This study explores the development of calcium-ion batteries (CIBs) by focusing on the design of a novel electrolyte to overcome key challenges, such as poor calcium plating/stripping. Hydrated vanadium pentoxide (H-V2O5) served as the cathode, and graphite acted as the anode. Tricalcium dicitrate tetrahydrate (Ca-citrate) salt was used for the first time in an ethylene carbonate/propylene carbonate (EC/PC) solvent system. Ca-citrate showed marked improvement in ionic conductivity (up to 2.6 × 10−1 S/cm) and electrochemical stability (~6 V) relative to traditional Ca-nitrate (2.5 V) and also displayed better capacity retention. To solve the solubility limitations of Ca-citrate in EC/PC, highly diluted (0.001 M) solution of EC/PC and modified electrolytes with cosolvents like poly(ethylene glycol) 200 (PEG 200) and trifluoroacetic anhydride (TFA) were studied. PEG 200 increased solubility and stability through hydrogen bonding, while TFA increased ionic mobility but decreased electrochemical stability. The PEG-modified electrolyte achieved a stability window of ~4 V with a charge/discharge capacity of ~198 mAh/g. Additionally, using ethylene glycol (EG) as an alternative solvent increased the electrochemically reversible, soluble, and capacitive Ca-citrate (up to 708 mAh/g, 85 mA/g). EG-based electrolyte showed high columbic efficiency (~99%–100%) and stable interfacial behavior.
| [1] |
S. Kim, L. Yin, M. H. Lee, et al., “High-Voltage Phosphate Cathodes for Rechargeable Ca-Ion Batteries,” ACS Energy Letters5 (2020): 3203-3211, https://doi.org/10.1021/acsenergylett.0c01663.
|
| [2] |
E. Kohan, R. Khoshnavazi, M. G. Hosseini, A. Salimi, and M. Salami-Kalajahi, “A Review on Instability Factors of Mono- and Divalent Metal Ion Batteries: From Fundamentals to Approaches,” Journal of Materials Chemistry A12 (2024): 30190-30248, https://doi.org/10.1039/D4TA05386A.
|
| [3] |
A. El Kharbachi, O. Zavorotynska, M. Latroche, F. Cuevas, V. Yartys, and M. Fichtner, “Exploits, Advances and Challenges Benefiting Beyond Li-Ion Battery Technologies,” Journal of Alloys and Compounds817 (2020): 153261, https://doi.org/10.1016/j.jallcom.2019.153261.
|
| [4] |
K. Fan, Y. Ying, X. Li, X. Luo, and H. Huang, “Theoretical Investigation of V3C2 MXene as Prospective High-Capacity Anode Material for Metal-Ion (Li, Na, K, and Ca) Batteries,” Journal of Physical Chemistry C123 (2019): 18207-18214, https://doi.org/10.1021/acs.jpcc.9b03963.
|
| [5] |
Y. Liang, H. Dong, D. Aurbach, and Y. Yao, “Current Status and Future Directions of Multivalent Metal-Ion Batteries,” Nature Energy5 (2020): 646-656, https://doi.org/10.1038/s41560-020-0655-0.
|
| [6] |
Q. Wei, L. Zhang, X. Sun, and T. L. Liu, “Progress and Prospects of Electrolyte Chemistry of Calcium Batteries,” Chemical Science13 (2022): 5797-5812, https://doi.org/10.1039/d2sc00267a.
|
| [7] |
M. Wang, C. Jiang, S. Zhang, X. Song, Y. Tang, and H. M. Cheng, “Reversible Calcium Alloying Enables a Practical Room-Temperature Rechargeable Calcium-Ion Battery With a High Discharge Voltage,” Nature Chemistry10 (2018): 667-672, https://doi.org/10.1038/s41557-018-0045-4.
|
| [8] |
A. Ponrouch, D. Tchitchekova, C. Frontera, F. Bardé, M. E. A. Dompablo, and M. R. Palacín, “Assessing Si-Based Anodes for Ca-Ion Batteries: Electrochemical Decalciation of CaSi2,” Electrochemistry Communications66 (2016): 75-78, https://doi.org/10.1016/j.elecom.2016.03.004.
