Manipulating Interphase Chemistry for Aqueous Zn Stabilization: The Role of Supersaturation.

The limited cycling durability of Zn anode, attributed to the absence of a robust electrolyte-derived solid electrolyte interphase (SEI), remains the bottleneck for the practical deployment of aqueous zinc batteries. Herein, we highlight the role of local supersaturation in governing the fundamental crystallization chemistry of Zn4SO4(OH)6·xH2O (ZSH) and propose a subtle supersaturation-controlled morphology strategy to tailor the interphase chemistry of Zn anode. By judiciously creating local high-supersaturation environment with organic caprolactam to manipulate the precipitation manner of zinc sulfate hydroxide (ZSH), lattice-lattice matched heterogeneous nucleation of ZSH (001) and Zn (002) is realized in aqueous ZnSO4, producing a dense, pseudo-coincidence interface capable of functioning as decent SEI.

Reducing Dead Species by Electrochemically-Densified Cathode-Interface-Reaction Layer towards High-Rate-Endurable Zn||I-Br Batteries.

Interhalogen-involved aqueous Zn||halogen batteries (AZHBs) are latent high-energy systems for grid-level energy storage, yet usually suffer from poor high-rate endurability caused by the formation of "dead species". Herein, via an electrochemically-densified cathode-interface-reaction layer (CIRL), Zn||I-Br batteries involving interhalogen reactions between the I cathode and Br from the electrolytes are initially achieved with excellent high-rate endurability. Different from that in diluted electrolytes, the CIRL formed in Br-concentrated electrolyte is denser and water-lean, which enables halogen species conversion with a more rapid charge transfer and lower activation energy.

Achieving Stable Orientational Zinc Deposition for Reversible Zinc Anode through Supramolecular Anchoring Mechanism.

Aqueous zinc-ion batteries have been impeded by the hydrogen evolution reaction (HER), uncontrolled zinc dendrites, and side reactions on the Zn anode. In this work, a Zn-polyphenol supramolecular network is rationally designed for stabilizing Zn anodes (ZPN@Zn) even at high current density. Theoretical calculations and experiments show that the zinc-polyphenol supramolecular layer effectively inhibits the hydrogen evolution reaction by capturing water molecules through strong hydrogen bonding networks while also facilitating the rapid replenishment of Zn ions at the interface through supramolecular anchoring.

Synergetic bifunctional Cu-In alloy interface enables Ah-level Zn metal pouch cells.

Rechargeable aqueous zinc-metal batteries, considered as the possible post-lithium-ion battery technology for large-scale energy storage, face severe challenges such as dendrite growth and hydrogen evolution side reaction (HER) on Zn negative electrode. Herein, a three-dimensional Cu-In alloy interface is developed through a facile potential co-replacement route to realize uniform Zn nucleation and HER anticatalytic effect simultaneously. Both theoretical calculations and experimental results demonstrate that this bifunctional Cu-In alloy interface inherits the merits of low Zn-nucleation overpotential and high HER overpotential from individual copper and indium constituents, respectively.

Regulating Zn Deposition Manner by Confining the Reactivity of Free Water in the Electric Double Layer.

Aqueous Zn ion batteries (AZIBs) are promising candidates of next-generation energy storage devices with high safety and theoretical capacity. However, the irreversibility of metallic Zn anode, attributed to dendrite growth and water decomposition, severely limits the cycling durability of AZIBs and restricts their further development. Herein, a facile surface engineering strategy is put forward to tackle the issue of poor reversibility of the Zn anode.

Pyrrolic-Nitrogen Chemistry in 1-(2-hydroxyethyl)imidazole Electrolyte Additives toward a 50,000-Cycle-Life Aqueous Zinc-Iodine Battery.

Rechargeable aqueous zinc iodine (Zn-I) batteries offer benefits such as low cost and high safety. Nevertheless, their commercial application is hindered by hydrogen evolution reaction (HER) and polyiodide shuttle, which result in a short lifespan. In this study, 1-(2-hydroxyethyl)imidazole (HEI) organic molecules featuring pyrrole-N groups are introduced as dually-functional electrolyte additives to simultaneously stabilize Zn anode and confine polyiodide through ion-dipole interactions.

