Synergetic modulation on ionic association and solvation structure by electron-withdrawing effect for aqueous zinc-ion batteries.

Aqueous zinc-ion batteries are emerging as one of the most promising large-scale energy storage systems due to their low cost and high safety. However, Zn anodes often encounter the problems of Zn dendrite growth, hydrogen evolution reaction, and formation of by-products. Herein, we developed the low ionic association electrolytes (LIAEs) by introducing 2, 2, 2-trifluoroethanol (TFE) into 30 m ZnCl2 electrolyte. Owing to the electron-withdrawing effect of -CF3 groups in TFE molecules, in LIAEs, the Zn2+ solvation structures convert from larger aggregate clusters into smaller parts and TFE will construct H-bonds with H2O in Zn2+ solvation structure simultaneously. Consequently, ionic migration kinetics are significantly enhanced and the ionization of solvated H2O is effectively suppressed in LIAEs. As a result, Zn anodes in LIAE display a fast plating/stripping kinetics and high Coulombic efficiency of 99.74%. The corresponding full batteries exhibit an improved comprehensive performance such as high-rate capability and long cycling life.

Towards More Sustainable Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are considered as the promising candidates for large-scale energy storage because of their high safety, low cost and environmental benignity. The large-scale applications of AZIBs will inevitably result in a large amount of spent AZIBs, which not only induce the waste of resources, but also pose environmental risks. Therefore, sustainable AZIBs have to be considered to minimize the risk of environmental pollution and maximize the utilization of spent compounds. Herein, this minireview focuses on the sustainability of AZIBs from material design and recycling techniques. The structure and degradation mechanism of AZIBs are discussed to guide the recycling design of the materials. Subsequently, the sustainability of component materials in AZIBs is further analysed to pre-evaluate their recycling behaviors and mentor the selection of more sustainable component materials, including active materials in cathodes, Zn anodes, and aqueous electrolytes, respectively. According to the features of component materials, corresponding green and economic approaches are further proposed to realize the recycling of active materials in cathodes, Zn anodes and electrolytes, respectively. These advanced technologies endow the recycling of component materials with high efficiency and a closed-loop control, ensuring that AZIBs will be the promising candidates of sustainable energy storage devices. This review will offer insight into potential future directions in the design of sustainable AZIBs.

The Construction of Anion-Induced Solvation Structures in Low-concentration Electrolyte for Stable Zinc Anodes.

Aqueous zinc-ion batteries (ZIBs) are promising large-scale energy storage devices because of their low cost and high safety. However, owing to the high activity of H2O molecules in electrolytes, hydrogen evolution reaction and side reactions usually take place on Zn anodes. Herein, additive-free PCA-Zn electrolyte with capacity of suppressing the activity of free and solvated H2O molecules was designed by selecting the cationophilic and solventophilic anions. In such electrolyte, contact ion-pairs and solvent-shared ion-pairs were achieved even at low concentration, where PCA- anions coordinate with Zn2+ and bond with solvated H2O molecules. Simultaneously, PCA- anions also induce the construction of H-bonds between free H2O molecules and them. Therefore, the activity of free and solvated H2O molecules is effectively restrained. Furthermore, since PCA- anions possess a strong affinity with metal Zn, they can also adsorb on Zn anode surface to protect Zn anode from the direct contact of H2O molecules, inhibiting the occurrence of water-triggered side reactions. As a result, plating/stripping behavior of Zn anodes is highly reversible and the coulombic efficiency can reach to 99.43 % in PCA-Zn electrolyte. To illustrate the feasibility of PCA-Zn electrolyte, the Zn||PANI full batteries were assembled based on PCA-Zn electrolyte and exhibited enhanced cycling performance.

An Air-Rechargeable Zn/Organic Battery with Proton Storage.

