Stable Anode Research Articles

Crystal Step‐Induced Uniform and Rapid Deposition on Zinc Anodes

AbstractAqueous Zn‐ion batteries have emerged as promising candidates for large‐scale energy storage owing to their high safety and low cost. However, dendrite growth and side reactions compromise the stability of the Zn anode in practical applications. Here, a novel Zn anode featuring well‐designed crystal steps along the (002) facets, referred to as Step‐Zn is introduced. The intersections of the (002) and (100) planes in these crystal steps create preferential adsorption sites for Zn2⁺ ions, promoting initial electro‐epitaxial growth of Zn that uniformly covers the crystal steps. This process effectively regulates subsequent Zn deposition, ensuring fast reaction kinetics and smooth morphology without dendrite formation. Consequently, the unique Step‐Zn anode exhibits excellent cycle life over 6000 times at 3 mA cm−2 and low greatly reduced polarization voltage under high areal currents and capacities. Integrated with activated carbon (AC) cathode, the Step‐Zn||AC full cell demonstrates excellent durability over 10 000 cycles at 5 A g−1. This work offers valuable insights into controlling Zn deposition modes by engineering the surface microstructure of Zn anodes with greatly extended cycling stability.

Silver bridging TiO2 nanotubes (TNTs) bases and PbO2 active layers to accelerate electron transfer over PbO2/SnO2-Sb/TNTs-Ag/Ti anode for efficient organic pollutants removal

In this work, excellent conductor element Ag was employed to bridge TiO2 nanotubes (TNTs) and PbO2 to construct an “expressway” for rapid electron transfer between the bases and active layers over the fabricated PbO2/SnO2-Sb/TNTs-Ag/Ti anode. Physicochemical characterizations reveal that elemental Ag can fill into the gaps between the TNTs, thus stabilizing structure and improving conductivity of the anode. Electrochemical and accelerated lifetime tests show the expanded reaction area (0.049–0.173 cm2), decreased charge transfer resistance (42.32–4.03 Ω cm−2), and prolonged lifetime (0.29–6.28 years). Furthermore, relatively higher average current efficiency (ACE) and less energy consumption (Esp) can be achieved during electrochemical oxidation of acid gold G (AY36) and rhodamine B (RhB) synthetic wastewaters, as well as shortening their degradation pathways. Our research looks forward to providing a novel Ag bridging design strategy for the synthesis of highly active and stable multilayer anodes.

Enhancing Zinc Anode Stability with Gallium Ion‐Induced Electrostatic Shielding and Oriented Plating

AbstractThe cost‐effectiveness and environmental benefits of aqueous zinc‐ion batteries (ZIBs) have attracted considerable attention. However, practical applications are hindered by side processes including dendritic growth and hydrogen evolution corrosion. Herein, gallium ions (Ga3+) have been chosen as a multifunctional electrolyte additive to improve the reversibility of zinc‐ion batteries (ZIBs). Remarkably, Ga3+ ions adhere to the anode surface, establishing a dynamic electrostatic shielding layer that modulates Zn2+ deposition and prevents side reactions. Typically, Ga3+ ions preferentially adsorb onto the (002) and (110) planes of Zn, facilitating preferential deposition on the (100) plane, resulting in a dendrites‐free zinc anode. Consequently, the Zn||Zn symmetrical cell with Ga3+‐modified electrolyte demonstrates a prolonged lifespan of 4000 h, while the Zn||Ti asymmetric cell exhibits an impressive coulombic efficiency of 99.12% for zinc stripping and plating at 2 mA cm−2. Additionally, the Zn||VO2 cell maintains high capacity retention after 1500 cycles at 5 A g−1. This work presents Ga3+ ions as an electrolyte additive, facilitating the development of a durable dynamic electrostatic shielding effect and preferential (100) plane electroplating, ensuring zinc deposition free from dendrite formation. Such discoveries form a basis for future investigations into novel materials to propel advancements in metal battery technology.