|
| [9] |
A. Ponrouch and M. R. Palacin, “On the Road Toward Calcium-Based Batteries,” Current Opinion in Electrochemistry9 (2018): 1-7, https://doi.org/10.1016/j.coelec.2018.02.001.
|
| [10] |
L. Stievano, I. de Meatza, J. Bitenc, C. Cavallo, S. Brutti, and M. A. Navarra, “Emerging Calcium Batteries,” Journal of Power Sources482 (2021): 228875, https://doi.org/10.1016/j.jpowsour.2020.228875.
|
| [11] |
M. Li, J. Lu, X. Ji, et al., “Design Strategies for Nonaqueous Multivalent-Ion and Monovalent-Ion Battery Anodes,” Nature Reviews Materials5 (2020): 276-294, https://doi.org/10.1038/s41578-019-0166-4.
|
| [12] |
F. S. Genier, C. V. Burdin, S. Biria, and I. D. Hosein, “A Novel Calcium-Ion Solid Polymer Electrolyte Based on Crosslinked Poly(Ethylene Glycol) Diacrylate,” Journal of Power Sources414 (2019): 302-307, https://doi.org/10.1016/j.jpowsour.2019.01.017.
|
| [13] |
H. Tran, T. Mehta, M. Zeller, and R. H. Jarman, “Synthesis and Characterization of Mixed Phases in the Ca–Co–O System Using the Pechini Method,” Materials Research Bulletin48 (2013): 2450-2456, https://doi.org/10.1016/j.materresbull.2013.02.060.
|
| [14] |
R. J. Staniewicz, “A Study of the Calcium-Thionyl Chloride,” Journal of the Electrochemical Society127 (1980): 782-789, https://doi.org/10.1149/1.2129758.
|
| [15] |
A. Ponrouch, D. Tchitchekova, C. Frontera, F. Bardé, M. E. A. Dompablo, and M. R. Palacín, “Assessing Si-Based Anodes for Ca-Ion Batteries: Electrochemical Decalciation of CaSi2,” Electrochemistry Communications66 (2016): 75-78, https://doi.org/10.1016/j.elecom.2016.03.004.
|
| [16] |
D. Aurbach, R. Skaletsky, and Y. Gofer, “The Electrochemical Behavior of Calcium Electrodes in a Few Organic Electrolytes,” Journal of the Electrochemical Society138 (1991): 3536-3545, https://doi.org/10.1149/1.2085455.
|
| [17] |
N. T. Hahn, S. A. McClary, A. T. Landers, and K. R. Zavadil, “Efficacy of Stabilizing Calcium Battery Electrolytes Through Salt-Directed Coordination Change,” Journal of Physical Chemistry C126 (2022): 10335-10345, https://doi.org/10.1021/acs.jpcc.2c02587.
|
| [18] |
K. Xu, “Electrolytes and Interphases in Li-Ion Batteries and Beyond,” Chemical Reviews114 (2014): 11503-11618, https://doi.org/10.1021/cr500003w.
|
| [19] |
Y. Zhao, A. Wang, L. Ren, X. Liu, and J. Luo, “Revealing the Solid Electrolyte Interface on Calcium Metal Anodes,” Journal of Energy Chemistry70 (2022): 174-190, https://doi.org/10.1016/j.jechem.2022.02.022.
|
| [20] |
M. Cabello, F. Nacimiento, J. R. González, et al., “Advancing Towards a Veritable Calcium-Ion Battery: CaCo2O4 Positive Electrode Material,” Electrochemistry Communications67 (2016): 59-64, https://doi.org/10.1016/j.elecom.2016.03.016.
|
| [21] |
D. S. Tchitchekova, C. Frontera, A. Ponrouch, C. Krich, F. Bardé, and M. R. Palacín, “Electrochemical Calcium Extraction From 1D-Ca3Co2O6,” Dalton Transactions47 (2018): 11298-11302, https://doi.org/10.1039/c8dt01754a.
|
| [22] |
A. Torres, F. Bardé, and M. E. Arroyo-de Dompablo, “Evaluation of Cobalt Oxides for Calcium Battery Cathode Applications,” Solid State Ionics340 (2019): 115004, https://doi.org/10.1016/j.ssi.2019.115004.
