Advancements and Challenges in Aqueous Zinc-Iodine Batteries: Strategies for Enhanced Performance and Stability

Aqueous zinc-iodine batteries are considered to be one of the most promising devices for future electrical energy storage due to their low cost, high safety, high theoretical specific capacity, and multivalent properties. However, the shuttle effect currently faced by zinc-iodine batteries causes the loss of cathode active material and corrosion of the zinc anodes, limiting the large-scale application of zinc-iodine batteries. In this paper, the electrochemical processes of iodine conversion and the zinc anode, as well as the induced mechanism of the shuttle effect, are introduced from the basic configuration of the aqueous zinc-iodine battery. Then, the inhibition strategy of the shuttle effect is summarized from four aspects: the design of cathode materials, electrolyte regulation, the modification of the separator, and anode protection. Finally, the current status of aqueous zinc-iodine batteries is analyzed and recommendations and perspectives are presented. This review is expected to deepen the understanding of aqueous zinc-iodide batteries and is expected to guide the design of high-performance aqueous zinc-iodide batteries.

Aqueous rechargeable zinc-iodine batteries (ZIBs), including zinc-iodine redox flow batteries and static ZIBs, are promising candidates for future grid-scale electrochemical energy storage. They are safe with great theoretical capacity, high energy, and power density. Nevertheless, to make aqueous rechargeable ZIBs practically feasible, there are quite a few hurdles that need to be overcome, including self-discharge, sluggish kinetics, low energy density, and instability of Zn metal anodes. This article first reviews the electrochemistry in aqueous rechargeable ZIBs, including the flow and static battery configurations and their electrode reactions. Then the authors discuss the fundamental questions of ZIBs and highlight the key strategies and recent accomplishments in tackling the challenges. Last, they share their thoughts on the future research development in aqueous rechargeable ZIBs.

Aqueous zinc-iodine (Zn-I2) batteries are among the most promising energy storage technologies, offering high energy density, low cost, and intrinsic safety. However, their practical deployment is hindered by the polyiodide shuttle effect, leading to rapid capacity fading and poor cycling performance. This work demonstrates the application of a crystalline viologen-based covalent organic framework (TAB-DNP-BP COF), synthesized via a one-pot Zincke reaction, as an efficient iodine host material. The cationic backbone of the TAB-DNP-BP COF effectively confines iodine (I2) species and electrostatically traps polyiodides, suppressing their migration and protecting the zinc anode. Zinc-iodine batteries assembled with an I2-enriched TAB-DNP-BP COF (TAB-DNP-BP COF@I2) cathode deliver a high specific capacity of 337 mAh g-1 at 0.5 C, surpassing the performance of most reported COF-, MOF-, and cage-based systems, while exhibiting excellent cycling stability over 5000 cycles. This work highlights the potential of ionic COFs for stabilizing iodine chemistry and offers a promising strategy toward the development of high-performance, durable aqueous Zn-I2 batteries.

An ion exchange membrane-free, ultrastable zinc-iodine battery enabled by functionalized graphene electrodes

Electrochemically reversible redox couples that embrace more electron transfer at a higher potential are the eternal target for energy storage batteries. Here, we report a four-electron aqueous zinc-iodine battery by activating the highly reversible I2/I+ couple (1.83 V vs. Zn/Zn2+) in addition to the typical I−/I2 couple (1.29 V). This is achieved by intensive solvation of the aqueous electrolyte to yield ICl inter-halogens and to suspend its hydrolysis. Experimental characterization and modelling reveal that limited water activity and sufficient free chloride ions in the electrolyte are crucial for the four-electron process. The merits of the electrolyte also afford to stabilize Zn anode, leading to a reliable Zn-I2 aqueous battery of 6000 cycles. Owing to high operational voltage and capacity, energy density up to 750 Wh kg−1 based on iodine mass was achieved (15–20 wt% iodine in electrode). It pushes the Zn-I2 battery to a superior level among these available aqueous batteries.

Aqueous zinc metal batteries suffer from uncontrollable dendrite growth and undesirable side reactions, which drastically compromise the battery performance and practical application. To address these issues, an accordion-type multifunctional coating of Cu-V2CBr2 MXene with zincophilic and hydrophobic properties is developed by molten salt etching to achieve highly redox reversibile of zinc. Experimental results and theoretical calculations demonstrate that the -Br terminating groups have a strong electronegativity, which can electronically modify the surface of MXene, affecting the local electrochemical environment. This creates a low surface energy and a strongly hydrophobic surface, thereby inhibiting the side reactions. In addition, the in situ formation of copper nanoparticles within the interlayers provides abundant nucleation sites and promotes uniform electron distribution throughout the framework, thereby regulating Zn2+ ions flux and facilitating uniform zinc deposition. As a result, the symmetric cells demonstrate good rate performance and stable cycling performance for up to 1700h at 10mA cm-2. The full batteries paired with iodine-loaded porous carbon cathode exhibit an excellent capacity retention of 89.3% after 5000 cycles at 5 C. This work opens a new pathway to modulate the zinc anode interface process, which can also be extended to other aqueous batteries.