Electrochemical constructing versatile ZnAl-LDH artificial interface layer coated (002)-textured Zn for highly reversible zinc anodes

Rechargeable aqueous zinc-ion batteries (AZIBs), renowned for their high safety, cost-effectiveness, and high energy density, are regarded as an alternative for large-scale energy storage. However, persistent challenges remain in achieving highly reversible AZIBs, primarily centered around the notorious issues associated with the Zn anode. Here, a zincophilic Zn-Al layered double hydroxide (ZnAl-LDH) artificial interface layer coated highly (002)-textured Zn metal anode (SZ/LDH@Zn) with an integrated design are successively constructed by electrochemical methods. Comprehensive characterizations and theoretical calculations reveal that the preferred (002)-textured Zn couping with the zincophilic ZnAl-LDH coating layer not only can effectively regulate the interfacial electric field and Zn2+ flux distribution, guiding a uniform and horizontal Zn2+ deposition but also provide inherent Zn2+ diffusion channels, accelerating its interfacial transport kinetics. Moreover, the ZnAl-LDH layer with good chemical stability acted as a robust physical barrier, impeding direct contact between the electrolyte and Zn anode, thus curbing interfacial side reactions. As a result, the SZ/LDH@Zn||SZ/LDH@Zn symmetric cell delivers unprecedented cycling stability of 5500 h (about 230 days) at 1 mA cm−2, 1 mA h cm−2. The SZ/LDH@Zn||Cu asymmetric cell achieves superior reversibility with a high average Coulombic efficiency of 99.85 % over 3800 cycles. More significantly, the SZ/LDH@Zn||NaV3O8·xH2O full cell with a low N/P ratio (3.62) exhibits an impressive areal capacity of 5.36 mA h cm−2 and reliable operation over 1500 cycles. This work offers a facile and controllable electrochemical coupling strategy to build a highly stable Zn metal anode.

Rational design of epoxy functionalized ionic liquids electrolyte additive for hydrogen-free and dendrite-free aqueous zinc batteries

Despite the high safety and low cost associated with aqueous Zn-ion batteries (ZIBs), uncontrolled Zn dendrite growth and parasitic reactions induced by water significantly diminish their stability. Herein, a new epoxy functionalized ionic liquid, 4-methyl-4-glycidylmorpholin bis[(trifluoromethyl)sulfonyl]imide (MGM[TFSI]), has been developed to mitigate water reactivity for stable ZIBs. It was found that the MGM+ cation disrupts the hydrogen bond network of water, hindering its adsorption on Zn anodes, thereby suppressing water decomposition and enhancing anode stability. Additionally, preferential adsorption of MGM+ cations on the Zn anode surface mitigates tip effects, suppresses dendrite growth, and promotes the formation of a ZnF2 solid electrolyte interphase layer, effectively isolating the anode from the bulk electrolyte. As a result, benefiting from the well-designed MGM+-based electrolyte, Zn//Zn cells achieve significantly enhanced cycling stability, lasting over 2000 h at 1 mA cm−2 with 1 mAh cm−2. Furthermore, Zn//MnO2 full cells deliver remarkable stability, retaining approximately 89 % of their initial capacity after 3000 cycles at 5 A/g. This work proposes that the MGM[TFSI] additive can effectively regulate the interfacial chemistry of the Zn anode, providing an opportunity to design advanced electrolytes for highly reversible ZIBs and beyond.

A bifunctional thiobenzamide additive for improvement of cathode kinetics and anode stability in lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) are considered as the key candidates for the next generation of energy storage devices. However, the practical applications of LSBs are hindered by the slow conversion of sulfur species and the inhomogeneous Li+ precipitation /stripping of lithium anode. Here, we report a bifunctional thiobenzamide electrolyte additive, 4-(trifluoromethyl) thiobenzamide (TFBCA), which synergistically improves cathode redox kinetics and anode stability. Polysulfides (LiPSn) are in-situ transferred to more reactive polysulfide intermediates (T-Sn-T), which significantly improve the liquid–solid reduction process by promoting the deposition dimension of Li2S. A LiF/Li3N-rich solid electrolyte interphase is formed with TFBCA, the uniform lithium deposition is achieved and the growth of lithium dendrites is suppressed. Correspondingly, LSBs with TFBCA show a high capacity (888 mAh·g−1 at 5C) and cycling stability (0.055 % per cycle after 600 cycles at 2C). Even under high sulfur loading (7.1 mg·cm−2) and low E/S ratio of 7, the LSBs also exhibit an areal capacity of 7 mAh·cm−2 after 50 cycles, and an energy density of 314 Wh·kg−1 is achieved for the pouch cell. This work demonstrates an efficient additive strategy through molecular structure design to construct high-performance LSBs.

