Graphical Abstract

Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Search articles, authors, keywords, DOl and etc.
Recently, multivalent metal-ion batteries have attracted considerable interests on the merits of their natural abundance and multi- electron redox property. However, the development of Ca-ion battery is still in their preliminary stage because of the lack of suitable electrode material. The Ca-storage performance of the existing materials is still unsatisfactory with low capacity, poor cyclic stability, as well as sloping discharge profiles, which cannot provide stable energy output. In this work, transition metal oxide Sn-doped In2O3 (ITO) has been explored as the aqueous Ca-ion battery anode, which could deliver a high discharge capacity of 71.2 mAh·g-1 with an ultra-flat discharge voltage plateau. The Ca storage mechanism was revealed to be reversible conversion reaction based on ex-situ X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) characterizations. A flexible aqueous Ca-ion battery was subsequently assembled with zinc hexacyanoferrate (ZnHCF) cathode and ITO anode sandwiched by hydrogel electrolyte, which could deliver a high specific capacity of 75.3 mAh·g-1 at 0.4 A·g-1 with a flat output voltage plateau at around 0.8 V. The bendable and flexible Ca-ion battery with decent voltage output will pave the way for the energy storage devices towards practical applications in flexible and wearable electronics.
Li, C. W.; Zhang, Q. C.; Sun, J.; Li, T. T.; E, S. F.; Zhu, Z. Z.; He, B.; Zhou, Z. Y.; Li, Q. L.; Yao, Y. G. High-performance quasi-solid-state flexible aqueous rechargeable Ag-Zn battery based on metal-organic framework-derived Ag nanowires. ACS Energy Lett. 2018, 3, 2761- 2768.
Li, H. F.; Tang, Z. J.; Liu, Z. X.; Zhi, C. Y. Evaluating flexibility and wearability of flexible energy storage devices. Joule 2019, 3, 613-619.
Liu, Z. X.; Li, H. F.; Zhu, M. S.; Huang, Y.; Tang, Z. J.; Pei, Z. X.; Wang, Z. F.; Shi, Z. C.; Liu, J.; Huang, Y. et al. Towards wearable electronic devices: A quasi-solid-state aqueous lithium-ion battery with outstanding stability, flexibility, safety and breathability. Nano Energy 2018, 44, 164-173.
Zhang, L. Y.; Chen, L.; Zhou, X. F.; Liu, Z. P. Towards high- voltage aqueous metal-ion batteries beyond 1.5 V: The zinc/zinc hexacyanoferrate system. Adv. Energy Mater. 2015, 5, 1400930.
Chao, D. L.; Zhou, W. H.; Xie, F. X.; Ye, C.; Li, H.; Jaroniec, M.; Qiao, S. Z. Roadmap for advanced aqueous batteries: From design of materials to applications. Sci. Adv. 2020, 6, eaba4098.
Yang, W. H.; Du, X. F.; Zhao, J. W.; Chen, Z.; Li, J. J.; Xie, J.; Zhang, Y. J.; Cui, Z. L.; Kong, Q. Y.; Zhao, Z. M. et al. Hydrated eutectic electrolytes with ligand-oriented solvation shells for long-cycling zinc-organic batteries. Joule 2020, 4, 1557-1574.
Ma, L. T.; Chen, S. M.; Long, C. B.; Li, X. L.; Zhao, Y. W.; Liu, Z. X.; Huang, Z. D.; Dong, B. B.; Zapien, J. A.; Zhi, C. Y. Achieving high- voltage and high-capacity aqueous rechargeable zinc ion battery by incorporating two-species redox reaction. Adv. Energy Mater. 2019, 9, 1902446.
Xie, J.; Yu, F.; Zhao, J. W.; Guo, W.; Zhang, H. L.; Cui, G. L.; Zhang, Q. C. An irreversible electrolyte anion-doping strategy toward a superior aqueous Zn-organic battery. Energy Storage Mater. 2020, 33, 283-289.
Gao, Y. N.; Yang, H. Y.; Wang, X. R.; Bai, Y.; Zhu, N.; Guo, S. N.; Suo, L. M.; Li, H.; Xu, H. J.; Wu, C. The compensation effect mechanism of Fe-Ni mixed prussian blue analogues in aqueous rechargeable aluminum-ion batteries. ChemSusChem 2020, 13, 732-740.
Adil, M.; Sarkar, A.; Roy, A.; Panda, M. R.; Nagendra, A.; Mitra, S. Practical aqueous calcium-ion battery full-cells for future stationary storage. ACS Appl. Mater. Interfaces 2020, 12, 11489-11503.
