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.

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.

Passivation Layers in Mg-Metal Batteries: Robust Interphases for Li-Metal Batteries.

In advanced batteries, interphases serve as the key component in stabilizing the electrolyte with reactive electrode materials far beyond thermodynamic equilibria. While an active interphase facilitates the transport of working ions, an inactive interphase obstructs ion flow, constituting the primary barrier to the realization of battery chemistries. Here, a successful transformation of a traditionally inactive passivating layer on Mg-metal anode, characteristic of Mg-metal batteries with typical carbonate electrolytes, into an active and robust interphase in the Li-metal scenario is presented. By further strategically designing magnesiated Li+ electrolytes, the in situ development of this resilient interphase on Li-metal anodes, imparting enduring stability to Li-metal batteries with nickel-rich cathodes is induced. It is identified that the strong affinity between Mg2+ and anions in magnesiated Li+ electrolytes assembles ionic clusters with a bias for reducibility, thereby catalyzing the creation of anion-derived interphases rich in inorganic constituents. The prevalence of ionic clusters induced by magnesiation of electrolytes has brought properties only available in high-concentration electrolytes, suggesting a fresh paradigm of tailing electrolytes for highly reversible LMBs.

Engineering High-Performance Li Metal Batteries through Dual-Gradient Porous Cu-CuZn Host.

Porous copper (Cu) current collectors show promise in stabilizing Li metal anodes (LMAs). However, insufficient lithiophilicity of pure Cu and limited porosity in three-dimensional (3D) porous Cu structures led to an inefficient Li-Cu composite preparation and poor electrochemical performance of Li-Cu composite anodes. Herein, we propose a porous Cu-CuZn (DG-CCZ) host for Li composite anodes to tackle these issues. This architecture features a pore size distribution and lithiophilic-lithiophobic characteristics designed in a gradient distribution from the inside to the outside of the anode structure. This dual-gradient porous Cu-CuZn exhibits exceptional capillary wettability to molten Li and provides a high porosity of up to 66.05%. This design promotes preferential Li deposition in the interior of the porous structure during battery operation, effectively inhibiting Li dendrite formation. Consequently, all cell systems achieve significantly improved cycling stability, including Li half-cells, Li-Li symmetric cells, and Li-LFP full cells. When paired synergistically with the double-coated LiFePO4 cathode, the pouch cell configured with multiple electrodes demonstrates an impressive discharge capacity of 159.3 mAh g-1 at 1C. We believe this study can inspire the design of future 3D Li anodes with enhanced Li utilization efficiency and facilitate the development of future high-energy Li metal batteries.

Chlorine bridge bond-enabled binuclear copper complex for electrocatalyzing lithium-sulfur reactions.

Engineering atom-scale sites are crucial to the mitigation of polysulfide shuttle, promotion of sulfur redox, and regulation of lithium deposition in lithium-sulfur batteries. Herein, a homonuclear copper dual-atom catalyst with a proximal distance of 3.5 Å is developed for lithium-sulfur batteries, wherein two adjacent copper atoms are linked by a pair of symmetrical chlorine bridge bonds. Benefiting from the proximal copper atoms and their unique coordination, the copper dual-atom catalyst with the increased active interface concentration synchronously guide the evolutions of sulfur and lithium species. Such a delicate design breaks through the activity limitation of mononuclear metal center and represents a catalyst concept for lithium-sulfur battery realm. Therefore, a remarkable areal capacity of 7.8 mA h cm-2 is achieved under the scenario of sulfur content of 60 wt.%, mass loading of 7.7 mg cm-2 and electrolyte dosage of 4.8 µL mg-1.

Steering Bidirectional Sulfur Redox via Geometric/Electronic Mediator Comodulation for Li-S Batteries.

Mediator design has stimulated ever-increasing attention to help tackle a surge of detrimental caveats in Li-S realms, mainly pertaining to rampant polysulfide shuttling and sluggish redox kinetics. Nevertheless, universal designing philosophy, despite being highly sought-after, remains still elusive to date. Herein, we present a generic and simple material strategy to allow the target fabrication of advanced mediator toward boosted sulfur electrochemistry. This trick is done by the geometric/electronic comodulation of a prototype VN mediator, where the interplay of its triple-phase interface, favorable catalytic activity, and facile ion diffusivity is conducive to steering bidirectional sulfur redox kinetics. In laboratory tests, the thus-derived Li-S cells manifest impressive cyclic performances with a capacity decay rate of 0.07% per cycle over 500 cycles at 1.0 C. Moreover, under a sulfur loading of 5.0 mg cm-2, the cell could sustain a durable areal capacity of 4.63 mAh cm-2. Our work is anticipated to lay a theory-to-application foundation for rationalizing the design and modulation of reliable polysulfide mediators in working Li-S batteries.

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.

