be used as cathode materials. 2 We have recently reported on the feasibility and reversibility of calcium plating in conventional alkyl carbonate electrolytes at moderate temperatures 3 which opens the way to the development of a new rechargeable battery technology using calcium anodes. This is especially attractive given the abundance of calcium on the earth crust 4 , the high capacity of calcium anodes (1340 mAh/g), its negative reduction potential (only 170 mV above that of lithium metal) and the lower charge to radius ratio for calcium ions which holds promise of better kin...

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Assessing Si-based anodes for Ca-ion batteries: Electrochemical decalciation of CaSi2

Cited by 64 publications

References 16 publications

Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

Discovery of Calcium‐Metal Alloy Anodes for Reversible Ca‐Ion Batteries

A Joint Computational and Experimental Evaluation of CaMn₂O₄ Polymorphs as Cathode Materials for Ca Ion Batteries

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Assessing Si-based anodes for Ca-ion batteries: Electrochemical decalciation of CaSi2

Cited by 64 publications

References 16 publications

Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

Calcium‐Ion Batteries: Current State‐of‐the‐Art and Future Perspectives

Discovery of Calcium‐Metal Alloy Anodes for Reversible Ca‐Ion Batteries

A Joint Computational and Experimental Evaluation of CaMn2O4 Polymorphs as Cathode Materials for Ca Ion Batteries

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A Joint Computational and Experimental Evaluation of CaMn₂O₄ Polymorphs as Cathode Materials for Ca Ion Batteries