Aqueous Zn batteries (AZBs) have attracted extensive attention due to good safety, cost-effectiveness, and environmental benignity. However, the sluggish kinetics of divalent zinc ion and the growth of Zn dendrites severely deteriorate the cycling stability and specific capacity. The authors demonstrate modulation of the interfacial redox process of zinc via the dynamic coordination chemistry of phytic acid with zinc ions. The experimental results and theoretical calculation reveal that the in-situ formation of such inorganic-organic films as a dynamic solid-electrolyte interlayer is efficient to buffer the zinc ion transfer via the energy favorable coordinated hopping mechanism for the reversible zinc redox reactions. Especially, along the interfacial coating layer with porous channel structure is able to regulate the solvation structure of zinc ions along the dynamic coordination of the phytic acid skeleton, efficiently inhibiting the surface corrosion of zinc and dendrite growth. Therefore, the resultant Zn anode achieves low voltage hysteresis and long cycle life at rigorous charge and discharge circulation for fabricating highly robust rechargeable batteries. Such an advanced strategy for modulating ion transport demonstrates a highly promising approach to addressing the basic challenges for zinc-based rechargeable batteries, which can potentially be extended to other aqueous batteries.

Strong adsorption Fe[sbnd]N[sbnd]C catalytic cathode for 50,000 cycles aqueous zinc-iodine batteries

Electrode and electrolyte additive synergy effect for improving the capacity and supporting a high voltage plateau of aqueous rechargeable zinc iodine batteries

Aqueous zinc-iodine batteries (ZIBs) based on the reversible conversion between various iodine species have garnered global attention due to their advantages of fast redox kinetics, good reversibility, and multielectron conversion feasibility. Although significant progress has been achieved in ZIBs with the two-electron I-/I2 pathway (2eZIBs), their relatively low energy density has hindered practical application. Recently, ZIBs with four-electron I-/I2/I+ electrochemistry (4eZIBs) have shown a significant improvement in energy density. Nonetheless, the practical use of 4eZIBs is challenged by poor redox reversibility due to polyiodide shuttling during I-/I2 conversion and I+ hydrolysis during I2/I+ conversion. In this Review, we thoroughly summarize the fundamental understanding of two ZIBs, including reaction mechanisms, limitations, and improvement strategies. Importantly, we provide an intuitive evaluation on the energy density of ZIBs to assess their practical potential and highlight the critical impacts of the Zn utilization rate. Finally, we emphasize the cost issues associated with iodine electrodes and propose potential closed-loop recycling routes for sustainable energy storage with ZIBs. These findings aim to motivate the practical application of advanced ZIBs and promote sustainable global energy storage.

Electrode and electrolyte regulation to promote coulombic efficiency and cycling stability of aqueous zinc-iodine batteries

Aqueous zinc-iodine batteries stand out as highly promising energy storage systems owing to the abundance of resources and non-combustible nature of water coupled with their high theoretical capacity. Nevertheless, the development of aqueous zinc-iodine batteries has been impeded by persistent challenges associated with iodine cathodes and Zn anodes. Key obstacles include the shuttle effect of polyiodine and the sluggish kinetics of cathodes, dendrite formation, the hydrogen evolution reaction (HER), and the corrosion and passivation of anodes. Numerous strategies aimed at addressing these issues have been developed, including compositing with carbon materials, using additives, and surface modification. This review provides a recent update on various strategies and perspectives for the development of aqueous zinc-iodine batteries, with a particular emphasis on the regulation of I2 cathodes and Zn anodes, electrolyte formulation, and separator modification. Expanding upon current achievements, future initiatives for the development of aqueous zinc-iodine batteries are proposed, with the aim of advancing their commercial viability.

Zinc-iodine aqueous batteries (ZIABs) are highly attractive for grid-scale energy storage due to their high theoretical capacities, environmental friendliness, and intrinsic non-flammability. However, because of the close redox potential of Zn stripping/platting and hydrogen evolution, slight overcharge of ZIABs would induce drastic side reactions, serious safety concerns, and battery failure. A novel type of stimulus-responsive zinc-iodine aqueous battery (SR-ZIAB) with fast overcharge self-protection ability is demonstrated by employing a smart pH-responsive electrolyte. Operando spectroelectrochemical characterizations reveal that the battery failure mechanism of ZIABs during overcharge arises from the increase of electrolyte pH induced by hydrogen evolution as well as the consequent irreversible formation of insulating ZnO at anode and soluble Zn(IO3 )2 at cathode. Under overcharge conditions, the designed SR-ZIABs can be rapidly switched off with capacity degrading to 6% of the initial capacity, thereby avoiding continuous battery damage. Importantly, SR-ZIABs can be switched on with nearly 100% of capacity recovery by re-adjusting the electrolyte pH. This work will inspire the development of aqueous Zn batteries with smart self-protection ability in the overcharge state.

The multielectron conversion electrochemistry of I-/I0/I+ enables high specific capacity and voltage in zinc-iodine batteries. Unfortunately, the I+ ions are thermodynamically unstable and are highly susceptible to hydrolysis. Current endeavors primarily focus on exploring interhalogen chemistry to activate the I0/I+ couple. However, the practical working voltage is below the theoretical level. In this study, the I0/I+ redox couple is fully activated, and I+ is efficiently stabilized by a chelation agent of cost-effective urea in the conventional aqueous electrolyte. A record-high plateau voltage of 1.8 V vs Zn/Zn2+ has been realized. Theoretical calculations combined with spectroscopy studies and electrochemical tests reveal that the coordination between the electron-deficient I+ and the electron-rich O and N atoms in urea molecules is thermodynamically favorable for I0/I+ conversion and inhibits the self-disproportionation of I+, which in turn promotes rapid kinetics and excellent reversibility of I0/I+. Moreover, urea decreases the water activity in the electrolyte by forming hydrogen bonds to further suppress the hydrolysis of I+. Accordingly, a high specific capacity of 419 mAh g-1 is delivered at 1C, and 147 mAh g-1 capacity is retained after 10,000 cycles at 5C. This work offers effective insights into formulating halogen-free electrolytes for high-performance aqueous zinc-iodine batteries.

Multifunctional porous carbon strategy assisting high-performance aqueous zinc-iodine battery