Optimized Charge Storage in Aza-Based Covalent Organic Frameworks by Tuning Electrolyte Proton Activity.

Proton activity in electrolytes plays a crucial role in deciding the electrochemical performance of aqueous batteries. On the one hand, it can influence the capacity and rate performance of host materials because of the high redox activity of protons. On the other hand, it can also cause a severe hydrogen evolution reaction (HER) when the protons are aggregated near the electrode/electrolyte interface. The HER dramatically limits the potential window and the cycling stability of the electrodes. Therefore, it is critical to clarify the impact of electrolyte proton activity on the battery macro-electrochemical performance. In this work, using an aza-based covalent organic framework (COF) as a representative host material, we studied the effect of electrolyte proton activity on the potential window, storage capacity, rate performance, and cycle stability in various electrolytes. A tradeoff relationship between proton redox reactions and the HER in the COF host is revealed by utilizing various in situ and ex situ characterizations. Moreover, the origin of proton activity in near-neutral electrolytes is discussed in detail and is confirmed to be related to the hydrated water molecules in the first solvation shell. A detailed analysis of the charge storage process in the COFs is presented. These understandings can be of importance for utilizing the electrolyte proton activity to build high-energy aqueous batteries.

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.

Bimetallic Selenide Decorated Nanoreactor Synergizing Confinement and Electrocatalysis of Se Species for 3D-Printed High-Loading K-Se Batteries.

The potassium-selenium (K-Se) battery has been considered an appealing candidate for next-generation energy storage systems owing to the high energy and low cost. Nonetheless, its development is plagued by the tremendous volume expansion and sluggish reaction kinetics of the Se cathode. Moreover, implementing favorable areal capacity and longevous cycling of a high-loading K-Se battery remains a daunting challenge facing commercial applications. Herein, we devise a Se and CoNiSe2 coembedded nanoreactor (Se/CoNiSe2-NR) affording low carbon content as an advanced cathode for K-Se batteries. We systematically uncover the enhanced K2Se2/K2Se adsorption and promoted K+ diffusion behavior with the incorporation of Co throughout theoretical simulation and electrokinetic analysis. As a result, Se/CoNiSe2-NR harvests high cycling stability with a capacity decay rate of 0.038% per cycle over 950 cycles at 1.0 C. More encouragingly, equipped with a 3D-printed Se/CoNiSe2-NR electrode with tunable Se loadings, K-Se full batteries enable steady cycling at an elevated Se loading of 3.8 mg cm-2. Our endeavor ameliorates the capacity and lifetime performance of the emerging K-Se device, thereby offering a meaningful tactic in pursuing its practical application.

Enhanced Dual-Directional Sulfur Redox via a Biotemplated Single-Atomic Fe-N2 Mediator Promises Durable Li-S Batteries.

The lithium-sulfur (Li-S) battery is considered as an appealing candidate for next-generation electrochemical energy storage systems because of high energy and low cost. Nonetheless, its development is plagued by the severe polysulfide shuttling and sluggish reaction kinetics. Although single-atom catalysts (SACs) have emerged as a promising remedy to expedite sulfur redox chemistry, the mediocre single-atom loading, inferior atomic utilization, and elusive catalytic pathway handicap their practical application. To tackle these concerns, in this work, unsaturated Fe single atoms with high loading capacity (≈6.32 wt%) are crafted on a 3D hierarchical C3 N4 architecture (3DFeSA-CN) by means of biotemplated synthesis. By electrokinetic analysis and theoretical calculations, it is uncovered that the 3DFeSA-CN harnesses robust electrocatalytic activity to boost dual-directional sulfur redox. As a result, S@3DFeSA-CN can maintain a durable cyclic performance with a negligible capacity decay rate of 0.031% per cycle over 2000 cycles at 1.0 C. More encouragingly, an assembled Li-S battery with a sulfur loading of 5.75 mg cm-2 can harvest a high areal capacity of 6.18 mAh cm-2 . This work offers a promising solution to optimize the carbonaceous support and coordination environment of SACs, thereby ultimately elevating dual-directional sulfur redox in pragmatic Li-S batteries.

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.

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.

A Dual-Functional Fibrous Skeleton Implanted with Single-Atomic Co-Nx Dispersions for Longevous Li-S Full Batteries.

