Tailoring Localized Electrolyte via a Dual-Functional Protein Membrane toward Stable Zn Anodes.

Considerable attention has been by far paid to stabilizing metallic Zn anodes, where side reactions and dendrite formation still remain detrimental to their practical advancement. Electrolyte modification or protected layer design is widely reported; nonetheless, an effective maneuver to synergize both tactics has been rarely explored. Herein, we propose a localized electrolyte optimization via the introduction of a dual-functional biomass modificator over the Zn anode. Instrumental characterization in conjunction with molecular dynamics simulation indicates local solvation structure transformation owing to the limitation of bound water with intermolecular hydrogen bonds, effectively suppressing hydrogen evolutions. Meanwhile, the optimized nucleation throughout the protein membrane allows uniform Zn deposition. Accordingly, the symmetric cell exhibits an elongated lifespan of 3280 h at 1.0 mA cm-2/1.0 mAh cm-2, while the capacity retention of the full cell sustains 91.1% after 2000 cycles at 5.0 A g-1. The localized electrolyte tailoring via protein membrane introduction might offer insights into operational metal anode protection.

Establishing Pinhole Deposition Mode of Zn via Scalable Monolayer Graphene Film.

The uneven texture evolution of Zn during electrodeposition would adversely impact upon the lifespan of aqueous Zn metal batteries. To address this issue, tremendous endeavors are made to induce Zn(002) orientational deposition employing graphene and its derivatives. Nevertheless, the effect of prototype graphene film over Zn deposition behavior has garnered less attention. Here, it is attempted to solve such a puzzle via utilizing transferred high-quality graphene film with controllable layer numbers in a scalable manner on a Zn foil. The multilayer graphene fails to facilitate a Zn epitaxial deposition, whereas the monolayer film with slight breakages steers a unique pinhole deposition mode. In-depth electrochemical measurements and theoretical simulations discover that the transferred graphene film not only acts as an armor to inhibit side reactions but also serves as a buffer layer to homogenize initial Zn nucleation and decrease Zn migration barrier, accordingly enabling a smooth deposition layer with closely stacked polycrystalline domains. As a result, both assembled symmetric and full cells manage to deliver satisfactory electrochemical performances. This study proposes a concept of "pinhole deposition" to dictate Zn electrodeposition and broadens the horizons of graphene-modified Zn anodes.

A Holistic Additive Protocol Steers Dendrite-Free Zn(101) Orientational Electrodeposition.

Orientation guidance has shown its cutting edges in electrodeposition modulation to promote Zn anode stability toward commercialized standards. Nevertheless, large-scale orientational deposition is handicapped by the competition between Zn-ion reduction and mass transfer. Herein, a holistic electrolyte additive protocol is put forward via incorporating bio-derived dextrin molecules into a zinc sulfate electrolyte bath. Electrochemical tests in combination with molecular dynamics simulations demonstrate the alleviation of concentration polarization throughout accelerating Zn2+ diffusion and retarding their reduction. The predominant (101) texture on inert current collectors (i.e., Cu, Ti, and stainless steel) and (101)/(002) textures on Zn foils afford homogeneous electrical field distribution, which is contributed by the work difference to form the 2D nucleus and the adsorption of dextrin molecules, respectively. Consequently, the symmetric cell harvests a longevous cycling lifespan of over 4000 h at 0.5 mA cm-2 /0.5 mAh cm-2 while the Zn@Cu electrode sustains for 240 h at a high depth of discharge of 40%.

Hydrogel Electrolyte Enabled High-Performance Flexible Aqueous Zinc Ion Energy Storage Systems toward Wearable Electronics.

To cater to the swift advance of flexible wearable electronics, there is growing demand for flexible energy storage system (ESS). Aqueous zinc ion energy storage systems (AZIESSs), characterizing safety and low cost, are competitive candidates for flexible energy storage. Hydrogels, as quasi-solid substances, are the appropriate and burgeoning electrolytes that enable high-performance flexible AZIESSs. However, challenges still remain in designing suitable and comprehensive hydrogel electrolyte, which provides flexible AZIESSs with high reversibility and versatility. Hence, the application of hydrogel electrolyte-based AZIESSs in wearable electronics is restricted. A thorough review is required for hydrogel electrolyte design to pave the way for high-performance flexible AZIESSs. This review delves into the engineering of desirable hydrogel electrolytes for flexible AZIESSs from the perspective of electrolyte designers. Detailed descriptions of hydrogel electrolytes in basic characteristics, Zn anode, and cathode stabilization effects as well as their functional properties are provided. Moreover, the application of hydrogel electrolyte-based flexible AZIESSs in wearable electronics is discussed, expecting to accelerate their strides toward lives. Finally, the corresponding challenges and future development trends are also presented, with the hope of inspiring readers.

Rationalized Electroepitaxy toward Scalable Single-Crystal Zn Anodes.