Air-rechargeable zinc batteries are a promising candidate for self-powered battery systems since air is ubiquitous and cost-free. However, they are still in their infancy and their electrochemical performance is unsatisfactory due to the bottlenecks of materials and device design. Therefore, it is of great significance to develop creative air-rechargeable Zn battery systems. Herein, an air-rechargeable Zn battery with H+-based chemistry was developed in a mild ZnSO4 electrolyte for the first time, where benzo[i]benzo[6,7]quinoxalino[2,3-a]benzo[6,7]quinoxalino[2,3-c]phenazine-5,8,13,16,21,24-hexaone (BQPH) was employed as cathode material. In this Zn/BQPH battery, a Zn2+ coordination with adjacent C═O and C═N groups leads to an inhomogeneous charge distribution in the BQPH molecule, which induces the H+ uptake on the remaining four pairs of the C═O and C═N groups in subsequent discharge processes. Interestingly, the large potential difference between the discharged cathode of the Zn/BQPH battery and oxygen triggers the redox reaction between them spontaneously, in which the discharged cathode can be oxidized by oxygen in air. In this process, the cathode potential will gradually rise along with H+ removal, and the discharged Zn/BQPH battery can be air-recharged without an external power supply. As a result, the air-rechargeable Zn/BQPH batteries exhibit enhanced electrochemical performance by fast H+ uptake/removal. This work will broaden the horizons of air-rechargeable zinc batteries and provide a guidance to develop high-performance and sustainable aqueous self-powered systems.

Direct Self-Assembly of MXene on Zn Anodes for Dendrite-Free Aqueous Zinc-Ion Batteries.

Metallic zinc is a promising anode candidate of aqueous zinc-ion batteries owing to its high theoretical capacity and low redox potential. However, Zn anodes usually suffer from dendrite and side reactions, which will degrade their cycle stability and reversibility. Herein, we developed an in situ spontaneously reducing/assembling strategy to assemble a ultrathin and uniform MXene layer on the surface of Zn anodes. The MXene layer endows the Zn anode with a lower Zn nucleation energy barrier and a more uniformly distributed electric field through the favorable charge redistribution effect in comparison with pure Zn. Therefore, MXene-integrated Zn anode exhibits obviously low voltage hysteresis and excellent cycling stability with dendrite-free behaviors, ensuring the high capacity retention and low polarization potential in zinc-ion batteries.

Thermal-Gated Polymer Electrolytes for Smart Zinc-Ion Batteries.

Smart self-protection is essential for addressing safety issues of energy-storage devices. However, conventional strategies based on sol-gel transition electrolytes often suffer from unstable self-recovery performance. Herein, smart separators based on thermal-gated poly(N-isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc-ion batteries (ZIBs). Such PNIPAM-based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self-protection of ZIBs at high temperatures. Furthermore, the thermal-gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature-dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal-responsive energy-storage devices with safe and controlled energy delivery.

Recent Progress in the Electrolytes of Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) have garnered tremendous attention in the field of next energy storage devices due to their high safety, low cost, abundant resources, and eco-friendliness. As an important component of the zinc-ion battery, the electrolyte plays a vital role in the electrochemical properties, since it will provide a pathway for the migrations of the zinc ions between the cathode and anode, and determine the ionic conductivity, electrochemically stable potential window, and reaction mechanism. In this Minireview, a brief introduction of electrochemical principles of the aqueous ZIBs is discussed and the recent advances of various aqueous electrolytes for ZIBs, including liquid, gel, and multifunctional hydrogel electrolytes are also summarized. Furthermore, the remaining challenges and future directions of electrolytes in aqueous ZIBs are also discussed, which could provide clues for the following development.

A Self-Healing Integrated All-in-One Zinc-Ion Battery.

The self-healing of zinc-ion batteries (ZIBs) will not only significantly improve the durability and extend the lifetime of devices, but also decrease electronic waste and economic cost. A poly(vinyl alcohol)/zinc trifluoromethanesulfonate (PVA/Zn(CF3 SO3 )2 ) hydrogel electrolyte was fabricated by a facile freeze/thaw strategy. PVA/Zn(CF3 SO3 )2 hydrogels possess excellent ionic conductivity and stable electrochemical performance. Such hydrogel electrolytes can autonomously self-heal by hydrogen bonding without any external stimulus. All-in-one integrated ZIBs can be assembled by incorporating the cathode, separator, and anode into hydrogel matrix since the fabrication of PVA/Zn(CF3 SO3 )2 hydrogel is a process of converting the liquid to quasi-solid state. The ZIBs show an outstanding self-healing and can recover electrochemical performance completely even after several cutting/healing cycles.

The Construction of Binary Phase Electrolyte Interface for Highly Stable Zinc Anodes.