Although lithium-sulfur (Li-S) batteries have long been touted as next-generation energy storage devices, the rampant dendrite growth at the anode side and sluggish redox kinetics at the cathode side drastically impede their practical application. Herein, a dual-functional fibrous skeleton implanted with single-atom Co-Nx dispersion is devised as an advanced modificator to realize concurrent regulation of both electrodes. The rational integration of single-atomic Co-Nx sites could convert the fibrous carbon skeleton from lithiophobic to lithiophilic, helping assuage the dendritic formation for the Li anode. Meanwhile, the favorable electrocatalytic activity from the Co-Nx species affording a lightweight feature effectively enables expedited bidirectional conversion kinetics of sulfur electrochemistry, thereby inhibiting the polysulfide shuttle. Moreover, the interconnected porous framework endows the entire skeleton with good mechanical robustness and fast electron/ion transportation. Benefiting from the synergistic effects between atomically dispersed Co-Nx sites and three-dimensional conductive networks, the integrated Li-S full batteries can achieve a reversible areal capacity (>7.0 mAh cm-2) at a sulfur loading of 6.9 mg cm-2. This work might be beneficial to the development of practically viable Li-S batteries harnessing single-atom mediators.

3D Printing of a V8 C7 -VO2 Bifunctional Scaffold as an Effective Polysulfide Immobilizer and Lithium Stabilizer for Li-S Batteries.

Lithium-sulfur (Li-S) batteries have heretofore attracted tremendous interest due to low cost and high energy density. In this realm, both the severe shuttling of polysulfide and the uncontrollable growth of dendritic lithium have greatly hindered their commercial viability. Recent years have witnessed the rapid development of rational approaches to simultaneously regulate polysulfide behaviors and restrain lithium dendritic growth. Nevertheless, the major obstacles for high-performance Li-S batteries still lie in little knowledge of bifunctional material candidates and inadequate explorations of advanced technologies for customizable devices. Herein, a "two-in-one" strategy is put forward to elaborate V8 C7 -VO2 heterostructure scaffolds via the 3D printing (3DP) technique as dual-effective polysulfide immobilizer and lithium dendrite inhibitor for Li-S batteries. A thus-derived 3DP-V8 C7 -VO2 /S electrode demostrates excellent rate capability (643.5 mAh g-1 at 6.0 C) and favorable cycling stability (a capacity decay of 0.061% per cycle at 4.0 C after 900 cycles). Importantly, the integrated Li-S battery harnessing both 3DP hosts realizes high areal capacity under high sulfur loadings (7.36 mAh cm-2 at a sulfur loading of 9.2 mg cm-2 ). This work offers insight into solving the concurrent challenges for both S cathode and Li anode throughout 3DP.

Universal in Situ Crafted MOx-MXene Heterostructures as Heavy and Multifunctional Hosts for 3D-Printed Li-S Batteries.

The Li-S battery has emerged as a promising next-generation system for advanced energy storage. Notwithstanding the recent progress, the problematic polysulfide shuttling, retarded sulfur redox, and low output of volumetric capacity remain daunting challenges toward its practicability. In response, this work demonstrates herein a universal approach to in situ craft MOx-MXene (M: Ti, V, and Nb) heterostructures as heavy and multifunctional hosts to harvest good battery performances with synchronous polysulfide immobilization and conversion. Theoretical calculations indicate that the in situ implanted oxides boost the reaction kinetics of polysulfide transformation without affecting the intrinsic conductivity of MXene. As a result, the representative VOx-V2C/S electrode enables a high volumetric capacity (offering 1645.98 mAh cm-3 at 0.2 C) and cycling stability (retaining 631.17 mAh cm-3 after 1500 cycles at 2.0 C with a capacity decay of 0.03% per cycle). More encouragingly, 3D-printed sulfur electrodes harnessing VOx-V2C hosts readily harvest an areal capacity of 9.74 mAh cm-2 at 0.05 C under an elevated sulfur loading of 10.78 mg cm-2, holding promise for the development of practically viable Li-S batteries.

Defective VSe2-Graphene Heterostructures Enabling In Situ Electrocatalyst Evolution for Lithium-Sulfur Batteries.

Electrocatalysts remain vitally important for the rational management of intermediate polysulfides (LiPSs) in the realm of Li-S batteries. In terms of transition-metal-based candidates, in situ evolution of electrocatalysts in the course of an electrochemical process has been acknowledged; nevertheless, consensus has not yet been reached on their real functional states as well as catalytic mechanisms. Herein, we report an all-chemical vapor deposition design of the defective vanadium diselenide (VSe2)-vertical graphene (VG) heterostructure on carbon cloth (CC) targeting a high-performance sulfur host. The electrochemistry induces the sulfurization of VSe2 to VS2 at Se vacancy sites, which propels the adsorption and conversion of LiPSs. Accordingly, the VSe2-VG@CC/S electrode harvests an excellent cycling stability at 5.0 C with a capacity decay of only 0.039% per cycle over 800 cycles, accompanied by a high areal capacity of 4.9 mAh cm-2 under an elevated sulfur loading of 9.6 mg cm-2. Theoretical simulation combined with operando characterizations reveals the key role played by the Se vacancy with respect to the electrocatalyst evolution and LiPS regulation. This work offers insight into the rational design of heterostructure sulfur hosts throughout defect engineering.