Abstract:Aqueous zinc ion batteries (AZIBs) are receiving increasing attention for large-scale energy storage systems owing to their appealing features with intrinsic safety, low cost, and scalability. Unfortunately, the water-induced parasitic reactions and dendrite growth on the Zn anode severely impede the further development of AZIBs. Herein, a thiourea additive is introduced into ZnSO 4 electrolyte to construct unique metal-molecule interface for simultaneously regulating the Zn anode interface chemistry and the b… Show more
“…The 2 H chemical shift in D 2 O increased from 4.7015 to 4.7172 ppm with the addition of 2 m ZnSO 4 , suggesting the weaken OH bond with the D 2 O molecule due to the strong coordination between Zn 2+ and D 2 O ( Figure a). [ 15 ] Notably, with pure BC membrane and ZnHAP/BC separator added into the 2 m ZnSO 4 solution, the 2 H chemical shift increase to higher value of 4.7210 and 4.7192 ppm, indicating the formation of H‐bonds between BC and D 2 O, thus resulting in a weak interaction between Zn 2+ ions and water molecules and the restricted water reactivity. The H‐bond formation between the separator and H 2 O was also confirmed by the Raman spectra.…”
Uncontrollable dendrite growth and sluggish ion‐transport kinetics are considered as the main obstacles for the further development of high‐performance aqueous zinc ion batteries (AZIBs). Here, a nature‐inspired separator (ZnHAP/BC) is developed to tackle these issues via the hybridization of the biomass‐derived bacterial cellulose (BC) network and nano‐hydroxyapatite particles (HAP). The as‐prepared ZnHAP/BC separator not only regulates the desolvation process of the hydrated Zn2+ ions (Zn(H2O)62+) by suppressing the water reactivity through the surface functional groups, alleviating the water‐induced side‐reactions, but also boosts the ion‐transport kinetics and homogenize the Zn2+ flux, resulting in a fast and uniform Zn deposition. Remarkably, the Zn|Zn symmetric cell with ZnHAP/BC separator harvests a long‐term stability over 1600 h at 1 mA cm−2, 1 mAh cm−2 and endures stable cycling over 1025 and 611 h even at a high depth of discharge (DOD) of 50% and 80%, respectively. The Zn|V2O5 full cell with a low negative/positive (N/P) capacity ratio of 2.7 achieves a superior capacity retention of 82% after 2500 cycles at 10 A g−1. Furthermore, the Zn/HAP separator can be totally degraded within 2 weeks. This work develops a novel nature‐derived separator and provides insights in constructing functional separators toward sustainable and advanced AZIBs.
“…The 2 H chemical shift in D 2 O increased from 4.7015 to 4.7172 ppm with the addition of 2 m ZnSO 4 , suggesting the weaken OH bond with the D 2 O molecule due to the strong coordination between Zn 2+ and D 2 O ( Figure a). [ 15 ] Notably, with pure BC membrane and ZnHAP/BC separator added into the 2 m ZnSO 4 solution, the 2 H chemical shift increase to higher value of 4.7210 and 4.7192 ppm, indicating the formation of H‐bonds between BC and D 2 O, thus resulting in a weak interaction between Zn 2+ ions and water molecules and the restricted water reactivity. The H‐bond formation between the separator and H 2 O was also confirmed by the Raman spectra.…”
Uncontrollable dendrite growth and sluggish ion‐transport kinetics are considered as the main obstacles for the further development of high‐performance aqueous zinc ion batteries (AZIBs). Here, a nature‐inspired separator (ZnHAP/BC) is developed to tackle these issues via the hybridization of the biomass‐derived bacterial cellulose (BC) network and nano‐hydroxyapatite particles (HAP). The as‐prepared ZnHAP/BC separator not only regulates the desolvation process of the hydrated Zn2+ ions (Zn(H2O)62+) by suppressing the water reactivity through the surface functional groups, alleviating the water‐induced side‐reactions, but also boosts the ion‐transport kinetics and homogenize the Zn2+ flux, resulting in a fast and uniform Zn deposition. Remarkably, the Zn|Zn symmetric cell with ZnHAP/BC separator harvests a long‐term stability over 1600 h at 1 mA cm−2, 1 mAh cm−2 and endures stable cycling over 1025 and 611 h even at a high depth of discharge (DOD) of 50% and 80%, respectively. The Zn|V2O5 full cell with a low negative/positive (N/P) capacity ratio of 2.7 achieves a superior capacity retention of 82% after 2500 cycles at 10 A g−1. Furthermore, the Zn/HAP separator can be totally degraded within 2 weeks. This work develops a novel nature‐derived separator and provides insights in constructing functional separators toward sustainable and advanced AZIBs.