Zn-anode stability in additive added perchlorate electrolyte for aqueous Zn-MnO2 battery

Extensive research has been conducted on aqueous Zn-MnO2 batteries in the most common ZnSO4 electrolyte. However, the present study focuses on Zn anode stability and subsequent pairing with the commonly utilized MnO2 cathode in a low-concentration aqueous Zn (ClO4)2 electrolyte containing an organic additive, triethyl phosphate (TEP). The structural stability of Zn anodes in optimized additive-added and additive-free electrolytes is analyzed by assembling series of Zn∥Zn symmetry cells under various electrochemical conditions with varying depth of discharges between 20 and 60 %. As such, additive added electrolyte stabilizes the Zn anode over 250 h under high areal capacity/low areal current density of 38.3 mAh cm−2/11.3 mA cm−2 with 60 % depth of discharge at long half-cycle time of 29.5 h. The Zn-MnO2 paired cells in the Zn (ClO4)2 electrolyte with and without additives registered reversible capacities of 262 and 247 mAh g−1, respectively, at 0.05 A g−1. These electrochemical features are completely different from those of the common ZnSO4 electrolyte, whose electrochemical mechanism is still a subject of debate.

Free‐Standing Si@C/CNFs Prepared by Simple Electrospinning as a Stable Anode for Lithium‐Ion Batteries

AbstractThe development of free‐standing and foldable electrodes with excellent electrochemical performance is paramount for flexible electronic devices. However, the silicon‐based free‐standing anodes lack a straightforward preparation process. Herein, we successfully designed a hierarchical Si@C/CNFs composite material by combining hydrothermal and electrospinning techniques, in which the carbon‐coated silicon (Si@C) is served as the primary nanostructure and carbon nanofibers (CNFs) from electrospinning are maintained as the network matrix, resulting in a free‐standing anode. Owing to the amorphous carbon coating on Si nanoparticles and the formation of a 3D network structure of CNFs, which tightly encases the primary Si@C nanostructure, the Si@C/CNFs electrode demonstrates exceptional conductivity and flexibility. This dual carbon‐layer structure further enhances kinetics and mitigates the volume expansion of Si nanoparticles. The Si@C/CNFs electrode exhibits a high specific capacity (1573 mAh g−1 at 0.1 A g−1), exceptional rate capability, and excellent cycling stability (78.5 % capacity retention after 100 cycles). Thus, Si@C/CNFs can be a promising material for the anode electrode in flexible lithium‐ion batteries.

Interfacial Zn2+-solvation regulator towards reversible and stable Zn anode

Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface, predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution. Particularly, the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn2+-solvation and deposition behavior demand comprehensive investigation. Organic molecules endowed with special functional groups (such as hydroxyl, carboxyl, etc.) have the potential to significantly optimize the solvation structure of Zn2+ and regulate the interfacial electric double layer (EDL). By increasing nucleation overpotential and decreasing interfacial free energy, these functional groups facilitate a lower critical nucleation radius, thereby forming an asymptotic nucleation model to promote uniform Zn deposition. Herein, this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure. The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques, indicating that the H-Zn anode exhibits dendrite-free growth, no by-products, and weak hydrogen evolution, in sharp contrast to the bare Zn. Consequently, the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h. Moreover, the H-Zn//NH4V4O10 (NVO) full battery showcases exceptional cycle stability, retaining 95.04% capacity retention after 400 cycles at a large current density of 5 A g−1. This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.

Nanodiamond-Assisted High-Performance Sodium-Ion Batteries with Weakly Solvated Ether Electrolyte at -40°C.

Realizing high performances of sodium-ion batteries (SIBs) working at low temperatures is a pressing need for the commercial applications of SIBs. In this work, nanodiamonds (NDs) are introduced in diglyme electrolytes (ND-Diglyme) to significantly improve the low-temperature performances of SIBs. The corresponding SIB achieves an initial reversible specific capacity of 324mA h g-1 at -40°C (slightly decreased from 357mA h g-1 at 25°C) and shows a capacity retention ratio of ≈82% after 100 cycles at 0.1 A g-1. Moreover, it shows a capacity as high as 40mA h g-1 at 1 A g-1, nearly five times the date of the pure Diglyme electrolyte. Experimentally reveals that introducing NDs is helpful in inhibiting dendrite growth and improving the cyclic stability of anode at LT, because the ND with strong adsorption to sodium ions can not only assist in forming an effective solid electrolyte interface rich with NaF and Na2CO3 but also effectively reduce the activation energy (decreased from 426.68 to 370.51 meV) during the charge transfer processes. Hence, the proposed ND-assisted weakly ether electrolyte in this study presents a viable electrolyte additive solution to fulfill the rising low-temperature demands of SIBs.

Entropy-Driven 60mol% Li Electrolyte for Li Metal-Free Batteries.