Wang, F.; Fan, X. L.; Gao, T.; Sun, W.; Ma, Z. H.; Yang, C. Y.; Han, F. D.; Xu, K.; Wang, C. S. High-voltage aqueous magnesium ion batteries. ACS Cent. Sci. 2017, 3, 1121-1128.
Wang, P. P.; Chen, Z.; Wang, H.; Ji, Z. Y.; Feng, Y. P.; Wang, J. Q.; Liu, J.; Hu, M. M.; Fei, J. B.; Gan, W. et al. A high-performance flexible aqueous Al ion rechargeable battery with long cycle life. Energy Storage Mater. 2020, 25, 426-435.
Li, Z. Y.; Vinayan, B. P.; Jankowski, P.; Njel, C.; Roy, A.; Vegge, T.; Maibach, J.; Lastra, J. M. G.; Fichtner, M.; Zhao-Karger, Z. Multi-electron reactions enabled by anion-based redox chemistry for high-energy multivalent rechargeable batteries. Angew. Chem. , Int. Ed. 2020, 59, 11483-11490.
Ma, L. T.; Li, X. L.; Zhang, G. B.; Huang, Z. D.; Han, C. P.; Li, H. F.; Tang, Z. J.; Zhi, C. Y. Initiating a wearable solid-state Mg hybrid ion full battery with high voltage, high capacity and ultra-long lifespan in air. Energy Storage Mater. 2020, 31, 451-458.
Ponrouch, A.; Frontera, C.; Bardé, F.; Palacín, M. R. Towards a calcium-based rechargeable battery. Nat. Mater. 2016, 15, 169-172.
Wang, M.; Jiang, C. L.; Zhang, S. Q.; Song, X. H.; Tang, Y. B.; Cheng, H. M. Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage. Nat. Chem. 2018, 10, 667-672.
Wu, N. Z.; Yao, W. J.; Song, X. H.; Zhang, G.; Chen, B. J.; Yang, J. H.; Tang, Y. B. A calcium-ion hybrid energy storage device with high capacity and long cycling life under room temperature. Adv. Energy Mater. 2019, 9, 1803865.
Arroyo-de Dompablo, M. E.; Ponrouch, A.; Johansson, P.; Palacín, M. R. Achievements, challenges, and prospects of calcium batteries. Chem. Rev. 2020, 120, 6331-6357.
Lang, J. H.; Jiang, C. L.; Fang, Y.; Shi, L.; Miao, S. J.; Tang, Y. B. Room-temperature rechargeable Ca-ion based hybrid batteries with high rate capability and long-term cycling life. Adv. Energy Mater. 2019, 9, 1901099.
Ji, B. F.; He, H. Y.; Yao, W. J.; Tang, Y. B. Recent advances and perspectives on calcium-ion storage: Key materials and devices. Adv. Mater. 2021, 33, 2005501.
Vo, T. N.; Hur, J.; Kim, I. T. Enabling high performance calcium-ion batteries from prussian blue and metal-organic compound materials. ACS Sustain. Chem. Eng. 2020, 8, 2596-2601.
Adil, M.; Dutta, P. K.; Mitra, S. An aqueous Ca-ion full cell comprising BaHCF cathode and MCMB anode. ChemistrySelect 2018, 3, 3687-3690.
Lee, C.; Jeong, S. K. A novel strategy to improve the electrochemical performance of a prussian blue analogue electrode for calcium-ion batteries. Electrochemistry 2018, 86, 134-137.
Tojo, T.; Sugiura, Y.; Inada, R.; Sakurai, Y. Reversible calcium ion batteries using a dehydrated prussian blue analogue cathode. Electrochim. Acta 2016, 207, 22-27.
Kuperman, N.; Padigi, P.; Goncher, G.; Evans, D.; Thiebes, J.; Solanki, R. High performance prussian blue cathode for nonaqueous Ca-ion intercalation battery. J. Power Sources 2017, 342, 414-418.
Xu, X. M.; Xiong, F. Y.; Meng, J. S.; Wang, X. P.; Niu, C. J.; An, Q. Y.; Mai, L. Q. Vanadium-based nanomaterials: A promising family for emerging metal-ion batteries, Adv. Funct. Mater. 2020, 30, 1904398.
Nolis, G. M.; Adil, A.; Yoo, H. D.; Hu, L. H.; Bayliss, R. D.; Lapidus, S. H.; Berkland, L.; Phillips, P. J.; Freeland, J. W.; Kim, C. et al. Electrochemical reduction of a spinel-type manganese oxide cathode in aqueous electrolytes with Ca2+ or Zn2+. J. Phys. Chem. C 2018, 122, 4182-4188.