“…The adsorption of Ac − anions on the Zn anode could correspondingly reduce the population of OTF − anions in the vicinity of Zn anodes and thus limit the decomposition of OTF − anions. 37 Without the addition of acetate salt, substantial decomposition of OTF − anions could be evidenced by the formation of CF 3 , ZnF 2 , and ZnSO 3 /ZnSO 4 in X-ray photoelectron spectroscopy (XPS) (Figures 3d,e and S17a). However, the functions of decomposition products are highly correlated with the specific decomposition mechanism of OTF − anions in the electrolytes.…”
A robust solid electrolyte interface (SEI) is crucial to widen the electrochemical stability window of the electrolyte and enable sustainably stable electrode reactions in aqueous Zn ion batteries. Different from the SEI in nonaqueous electrolytes, it is of great importance to form a functional and stable SEI due to parasitic reactions with water in aqueous Zn ion batteries. However, the concrete SEI formation in aqueous electrolytes has been elusive so far. Here, we regulate and unravel the decomposition mechanisms of organic Zn salts at the Zn anode− electrolyte interface in the widely studied zinc triflate-based aqueous electrolytes. By introducing a buffering adsorption layer with an optimal concentration of acetate anions, the uncontrollable decomposition of organic zinc triflate salt is greatly inhibited on Zn anodes, resulting in a stable interface. The average Coulombic efficiency of the Zn anode thus can reach as high as 99.95% and stable cycling for 4200 h. With the cooperation of buffering adsorption layers, the tetraethyl ammonium trifluoromethanesulfonate additive as the decomposition promoter could further regulate the decomposition of triflate anions for the formation of robust SEI layers for Zn anodes in electrolytes with a dilute salt concentration. Zn−polyaniline (PANI) full cells demonstrate stable cycling with controlled N/P ratios in such electrolytes. This work proposes an insightful perspective on rational regulation of the decomposition pathway of electrolyte components by forming a stable electrode−electrolyte interface for improved electrochemical performance of aqueous Zn ion batteries.
“…Figure S3 shows the cyclic voltammetry (CV) profiles of the symmetric cells with the ABA@Zn anodes at various reaction times. The cathodic overpotential of CV reflects the nucleation barrier for Zn deposition, 27 and thus, it is used to determine the optimized ABA fabrication time. The Zn deposition overpotentials of different samples are listed in Figure S4.…”
Aqueous zinc batteries are appealing devices for cost-effective and environmentally sustainable energy storage. However, the critical issues of uncontrolled dendrite propagation and side reactions with Zn anodes have hindered their practical applications. Inspired by the functions of the rosin flux in soldering, an abietic acid (ABA) layer is fabricated on the surface of Zn anodes (ABA@Zn). The ABA layer protects the Zn anode from corrosion and the concomitant hydrogen evolution reaction. It also facilitates fast interfacial charge transfer and horizontal growth of the deposited Zn by reducing the surface tension of the Zn anode. Consequently, promoted redox kinetics and reversibility are simultaneously achieved by the ABA@Zn. It demonstrates stable Zn plating/stripping cycling over 5100 h and a high critical current of 8.0 mA cm −2 . Moreover, the assembled ABA@Zn|(NH 4 ) 2 V 6 O 16 full cell delivers outstanding long-term cycling stability with an 89% capacity retention after 3000 cycles. This work provides a straightforward yet effective solution to the key issues of aqueous zinc batteries.
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