Metal zinc is a promising anode candidate of aqueous zinc-ion batteries due to high theoretical capacity, low cost, and high safety. However, it often suffers from hydrogen evolution reaction (HER), dendrite growth, and formation of by-products. Herein, a triethyl phosphate (TEP)/H2 O binary phase electrolyte (BPE) interface is developed by introducing TEP-based electrolyte-wetted hydrophobic polypropylene (PP) separator onto the Zn anode surface. The equilibrium of the BPE interface depends on the comparable surface tensions of H2 O-based and TEP-based electrolytes on hydrophobic PP separator surfaces. The BPE interface induces Zn2+ solvation structure conversion from [Zn(H2 O)x ]2+ to [Zn(TEP)n (H2 O)y ]2+ , where most solvated H2 O molecules are removed. In [Zn(TEP)n (H2 O)y ]2+ , the residual H2 O molecules can be further constrained by the formation of H bonds between TEP and H2 O molecules. Consequently, the ionization of solvated H2 O molecules is effectively suppressed, and HER and by-products are effectively restricted on Zn anode surfaces in BPE. As a result, Zn anodes exhibit a high Coulombic efficiency of 99.12% and superior cycling performance of 6000 h, which is much higher than the case in single-phase aqueous electrolytes. To illustrate the feasibility of BPE in full cells, the Zn/Alx V2 O5 batteries are assembled based on the BPE and exhibited enhanced cycling performance.

A Binary Hydrate-Melt Electrolyte with Acetate-Oriented Cross-Linking Solvation Shells for Stable Zinc Anodes.

Aqueous zinc-ion batteries (ZIBs) with low cost and high safety are promising energy-storage devices. However, ZIBs with metal Zn anodes usually suffer from low coulombic efficiency and poor cycling performance due to the occurrence of side reactions on the Zn anodes. Here, a binary hydrate-melt ZnCl2 /Zn(OAc)2 electrolyte is designed to suppress the hydrogen evolution reaction and by-product formation on Zn anodes by adjusting the Zn2+ solvation structure. In the solvation structure of the hydrate-melt ZnCl2 /Zn(OAc)2 electrolyte, the carboxylate group in OAc- will coordinate with the Zn2+ , which will weaken the interaction between Zn2+ and H2 O molecules to achieve higher ionization energy of H2 O molecules. Simultaneously, these carboxylate groups of OAc- can serve as H-bond acceptors to construct H-bonds with H2 O molecules in their neighboring solvation structures, forming a cross-linking H-bond network. Such a cross-linking H-bond network further suppresses the water activity in ZnCl2 /Zn(OAc)2 electrolyte. As a result, in such an electrolyte, the side reactions are effectively restricted on Zn anodes and thus Zn anodes can achieve a high coulombic efficiency of 99.59% even after cycling. To illustrate the feasibility of the ZnCl2 /Zn(OAc)2 electrolyte in aqueous ZIBs, Zn||p-chloranil cells are assembled based on the ZnCl2 /Zn(OAc)2 electrolyte. The resultant Zn||p-chloranil cells exhibit enhanced cycling performance compared with the cases with a conventional ZnSO4 electrolyte.

A Universal Compensation Strategy to Anchor Polar Organic Molecules in Bilayered Hydrated Vanadates for Promoting Aqueous Zinc-Ion Storage.

The electrochemical performance of layered vanadium oxides is often improved by introducing guest species into their interlayer. Guest species with high stability in the interlayer and weak interaction with Zn2+ during charge/discharge process are desired to promoting reversible Zn2+ transfer. Herein, a universal compensation strategy was developed to introduce various polar organic molecules into the interlayer of Alx V2 O5 ·nH2 O by replacing partial crystal water. The high-polar groups in the organic molecules have a strong electrostatic attraction with pre-intercalated Al3+ , which ensures that organic molecules can be anchored in the interlayer of hydrated vanadates. Simultaneously, the low-polar groups endow organic molecules with a weak interaction with Zn2+ during cycling, thus liberalizing reversible Zn2+ transfer. As a result, Alx V2 O5 with polar organic molecules displays enhanced electrochemical performance. Furthermore, based on above cathode material, a pouch cell was assembled by further integrating a dendrite-free N-doped carbon nanofiber@Zn anode, displaying an energy density of 50 Wh kg-1 . This work provides a path for designing stable guest species with a weak interaction with Zn2+ in the interlayer of layered vanadium oxide towards high-performance cathode materials of aqueous Zn batteries.