Electroepitaxy is recognized as an effective approach to prepare metal electrodes with nearly complete reversibility. Nevertheless, large-scale manipulation is still not attainable owing to complicated interfacial chemistry. Here, the feasibility of extending Zn electroepitaxy toward the bulk phase over a mass-produced mono-oriented Cu(111) foil is demonstrated. Interfacial Cu-Zn alloy and turbulent electroosmosis are circumvented by adopting a potentiostatic electrodeposition protocol. The as-prepared Zn single-crystalline anode enables stable cycling of symmetric cells at a stringent current density of 50.0 mA cm-2 . The assembled full cell further sustaines a capacity retention of 95.7% at 5.0 A g-1 for 1500 cycles, accompanied by a controllably low N/P ratio of 7.5. In addition to Zn, Ni electroepitaxy can be realized by using the same approach. This study may inspire rational exploration of the design of high-end metal electrodes.

Synchronous Dual Electrolyte Additive Sustains Zn Metal Anode with 5600†h Lifespan.

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+ , thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm-2 /1.0 mAh cm-2 .

Mosaic Nanocrystalline Graphene Skin Empowers Highly Reversible Zn Metal Anodes.

Constructing a conductive carbon-based artificial interphase layer (AIL) to inhibit dendritic formation and side reaction plays a pivotal role in achieving longevous Zn anodes. Distinct from the previously reported carbonaceous overlayers with singular dopants and thick foreign coatings, a new type of N/O co-doped carbon skin with ultrathin feature (i.e., 20 nm thickness) is developed via the direct chemical vapor deposition growth over Zn foil. Throughout fine-tuning the growth conditions, mosaic nanocrystalline graphene can be obtained, which is proven crucial to enable the orientational deposition along Zn (002), thereby inducing a planar Zn texture. Moreover, the abundant heteroatoms help reduce the solvation energy and accelerate the reaction kinetics. As a result, dendrite growth, hydrogen evolution, and side reactions are concurrently mitigated. Symmetric cell harvests durable electrochemical cycling of 3040 h at 1.0 mA cm-2 /1.0 mAh cm-2 and 136 h at 30.0 mA cm-2 /30.0 mAh cm-2 . Assembled full battery further realizes elongated lifespans under stringent conditions of fast charging, bending operation, and low N/P ratio. This strategy opens up a new avenue for the in situ construction of conductive AIL toward pragmatic Zn anode.

Direct-Chemical Vapor Deposition-Enabled Graphene for Emerging Energy Storage: Versatility, Essentiality, and Possibility.

The direct chemical vapor deposition (CVD) technique has stimulated an enormous scientific and industrial interest to enable the conformal growth of graphene over multifarious substrates, which readily bypasses tedious transfer procedure and empowers innovative materials paradigm. Compared to the prevailing graphene materials (i.e., reduced graphene oxide and liquid-phase exfoliated graphene), the direct-CVD-enabled graphene harnesses appealing structural advantages and physicochemical properties, accordingly playing a pivotal role in the realm of electrochemical energy storage. Despite conspicuous progress achieved in this frontier, a comprehensive overview is still lacking by far and the synthesis-structure-property-application nexus of direct-CVD-enabled graphene remains elusive. In this topical review, rather than simply compiling the state-of-the-art advancements, the versatile roles of direct-CVD-enabled graphene are itemized as (i) modificator, (ii) cultivator, (iii) defender, and (iv) decider. Furthermore, essential effects on the performance optimization are elucidated, with an emphasis on fundamental properties and underlying mechanisms. At the end, perspectives with respect to the material production and device fabrication are sketched, aiming to navigate the future development of direct-CVD-enabled graphene en-route toward pragmatic energy applications and beyond.

Artificial Interphase Layer for Stabilized Zn Anodes: Progress and Prospects.

The burgeoning Li-ion battery is regarded as a powerful energy storage system by virtue of its high energy density. However, inescapable issues concerning safety and cost aspects retard its prospect in certain application scenarios. Accordingly, strenuous efforts have been devoted to the development of the emerging aqueous Zn-ion battery (AZIB) as an alternative to inflammable organic batteries. In particular, the instability from the anode side severely impedes the commercialization of AZIB. Constructing an artificial interphase layer (AIL) has been widely employed as an effective strategy to stabilize the Zn anode. This review specializes in the state-of-the-art of AIL design for Zn anode protection, encompassing the preparation methods, mechanism investigations, and device performances based on the classification of functional materials. To begin with, the origins of Zn instability are interpreted from the perspective of electrical field, mass transfer, and nucleation process, followed by a comprehensive summary with respect to functions of AIL and its designing criteria. In the end, current challenges and future outlooks based upon theoretical and experimental considerations are included.

An Anode-Free Potassium-Metal Battery Enabled by a Directly Grown Graphene-Modulated Aluminum Current Collector.