|
| [23] |
M. S. Chae, H. H. Kwak, and S.-T. Hong, “Calcium Molybdenum Bronze as a Stable High-Capacity Cathode Material for Calcium-Ion Batteries,” ACS Applied Energy Materials3 (2020): 5107-5112, https://doi.org/10.1021/acsaem.0c00567.
|
| [24] |
M. E. Arroyo-de Dompablo, C. Krich, J. Nava-Avendaño, M. R. Palacín, and F. Bardé, “In Quest of Cathode Materials for Ca Ion Batteries: The CaMo3 Perovskites (M = Mo, Cr, Mn, Fe, Co, and Ni),” Physical Chemistry Chemical Physics18 (2016): 19966-19972, https://doi.org/10.1039/c6cp03381d.
|
| [25] |
L. Liu, Y. C. Wu, P. Rozier, P. L. Taberna, and P. Simon, “Ultrafast Synthesis of Calcium Vanadate for Superior Aqueous Calcium-Ion Battery,” Research2019 (2019): 6585686, https://doi.org/10.34133/2019/6585686.
|
| [26] |
B. Jeon, H. H. Kwak, and S.-T. Hong, “Bilayered Ca0.28V2O5·H2O: High-Capacity Cathode Material for Rechargeable Ca-Ion Batteries and Its Charge Storage Mechanism,” Chemistry of Materials34 (2022): 1491-1498, https://doi.org/10.1021/acs.chemmater.1c02774.
|
| [27] |
W. Lu, J. Wang, G. Sai Gautam, and P. Canepa, “Searching Ternary Oxides and Chalcogenides as Positive Electrodes for Calcium Batteries,” Chemistry of Materials33 (2021): 5809-5821, https://doi.org/10.1021/acs.chemmater.1c01992.
|
| [28] |
J. Wang, J. Wang, Y. Jiang, et al., “CaV6O16·2.8H2O With Ca2+ Pillar and Water Lubrication as a High-Rate and Long-Life Cathode Material for Ca-Ion Batteries,” Advanced Functional Materials32 (2022): 2113030, https://doi.org/10.1002/adfm.202113030.
|
| [29] |
A. L. Lipson, B. Pan, S. H. Lapidus, C. Liao, J. T. Vaughey, and B. J. Ingram, “Rechargeable Ca-Ion Batteries: A New Energy Storage System,” Chemistry of Materials27 (2015): 8442-8447, https://doi.org/10.1021/acs.chemmater.5b04027.
|
| [30] |
T. Shiga, H. Kondo, Y. Kato, and M. Inoue, “Insertion of Calcium Ion Into Prussian Blue Analogue in Nonaqueous Solutions and Its Application to a Rechargeable Battery With Dual Carriers,” Journal of Physical Chemistry C119 (2015): 27946-27953, https://doi.org/10.1021/acs.jpcc.5b10245.
|
| [31] |
M. Adil, A. Sarkar, A. Roy, M. R. Panda, A. Nagendra, and S. Mitra, “Practical Aqueous Calcium-Ion Battery Full-Cells for Future Stationary Storage,” ACS Applied Materials & Interfaces12 (2020): 11489-11503, https://doi.org/10.1021/acsami.9b20129.
|
| [32] |
S. Gheytani, Y. Liang, F. Wu, et al., “An Aqueous Ca-Ion Battery,” Advanced Science4 (2017): 1700465, https://doi.org/10.1002/advs.201700465.
|
| [33] |
Z. Meng, A. Reupert, Y. Tang, et al., “Long-Cycle-Life Calcium Battery With a High-Capacity Conversion Cathode Enabled by a Ca2+/Li+ Hybrid Electrolyte,” ACS Applied Materials & Interfaces14 (2022): 54616-54622, https://doi.org/10.1021/acsami.2c11337.
|
| [34] |
D. S. Tchitchekova, A. Ponrouch, R. Verrelli, et al., “Electrochemical Intercalation of Calcium and Magnesium in TiS2: Fundamental Studies Related to Multivalent Battery Applications,” Chemistry of Materials30 (2018): 847-856, https://doi.org/10.1021/acs.chemmater.7b04406.