Molecular Bridging Induced Anti-Salting-Out Effect Enabling High Ionic Conductive ZnSO-Based Hydrogel for Quasi-Solid-State Zinc Ion Batteries.

Hydrogel electrolytes (HEs) hold great promise in tackling severe issues emerging in aqueous zinc-ion batteries, but the prevalent salting-out effect of kosmotropic salt causes low ionic conductivity and electrochemical instability. Herein, a subtle molecular bridging strategy is proposed to enhance the compatibility between PVA and ZnSO from the perspective of hydrogen-bonding microenvironment re-construction. By introducing urea containing both an H-bond acceptor and donor, the broken H-bonds between PVA and HO, initiated by the SO -driven HO polarization, could be re-united via intense intermolecular hydrogen bonds, thus leading to greatly increased carrying capacity of ZnSO.

Hydrophobic Ion Barrier-Enabled Ultradurable Zn (002) Plane Orientation towards Long-Life Anode-Less Zn Batteries.

Gradual disability of Zn anode and high negative/positive electrode (N/P) ratio usually depreciate calendar life and energy density of aqueous Zn batteries (AZBs). Herein, within original Zn-free hydrated electrolytes, a steric hindrance/electric field shielding-driven "hydrophobic ion barrier" is engineered towards ultradurable (002) plane-exposed Zn stripping/plating to solve this issue. Guided by theoretical simulations, hydrophobic adiponitrile (ADN) is employed as a steric hindrance agent to ally with inert electric field shielding additive (Mn) for plane adsorption priority manipulation, thereby constructing the "hydrophobic ion barrier".

Superhalide-Anion-Motivator Reforming-Enabled Bipolar Manipulation toward Longevous Energy-Type Zn||Chalcogen Batteries.

Neutrophilic superhalide-anion-triggered chalcogen conversion-based Zn batteries, despite latent high-energy merit, usually suffer from a short lifespan caused by dendrite growth and shuttle effect. Here, a superhalide-anion-motivator reforming strategy is initiated to simultaneously manipulate the anode interface and Se conversion intermediates, realizing a bipolar regulation toward longevous energy-type Zn batteries. With ZnF chaotropic additives, the original large-radii superhalide zincate anion species in ionic liquid (IL) electrolytes are split into small F-containing species, boosting the formation of robust solid electrolyte interphases (SEI) for Zn dendrite inhibition.

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

Dynamically Ion-Coordinated Bipolar Organodichalcogenide Cathodes Enabling High-Energy and Durable Aqueous Zn Batteries.

Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue.

Hetero-Solvation-Diluted Strongly-Coordinated Zn-Cosolvent Pairs Downshifting Zn Electrode Potential for High-Voltage Hybrid Batteries.

Mild aqueous Zn batteries (AZBs) generally suffer a low-voltage/energy dilemma, which compromises their competitiveness for large-scale energy storage. Pushing Zn anode potential downshift is an admissible yet underappreciated approach for high-voltage/energy AZBs. Herein, with a mild hybrid electrolyte containing in situ-derived diluted strongly-coordinated Zn-cosolvent pairs, a considerable Zn anode potential downshift is initially achieved for high-voltage Zn-based hybrid batteries.

Crowding Effect-Induced Zinc-Enriched/Water-Lean Polymer Interfacial Layer Toward Practical Zn-Iodine Batteries.

Although the meticulous design of functional diversity within the polymer interfacial layer holds paramount significance in mitigating the challenges associated with hydrogen evolution reactions and dendrite growth in zinc anodes, this pursuit remains a formidable task. Here, a large-scale producible zinc-enriched/water-lean polymer interfacial layer, derived from carboxymethyl chitosan (CCS), is constructed on zinc anodes by integration of electrodeposition and a targeted complexation strategy for highly reversible Zn plating/stripping chemistry. Zinc ions-induced crowding effect between CCS skeleton creates a strong hydrogen bonding environment and squeezes the moving space for water/anion counterparts, therefore greatly reducing the number of active water molecules and alleviating cathodic I attack.

Lithium Bis(oxalate)borate Additive for Self-repairing Zincophilic Solid Electrolyte Interphases towards Ultrahigh-rate and Ultra-stable Zinc Anodes.