Potassium (K)-metal batteries have emerged as a promising energy-storage device owing to abundant K resources. An anode-free architecture that bypasses the need for anode host materials can deliver an elevated energy density. However, the poor efficiency of K plating/stripping on potassiophobic anode current collectors results in rapid K inventory loss and a short cycle life. Herein, commercial Al foils are decorated with an ultrathin graphene-modified layer (Al@G) through roll-to-roll plasma-enhanced chemical vapor deposition. By harnessing strong adhesion (10.52 N m-1 ) and a high surface energy (66.6 mJ m-2 ), the designed Al@G structure ensures a highly smooth and ordered K plating/stripping process. Consequently, during K-metal plating/stripping, Al@G can operate at a current density of up to 4.0 mA cm-2 and cyclic capacity of up to 4.0 mAh cm-2 , with an ultralong lifespan of up to 1000 h at 0.5 mA cm-2 and stable cycling of up to 750 h under periodic current fluctuations of 0.1-2.0 mA cm-2 . In addition, a novel anode-free K-metal full-cell prototype enabled by Al@G anode current collectors is constructed, demonstrating ameliorative cyclic stability.

Regulating Interfacial Ion Migration via Wool Keratin Mediated Biogel Electrolyte toward Robust Flexible Zn-Ion Batteries.

Aqueous Zn-ion batteries (ZIBs) have emerged as a promising energy supply for next-generation wearable electronics, yet they are still impeded by the notorious growth of zinc dendrite and uncontrollable side reaction. While the rational design of electrolyte composition or separator decoration can effectively restrain zinc dendrite growth, synchronously regulating the interfacial electrochemical performance by tackling the physical delamination venture between electrode and electrolyte remains a major obstacle for high-performance wearable aqueous ZIB. Herein, a category of hybrid biogel electrolyte containing carrageenan and wool keratin (CWK) is put forward to regulate the interfacial electrochemistry in aqueous ZIB. Systematic electrochemical kinetics analyses and ex situ scanning electrochemical microscopy (SECM) characterizations achieve comprehensive understanding of the keratin enhanced interfacial Zn2+ redox reaction. Thanks to the keratin triggered selective ion permeability, the as-designed CWK hybrid biogel electrolyte manifests a promoted Zn2+ transference number and excellent reversibility of Zn plating/stripping and outstanding Zn utilization (average Coulombic efficiency ≈98%). More impressively, the CWK hybrid biogel electrolyte also demonstrates cathode side-reaction depression and strengthened interfacial adhesion while assembled into a quasi-solid-state flexible ZIB. This work offers a strategy to synchronously solve concurrent challenges for both of Zn anode and cathode toward realistic wearable aqueous ZIB.

Crystalline tetra-aniline with chloride interactions towards a biocompatible supercapacitor.

Recent advances in wearable and implantable electronics have increased the demand for biocompatible integrated energy storage systems. Conducting polymers, such as polyaniline (PANi), have been suggested as promising electrode materials for flexible biocompatible energy storage systems, based on their intrinsic structural flexibility and potential polymer chain compatibility with biological interfaces. However, due to structural disorder triggering insufficient electronic conductivity and moderate electrochemical stability, PANi still cannot fully satisfy the requirements for flexible and biocompatible energy storage systems. Herein, we report a biocompatible physiological electrolyte activated flexible supercapacitor encompassing crystalline tetra-aniline (c-TANi) as the active electrode material, which significantly enhances the specific capacitance and electrochemical cycling stability with chloride electrochemical interactions. The crystallization of TANi endows it with sufficient electronic conductivity (8.37 S cm-1) and a unique Cl- dominated redox charge storage mechanism. Notably, a fully self-healable and biocompatible supercapacitor has been assembled by incorporating polyethylene glycol (PEG) with c-TANi as a self-healable electrode and a ferric-ion cross-linked sodium polyacrylate (Fe3+-PANa)/0.9 wt% NaCl as a gel electrolyte. The as-prepared device exhibits a remarkable capacitance retention even after multiple cut/healing cycles. With these attractive features, the c-TANi electrode presents a promising approach to meeting the power requirements for wearable or implantable electronics.

Interfacial Manipulation via In Situ Grown ZnSe Cultivator toward Highly Reversible Zn Metal Anodes.