|
| [35] |
J. Bitenc, A. Scafuri, K. Pirnat, et al., “Electrochemical Performance and Mechanism of Calcium Metal-Organic Battery,” Batteries & Supercaps4 (2020): 214-220, https://doi.org/10.1002/batt.202000197.
|
| [36] |
D. Bier, Z. Li, S. Klyatskaya, et al., “Long Cycle-Life Ca Batteries With Poly(Anthraquinonylsulfide) Cathodes and Ca-Sn Alloy Anodes,” Chemsuschem16 (2023): e202300932, https://doi.org/10.1002/cssc.202300932.
|
| [37] |
X. Liu, G. A. Elia, and S. Passerini, “Evaluation of Counter and Reference Electrodes for the Investigation of Ca Battery Materials,” Journal of Power Sources Advances2 (2020): 100008, https://doi.org/10.1016/j.powera.2020.100008.
|
| [38] |
J. Park, Z. L. Xu, G. Yoon, et al., “Stable and High-Power Calcium-Ion Batteries Enabled by Calcium Intercalation Into Graphite,” Advanced Materials32 (2020): e1904411, https://doi.org/10.1002/adma.201904411.
|
| [39] |
R. Cang, C. Zhao, K. Ye, et al., “Aqueous Calcium-Ion Battery Based on a Mesoporous Organic Anode and a Manganite Cathode With Long Cycling Performance,” Chemsuschem13 (2020): 3911-3918, https://doi.org/10.1002/cssc.202000812.
|
| [40] |
Z. Li, O. Fuhr, M. Fichtner, and Z. Zhao-Karger, “Towards Stable and Efficient Electrolytes for Room-Temperature Rechargeable Calcium Batteries,” Energy & Environmental Science12 (2019): 3496-3501, https://doi.org/10.1039/c9ee01699f.
|
| [41] |
A. Shyamsunder, L. E. Blanc, A. Assoud, and L. F. Nazar, “Reversible Calcium Plating and Stripping at Room Temperature Using a Borate Salt,” ACS Energy Letters4 (2019): 2271-2276, https://doi.org/10.1021/acsenergylett.9b01550.
|
| [42] |
P. Peljo and H. H. Girault, “Electrochemical Potential Window of Battery Electrolytes: The HOMO–LUMO Misconception,” Energy & Environmental Science11 (2018): 2306-2309, https://doi.org/10.1039/C8EE01286E.
|
| [43] |
N. Kumar and D. J. Siegel, “Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries,” Journal of Physical Chemistry Letters7 (2016): 874-881, https://doi.org/10.1021/acs.jpclett.6b00091.
|
| [44] |
J. B. Goodenough and Y. Kim, “Challenges for Rechargeable Li Batteries,” Chemistry of Materials22 (2010): 587-603, https://doi.org/10.1021/cm901452z.
|
| [45] |
J. Wang, J. Wang, Y. Jiang, et al., “CaV6O16 2.8 H2O With Ca2+ Pillar and Water Lubrication as a High-Rate and Long-Life Cathode Material for Ca-Ion Batteries,” Advanced Functional Materials32 (2022): 2113030, https://doi.org/10.1002/adfm.202113030.
|
| [46] |
Z. L. Xu, J. Park, J. Wang, et al., “A New High-Voltage Calcium Intercalation Host for Ultra-Stable and High-Power Calcium Rechargeable Batteries,” Nature Communications12 (2021): 3369, https://doi.org/10.1038/s41467-021-23703-x.
|
| [47] |
M. Adil, A. Ghosh, and S. Mitra, “Water-in-Salt Electrolyte-Based Extended Voltage Range, Safe, and Long-Cycle-Life Aqueous Calcium-Ion Cells,” ACS Applied Materials & Interfaces14 (2022): 25501-25515, https://doi.org/10.1021/acsami.2c04742.
|
| [48] |
A. Taghavi-Kahagh, H. Roghani-Mamaqani, and M. Salami-Kalajahi, “Powering the Future: A Comprehensive Review on Calcium-Ion Batteries,” Journal of Energy Chemistry90 (2024): 77-97, https://doi.org/10.1016/j.jechem.2023.10.043.
|
RIGHTS & PERMISSIONS
2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.