The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn -conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm , presenting a record-high cumulative capacity up to 45 Ah cm .

Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries.

A B- and F-enriched buffering interphase enables a high-rate and high-stability SiO/C anode.

A facile, universal surface engineering strategy is proposed to address the volume expansion and slow kinetic issues encountered by SiO/C anodes. A B-/F-enriched buffering interphase is introduced onto SiO/C by thermal treatment of pre-adsorbed lithium salts at 400 °C. The as-prepared anode integrates both high-rate performance and long-term cycling durability.

Hydrated Eutectic Electrolytes Stabilizing Quasi-Underpotential Mg Plating/Stripping for High-Voltage Mg Batteries.

Aqueous rechargeable Mg batteries (ARMBs) usually fail from severe anode passivation, alternatively, executing quasi-underpotential Mg plating/stripping chemistry (UPMC) on a proper heterogeneous metal substrate is a crucial remedy. Herein, a stable UPMC on Zn substrate is initially achieved in new hydrated eutectic electrolytes (HEEs), delivering an ultralow UPMC overpotential and high energy/voltage plateau of ARMBs. The unique eutectic property remarkably expands the lower limit of electrochemical stability window (ESW) of HEEs and undermines the competition between hydrogen evolution/corrosion reactions and UPMC, enabling a reversible UPMC.

Dynamically Interfacial pH-Buffering Effect Enabled by N-Methylimidazole Molecules as Spontaneous Proton Pumps toward Highly Reversible Zinc-Metal Anodes.

Aqueous zinc-metal batteries have attracted extensive attention due to their outstanding merits of high safety and low cost. However, the intrinsic thermodynamic instability of zinc in aqueous electrolyte inevitably results in hydrogen evolution, and the consequent generation of OH at the interface will dramatically exacerbate the formation of dead zinc and dendrites. Herein, a dynamically interfacial pH-buffering strategy implemented by N-methylimidazole (NMI) additive is proposed to remove the detrimental OH at zinc/electrolyte interface in real-time, thus eliminating the accumulation of by-products fundamentally.

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

High interfacial energy Li-electrolyte interface contributes to larger Li nucleation embryos and a more stable interface, so the interfacial energy is essential for highly reversible Li 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 Li 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.

Manipulating OH -Mediated Anode-Cathode Cross-Communication Toward Long-Life Aqueous Zinc-Vanadium Batteries.

The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al (SO ) is proposed as decent electrolyte additive to manipulate OH -mediated cross-communication between Zn anode and NaV O  ⋅ 1.5H O (NVO) cathode.

In Situ Polymerization of Ionic Liquid with Tunable Phase Separation for Highly Reversible and Ultralong Cycle Life Zn-Ion Battery.

Severe Zn dendrite growth and side reactions greatly limit the application of aqueous zinc-ion batteries. Herein, we design a layer of polyionic liquid (PCAVImBr) film with a tunable pore size and charge density on the Zn anode to endow homogenized distribution of an electronic field, acerated Zn permeation, and inhabitation of water entry. Such an optimal combination is achieved via a polymerization induced phase separation strategy, where the enhanced cross-linking density arrests the phase separation in a shallow depth and vice versa.

Achieving Ultrahigh-Rate and Low-Temperature Sodium Storage of FePS via In Situ Construction of Graphitized Porous N-Doped Carbon.

Sodium-ion batteries (SIBs) have become an important supplementation to lithium-ion batteries. Unfortunately, the low capacity and inferior low-temperature performance of traditional hard carbon led to limited energy density and a range of applications of SIBs. Herein, we present high-performance SIBs via embedding FePS in graphitized porous N-doped carbon (FPS/GPNC) using coordination polymerization reaction.

Improved Reversible Zinc Storage Achieved in a Constitutionally Crystalline-Stable Mn(VO ) Nanobelts Cathode.

Rechargeable zinc-ion batteries (ZIBs) are potential for grid-scale applications owing to their safety, low price, and available sources. The development of ZIBs cathode with high specific capacity, wide operating voltage window and stable cyclability is urgently needed in next-generation commercial batteries. Herein, we report a structurally crystalline-stable Mn(VO ) nanobelts cathode for ZIBs prepared via a facile hydrothermal method.