Wang, J. J.; Tan, S. S.; Xiong, F. Y.; Yu, R. H.; Wu, P. J.; Cui, L. M.; An, Q. Y. VOPO4·2H2O as a new cathode material for rechargeable Ca-ion batteries. Chem. Commun. 2020, 56, 3805-3808.
Xie, J.; Zhang, Q. C. Recent progress in multivalent metal (Mg, Zn, Ca, and Al) and metal-ion rechargeable batteries with organic materials as promising electrodes. Small 2019, 15, 1805061.
Hyoung, J.; Heo, J. W.; Hong, S. T. Investigation of electrochemical calcium-ion energy storage mechanism in potassium birnessite. J. Power Sources 2018, 390, 127-133.
Xu, X. M.; Duan, M. Y.; Yue, Y. F.; Li, Q.; Zhang, X.; Wu, L.; Wu, P. J.; Song, B.; Mai, L. Q. Bilayered Mg0.25V2O5·H2O as a stable cathode for rechargeable Ca-ion batteries. ACS Energy Lett. 2019, 4, 1328-1335.
Liu, Z. X.; Huang, Y.; Huang, Y.; Yang, Q.; Li, X. L.; Huang, Z. D.; Zhi, C. Y. Voltage issue of aqueous rechargeable metal-ion batteries. Chem. Soc. Rev. 2020, 49, 180-232.
Liu, Z. X.; Yang, Q.; Wang, D. H.; Liang, G. J.; Zhu, Y. H.; Mo, F. N.; Huang, Z. D.; Li, X. L.; Ma, L. T.; Tang, T. C. et al. A flexible solid-state aqueous zinc hybrid battery with flat and high-voltage discharge plateau. Adv. Energy Mater. 2019, 9, 1902473.
Zhao, Q.; Huang, W. W.; Luo, Z. Q.; Liu, L. J.; Lu, Y.; Li, Y. X.; Li, L.; Hu, J. Y.; Ma, H.; Chen, J. High-capacity aqueous zinc batteries using sustainable quinone electrodes, Sci. Adv. 2018, 4, eaao1761.
Chen, Z.; Wang, P. P.; Ji, Z. Y.; Wang, H.; Liu, J.; Wang, J. Q.; Hu, M. M.; Huang, Y. High-voltage flexible aqueous Zn-ion battery with extremely low dropout voltage and super-flat platform. Nano-Micro Lett. 2020, 12, 75.
Alsaif, M. M. Y. A.; Kuriakose, S.; Walia, S.; Syed, N.; Jannat, A.; Zhang, B. Y.; Haque, F.; Mohiuddin, M.; Alkathiri, T.; Pillai, N. et al. 2D SnO/In2O3 van der waals heterostructure photodetector based on printed oxide skin of liquid metals. Adv. Mater. Inter. 2019, 6, 1900007.
Reddy, I. N.; Reddy, C. V.; Cho, M.; Shim, J.; Kim, D. Structural, optical and XPS study of thermal evaporated In2O3 thin films. Mater. Res. Express 2017, 4, 086406.
Lou, S. F.; Cheng, X. Q.; Gao, J. L.; Li, Q.; Wang, L.; Cao, Y.; Ma, Y. L.; Zuo, P. J.; Gao, Y. Z.; Du, C. Y. et al. Pseudocapacitive Li+ intercalation in porous Ti2Nb10O29 nanospheres enables ultra-fast lithium storage. Energy Storage Mater. 2018, 11, 57-66.
Ho, W. H.; Li, C. F.; Liu, H. C.; Yen, S. K. Electrochemical performance of In2O3 thin film electrode in lithium cell. J. Power Sources 2008, 175, 897-902.
Niu, L.; Chen, L.; Zhang, J.; Jiang, P.; Liu, Z. P. Revisiting the open- framework zinc hexacyanoferrate: The role of ternary electrolyte and sodium-ion intercalation mechanism. J. Power Sources 2018, 380, 135-141.
Chen, L.; Bao, J. L.; Dong, X.; Truhlar, D. G.; Wang, Y.; Wang, C.; Xia, Y. Aqueous Mg-ion battery based on polyimide anode and prussian blue cathode. ACS Energy Lett. 2017, 2, 1115-1121.
Pang, Q.; Sun, C. L.; Yu, Y. H.; Zhao, K. N.; Zhang, Z. Y.; Voyles, P. M.; Chen, G.; Wei, Y. J.; Wang, X. D. H2V3O8 nanowire/graphene electrodes for aqueous rechargeable zinc ion batteries with high rate capability and large capacity. Adv. Energy Mater. 2018, 8, 1800144.