Stabilizing Zn/electrolyte Interphasial Chemistry by a Sustained-Release Drug Inspired Indium-Chelated Resin Protective Layer for High-Areal-Capacity Zn//V2O5 Batteries.

For zinc-metal batteries, the instable chemistry at Zn/electrolyte interphasial region results in severe hydrogen evolution reaction (HER) and dendrite growth, significantly impairing Zn anode reversibility. Moreover, an often-overlooked aspect is this instability can be further exacerbated by the interaction with dissolved cathode species in full batteries. Here, inspired by sustained-release drug technology, an indium-chelated resin protective layer (Chelex-In), incorporating a sustained-release mechanism for indium, is developed on Zn surface, stabilizing the anode/electrolyte interphase to ensure reversible Zn plating/stripping performance throughout the entire lifespan of Zn//V2O5 batteries. The sustained-release indium onto Zn electrode promotes a persistent anticatalytic effect against HER and fosters uniform heterogeneous Zn nucleation. Meanwhile, on the electrolyte side, the residual resin matrix with immobilized iminodiacetates anions can also repel detrimental anions (SO4 2- and polyoxovanadate ions dissolved from V2O5 cathode) outside the electric double layer. This dual synergetic regulation on both electrode and electrolyte sides culminates a more stable interphasial environment, effectively enhancing Zn anode reversibility in practical high-areal-capacity full battery systems. Consequently, the bio-inspired Chelex-In protective layer enables an ultralong lifespan of Zn anode over 2800 h, which is also successfully demonstrated in ultrahigh areal capacity Zn//V2O5 full batteries (4.79 mAh cm-2).

Simultaneous Inhibition of Zn Dendrites and Polyiodide Ions Shuttle Effect by an Anion Concentrated Electrolyte Membrane for Long Lifespan Aqueous Zinc-Iodine Batteries.

Aqueous zinc-iodine (Zn-I2) batteries have attracted extensive attention due to their merits of inherent safety, wide natural abundance, and low cost. However, their application is seriously hindered by the irreversible capacity loss resulting from both anode and cathode. Herein, an anion concentrated electrolyte (ACE) membrane is designed to manipulate the Zn2+ ion flux on the zinc anode side and restrain the shuttle effect of polyiodide ions on the I2 cathode side simultaneously to realize long-lifetime separator-free Zn-I2 batteries. The ACE membrane with abundant sulfonic acid groups possesses a multifunctional amalgamation of good mechanical strength, guided Zn2+ ion transport, and effective charge repulsion of polyiodide ions. Moreover, rich ether oxygen, carbonyl, and S-O bonds in anionic polymer chains will form hydrogen bonds with water to reduce the proportion of free water in the ACE membrane, inhibiting the water-induced interfacial side reactions of the Zn metal anode. Besides, DFT calculations and in-situ UV-vis and in situ Raman results reveal that the shuttle effect of polyiodide ions is also significantly suppressed. Therefore, the ACE membrane enables a long lifespan of Zn anodes (3700 h) and excellent cycling stability of Zn-I2 batteries (10000 cycles), thus establishing a substantial base for their practical applications.

A Janus Separator based on Cation Exchange Resin and Fe Nanoparticles-decorated Single-wall Carbon Nanotubes with Triply Synergistic Effects for High-areal Capacity Zn-I2 Batteries.

Zn-I2 batteries stand out in the family of aqueous Zn-metal batteries (AZMBs) due to their low-cost and immanent safety. However, Zn dendrite growth, polyiodide shuttle effect and sluggish I2 redox kinetics result in dramatically capacity decay of Zn-I2 batteries. Herein, a Janus separator composed of functional layers on anode/cathode sides is designed to resolve these issues simultaneously. The cathode layer of Fe nanoparticles-decorated single-wall carbon nanotubes can effectively anchor polyiodide and catalyze the redox kinetics of iodine species, while the anode layer of cation exchange resin rich in -SO3 - groups is beneficial to attract Zn2+ ions and repel detrimental SO4 2- /polyiodide, improving the stability of cathode/anode interfaces synergistically. Consequently, the Janus separator endows outstanding cycling stability of symmetrical cells and high-areal-capacity Zn-I2 batteries with a lifespan over 2500 h and a high-areal capacity of 3.6 mAh cm-2 .

High interfacial-energy heterostructure facilitates large-sized lithium nucleation and rapid Li+ desolvation process.

High interfacial energy Li0-electrolyte interface contributes to larger Li0 nucleation embryos and a more stable interface, so the interfacial energy is essential for highly reversible Li0 deposition/stripping. Herein, a high interfacial-energy artificial solid electrolyte interphase (SEI) with rich LiF embedded in lithiated poly-2-acrylamido-2-methylpropane sulfonic acid (PAMPS-Li) network is designed to realize favorable Li0 nucleation and rapid desolvation of Li+ simultaneously. The Li-F bonds in LiF (001) exhibit stronger ion-dipole interactions with Li atoms, offering higher interfacial energies. When the growth surface energy and total interfacial energy of Li0 are balanced, the high interfacial energy SEI with abundant LiF can promote the formation of larger Li0 nucleation embryos. In addition, the PAMPS-Li with immobilized anions presents weaker interaction with Li0 and possesses higher polymer-Li interfacial energy, and its amide and sulfonic acid groups exhibit higher binding energies with Li+. Therefore, PAMPS-Li can easily promote the Li+ to escape from the solvent sheath and weaken the desolvation energy barrier. The highly reversible Li0 deposition behavior with restricted side reactions is achieved based on the synergistic modification of high interfacial energy SEI with heterostructure. Most importantly, lifespan of multi-layered Li0 pouch cell (330 Wh kg-1) with a low N/P ratio (1.67) is over 100 cycles, verifying its potential practical application.