Room Temperature Calcium-Ion Battery Enabled by Calcium Citrate as a Calcium Salt

IF 11.1
Ameneh Taghavi-Kahagh, Hossein Roghani-Mamaqani, Mehdi Salami-Kalajahi
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Abstract

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.

Abstract Image

以柠檬酸钙为钙盐的室温钙离子电池
本研究探讨了钙离子电池(cib)的发展,重点是设计一种新型电解质,以克服诸如钙镀层/剥离不良等关键挑战。水合五氧化钒(H-V₂O₅)作为阴极,石墨作为阳极。首次将柠檬酸三钙盐应用于碳酸乙烯/碳酸丙烯(EC/PC)溶剂体系中。与传统的硝酸钙(2.5 V)相比,柠檬酸钙的离子电导率(高达2.6 × 10−1 S/cm)和电化学稳定性(~6 V)有显著提高,并且具有更好的容量保持能力。为了解决柠檬酸钙在EC/PC中的溶解度限制,研究了EC/PC的高度稀释(0.001 M)溶液和用聚乙二醇200 (PEG 200)和三氟乙酸酐(TFA)等助溶剂修饰的电解质。PEG 200通过氢键作用提高了溶解度和稳定性,TFA提高了离子迁移率,但降低了电化学稳定性。peg修饰的电解质稳定窗口为~4 V,充放电容量为~198 mAh/g。此外,使用乙二醇(EG)作为替代溶剂增加了电化学可逆、可溶性和电容性柠檬酸钙(高达708 mAh/g, 85 mA/g)。电解质具有较高的柱效率(~99% ~ 100%)和稳定的界面行为。
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CiteScore
4.60
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