Zn metal anode has garnered growing scientific and industrial interest owing to its appropriate redox potential, low cost, and high safety. Nevertheless, the instability of Zn anode caused by dendrite formation, hydrogen evolution, and side reactions has greatly hampered its commercialization. Herein, an in situ grown ZnSe overlayer is crafted over one side of commercial Zn foil via chemical vapor deposition in a scalable manner, aiming to achieve optimized electrolyte/Zn interfaces with large-scale viability. Impressively, thus-derived ZnSe coating functions as a cultivator to guide oriented growth of Zn (002) plane at the infancy stage of stripping/plating cycles, thereby inhibiting the formation of Zn dendrites and the occurrence of side reactions. As a result, high cyclic stability (1530 h at 1.0 mA cm-2 /1.0 mAh cm-2 ; 172 h at 30.0 mA cm-2 /10.0 mAh cm-2 ) in symmetric cells is harvested. Meanwhile, when paired with V2 O5 based cathode, assembled full cell achieves an outstanding capacity (194.5 mAh g-1 ) and elongated lifespan (a capacity retention of 84% after 1000 cycles) at 5.0 A g-1 . The reversible Zn anode enabled by the interfacial manipulation strategy via ZnSe cultivator is anticipated to satisfy the demand of commercial use.

Manipulating Electrocatalytic Li2 S Redox via Selective Dual-Defect Engineering for Li-S Batteries.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage, yet they are plagued by the notorious polysulfide shuttle effect and sluggish redox kinetics. While rationally designed redox mediators can facilitate polysulfide conversion, favorable bidirectional sulfur electrocatalysis remains a formidable challenge. Herein, selective dual-defect engineering (i.e., introducing both N-doping and Se-vacancies) of a common MoSe2 electrocatalyst is used to manipulate the bidirectional Li2 S redox. Systematic theoretical prediction and detailed electrokinetic analysis reveal the selective electrocatalytic effect of the two types of defects, thereby achieving a deeper mechanistic understanding of the bidirectional sulfur electrochemistry. The Li-S battery using this electrocatalyst exhibits excellent cyclability, with a low capacity decay rate of 0.04% per cycle over 1000 cycles at 2.0 C. More impressively, the potential for practical applications is highlighted by a high areal capacity (7.3 mAh cm-2 ) and the construction of a flexible pouch cell. Such selective electrocatalysis created by dual-defect engineering is an appealing approach toward working Li-S systems.

Identifying the Evolution of Selenium-Vacancy-Modulated MoSe2 Precatalyst in Lithium-Sulfur Chemistry.

Witnessing compositional evolution and identifying the catalytically active moiety of electrocatalysts is of paramount importance in Li-S chemistry. Nevertheless, this field remains elusive. We report the scalable salt-templated synthesis of Se-vacancy-incorporated MoSe2 architecture (SeVs-MoSe2 ) and reveal the phase evolution of the defective precatalyst in working Li-S batteries. The interaction between lithium polysulfides and SeVs-MoSe2 is probed to induce the transformation from SeVs-MoSe2 to MoSeS. Furthermore, operando Raman spectroscopy and ex situ X-ray diffraction measurements in combination with theoretical simulations verify that the effectual MoSeS catalyst could help promote conversion of Li2 S2 to Li2 S, thereby boosting the capacity performance. The Li-S battery accordingly exhibits a satisfactory rate and cycling capability even with and elevated sulfur loading and lean electrolyte conditions (7.67 mg cm-2 ; 4.0 µL mg-1 S ). This work elucidates the design strategies and catalytic mechanisms of efficient electrocatalysts bearing defects.

Inorganic Low k Cage-molecular Crystals.

For the interlayer dielectric in microelectronics, light element compounds are preferably accepted due to less electronic polarization. Here, the nontrivial dielectric nature of the Sb4O6 cage-molecular crystal, known as α-antimony trioxide (α-Sb2O3), is reported. The gas-phase synthesized α-Sb2O3 nanoflakes are of high crystal quality, from which the abnormal local admittance responses were revealed by scanning microwave impedance microscopy (sMIM). The remarkably low dielectric constant (k), 2.0∼2.5, is corroborated by the analysis of the thickness-dependent sMIM-capacitance signal. In light of the theoretical calculations, the ultralow molecular density and the significantly suppressed ionic polarization are both crucial to the highly reduced k. Combining with the excellent optical band gap, thermal stability, and breakdown strength, α-Sb2O3 is a promising low k dielectric.

Self-assembly of Au@Ag core-shell nanocuboids into staircase superstructures by droplet evaporation.

Plasmonic nanomaterials, along with their assemblies, provide numerous applications due to their profound optical properties. In this work, we report the self-assembly of Au@Ag core-shell nanocuboids (NCs) into staircase superstructures in both vertical and horizontal orientations through two-stage droplet evaporation. Each stair is composed of a uniform well-aligned monolayer of NCs. The gap distance between NCs can be greatly shrunk to boost the corresponding surface-enhanced Raman scattering (SERS) performance using an ethanol wash method. The SERS performance of the assembled NCs is calculated by finite-difference time-domain (FDTD) simulation, and studied against the step number using 4-mercaptobenzoic acid as a Raman reporter molecule. The increasing EF with the increase of layer number proves that the plasmon mode propagates well in our uniformly aligned assemblies.

Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling.