An Ultrastable Presodiated Titanium Disulfide Anode for Aqueous “Rocking‐Chair” Zinc Ion Battery

Abstract

Rechargeable aqueous Zn‐based batteries are attractive candidates as energy storage technology, but the uncontrollable Zn dendrites, low stripping/plating coulombic efficiency, and inefficient utilization of Zn metal limit the battery reliability and energy density. Herein, for the first time, a novel presodiated TiS2 (Na0.14TiS2) is proposed and investigated as an intercalated anode for aqueous Zn‐ion batteries, showing a capacity of 140 mAh g−1 with a suitable potential of 0.3 V (vs Zn2+/Zn) at 0.05 A g−1 and superior cyclability of 77% retention over 5000 cycles at 0.5 A g−1. The remarkable performance originates from the buffer phase formation of Na0.14TiS2 after chemically presodiating TiS2, which not only improves the structural reversibility and stability but also enhances the diffusion coefficient and electronic conductivity, and lowers cation migration barrier, as evidenced by a series of experimental and theoretical studies. Moreover, an aqueous “rocking‐chair” Zn‐ion full battery is successfully demonstrated by this Na0.14TiS2 anode and ZnMn2O4 cathode, which delivers a capacity of 105 mAh g−1 (for anode) with an average voltage of 0.95 V at 0.05 A g−1 and preserves 74% retention after 100 cycles at 0.2 A g−1, demonstrating the feasibility of Zn‐ion full batteries for energy storage applications.

Rechargeable Aqueous Zinc‐Ion Batteries with Mild Electrolytes: A Comprehensive Review

“…[171,172] The corrosion reactions between Zn metal and aqueous electrolyte (e. g., 3 M ZnSO 4 ) is not uniform, and the deepest corrosion pit reached upto 130 μm after a dwell time of 30 days. [173] Even though some novel intercalation-type anodes have been suggested (such as Na 0.14 TiS 2 [174] and Chevrel phase Zn 2 Mo 6 S 8 ), [112,175] the majority of ZIBs still use excess-mass Zn metal as anodes (in forms of foil [176,177] or powders) [11,21,22,178] for ample Zn 2 + supply. It is worth noting that Zn anodes with excess-mass (or shallow depth of discharge, DOD) will obviously depress the energy density of a fully packaged ZIBs, due to the heavy anode design with inefficient Zn utilization.…”

“…Indeed, an adequate intercalation anode should meet quite a number of requirements, including decent capacity, high Coulombic efficiency, proper redox potential, stable cycling stability, and good rate capability. [174] The first reported Zn 2 + -intercalated anode is Chevrel-phase Mo 6 S 8 . [175,195] This material can reversibly intercalate Zn 2 + and successively transform into ZnMo 6 S 8 (at 0.6-0.7 V vs. Zn 2 + /Zn) and then to Zn 2 Mo 6 S 8 (at 0.3-0.4 V), in both aqueous and non-aqueous electrolytes, delivering a reversible capacity of~90 mAh g À 1 .…”

“…[196] The potential application of this anode has been demonstrated by constructing a Mo 6 S 8 -ZnI 2 flow cells with a zinc-polyiodide (I-/I 3À )-based catholytes. The impressive work by Li et al [174] shows that a layered sulfide, TiS 2 , can be converted into an excellent interaction anode for ZIBs after being pre-sodiated (i. e., Na 0.14 TiS ). The Na 0.14 TiS 2 anode can accommodate 140 mAh g À 1 of Zn 2 + (at 0.3 V vs. Zn 2 + /Zn and 0.05 A g À 1 ) with high cycling stability (77 % capacity retention over 5000 cycles at 0.5 A g À 1 ), a large capacity considering the relatively high mass loading of (5.7 mg cm À 2 ).…”

Development and challenges of aqueous rechargeable zinc batteries

“…已有的水系可充锌电池负极主要包括Zn-free负极 和 Z n 金 属 负 极 . Z n -f r e e 负 极 材 料 主 要 包 括 ZnMo 6 S 8 [154] 、Mo 6 S 8 [97] 和Na 0.14 TiS 2 [155] 等嵌入/脱出机 制的材料, 以及一些能与锌离子进行可逆配合的材料, 如9,10-蒽醌 [156] .…”

A Novel Aqueous Zinc‐Ion Hybrid Supercapacitor Based on TiS2 (De)Intercalation Battery‐Type Anode

“…Recently, TiS 2 was used as (de)intercalation anode material for zinc-ion battery. [26] TiS 2 showed a low insertion potential of 0.3 V (vs Zn 2+ /Zn) in aqueous electrolyte. Using TiS 2 for the anode of zinc-ion battery can effectively avoid generation of zinc dendrite and byproduct.…”