Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

Abstract

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g−1 and 96 mAh g−1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

Toward High‐Performance Hybrid Zn‐Based Batteries via Deeply Understanding Their Mechanism and Using Electrolyte Additive

“…Although similar Zn‐based batteries, including LiMn 2 O 4 /Zn, Li 3 V 2 (PO 4 ) 3 /Zn, and LiV 2 (PO 4 ) 3 /Zn batteries, have been reported before, there has been little work focused on exploring the operational mechanism of the hybrid ions involved in the reaction. Therefore, to deeply understand the operational mechanism, operando synchrotron XRD of the hybrid Zn/LFP battery was first conducted to study the LFP phase evolution during the charge–discharge process.…”

“…Recently, the hybrid Zn‐based batteries were designed using the conventional cathode materials for LIBs or sodium ions batteries (e.g., LiFePO 4 or Na 0.44 MnO 2 ) and Zn foil anode . Theoretically, this novel hybrid battery can not only avoid the sluggish Zn‐ion diffusion kinetics in the cathode materials, but also broaden the research field of aqueous batteries by shifting from a single‐ion to a double‐ion mechanism . Despite different hybrid Zn‐based systems with advanced performance have been proposed recently, their hybrid working mechanism is still confusing.…”

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

“…Aqueous rechargeable zinc-ion batteries (ZIBs) are developed as a battery system, in which low-cost, non-toxic, and naturally abundant zinc metal is used as an anode and environment-friendly neutral aqueous Zn 2+ -containing solution serves as electrolyte [8]. In recent years, a series of high-performance cathode materials for ZIBs have also been studied such as Prussian blue analog [9][10][11], vanadium oxides [12][13][14][15][16][17][18][19], manganese oxides [20][21][22][23][24][25][26][27][28], and some metal sulfides [29][30][31]. Among these materials, MnO 2 is particularly concerned for its high theoretical specific capacity, low cost, eco-friendliness, and diverse crystallographic polymorphs (e.g., α-MnO 2 , δ-MnO 2 , and γ-MnO 2 ) [27,28,32].…”

An Efficient Evaluation of F-doped Polyanion Cathode Materials with Long Cycle Life for Na-Ion Batteries Applications

“…The diffraction peaks of prepared materials were related to the NASICON structure of rhombohedral phase with space group of R-3c 25–27 . The refined unit cell lattice parameters are presented in Fig.…”