Highly Li-concentrated electrolytes are acknowledged for their compatibility with Li metal negative electrodes and high voltage positive electrodes to achieve high-energy Li metal batteries, showcasing stable and facile interfaces for Li deposition/dissolution and high anodic stability. This study aims to explore a highly concentrated electrolyte by adopting entropy-driven chemistry for Li metal-free (so-called anode-free) batteries. The combination of lithium bis(fluorosulfonyl)amide (LiFSA) and lithium trifluoromethanesulfonate (LiOTf)salts in a pyrrolidinium-based ionic liquid is found to significantly modify the coordination structure, resulting in an unprecedented 60mol% Li concentration and a low solvent-to-salt ratio of 0.67:1 in the electrolyte system. This novel 60mol% Li electrolyte demonstrates unique coordination stricture, featuring a high ratio of monodentate-anion structures and aggregates, which facilitates an enhanced Li+ transference number and improved anodic stability. Moreover, the developed electrolyte provides a facile de-coordination process and leads to the formation of an anion-based solid electrolyte interface, which enables stable Li deposition/dissolution properties and demonstrates excellent cycling stability in the Li metal-free full cell with a Li[Ni0.8Co0.1Mn0.1]O2 (NCM811) positive electrode.

Stable Lithium Oxygen Batteries Enabled by Solvent-diluent Interaction in N,N-dimethylacetamide-based Electrolytes.

In the pursuit of next-generation ultrahigh-energy-density Li-O2 batteries, it is imperative to develop an electrolyte with stability against the strong oxidation environments. N,N-dimethylacetamide (DMA) is a recognized solvent known for its robust resistance to the highly reactive reduced oxygen species, yet its application in Li-O2 batteries has been constrained due to its poor compatibility with the Li metal anode. In this study, a rationally selected hydrofluoroether diluent, methyl nonafluorobutyl ether (M3), has been introduced into the DMA-based electrolyte to construct a localized high concentration electrolyte. The stable -CH3 and C-F bonds within the M3 structure could not only augment the fundamental properties of the electrolyte but also fortify its resilience against attacks from O2 - and 1O2. Additionally, the strong electron-withdrawing groups (-F) presented in the M3 diluent could facilitate coordination with the electron-donating groups (-CH3) in the DMA solvent. This intermolecular interaction promotes more alignments of Li+-anions with a small amount of M3 addition, leading to the construction of an anion-derived inorganic-rich SEI that enhances the stability of the Li anode. As a result, the Li-O2 batteries with the DMA/M3 electrolyte exhibit superior cycling performance at both 30 °C (359th) and -10 °C (120th).

Stable Lithium Oxygen Batteries Enabled by Solvent‐diluent Interaction in N,N‐dimethylacetamide‐based Electrolytes

AbstractIn the pursuit of next‐generation ultrahigh‐energy‐density Li−O2 batteries, it is imperative to develop an electrolyte with stability against the strong oxidation environments. N,N‐dimethylacetamide (DMA) is a recognized solvent known for its robust resistance to the highly reactive reduced oxygen species, yet its application in Li−O2 batteries has been constrained due to its poor compatibility with the Li metal anode. In this study, a rationally selected hydrofluoroether diluent, methyl nonafluorobutyl ether (M3), has been introduced into the DMA‐based electrolyte to construct a localized high concentration electrolyte. The stable −CH3 and C−F bonds within the M3 structure could not only augment the fundamental properties of the electrolyte but also fortify its resilience against attacks from O2− and 1O2. Additionally, the strong electron‐withdrawing groups (−F) presented in the M3 diluent could facilitate coordination with the electron‐donating groups (−CH3) in the DMA solvent. This intermolecular interaction promotes more alignments of Li+‐anions with a small amount of M3 addition, leading to the construction of an anion‐derived inorganic‐rich SEI that enhances the stability of the Li anode. As a result, the Li−O2 batteries with the DMA/M3 electrolyte exhibit superior cycling performance at both 30 °C (359th) and −10 °C (120th).

Advances in Functional Organosulfur-Based Mediators for Regulating Performance of Lithium Metal Batteries.

Rechargeable lithium metal batteries (LMBs) are promising next-generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur-based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium-sulfur, lithium-selenium, lithium-oxygen, lithium-intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries.

Motional Resistance as Highly Selective Descriptor to Probe Dynamic Formation of Surface Films on Zinc Anode

AbstractZinc anodes are expected as a promising alternative to lithium‐based anodes in energy storage systems due to their low cost, high theoretical capacity, and environmental friendliness. However, the development of efficient and stable zinc anode requires a fundamental understanding of the interfacial processes occurring during zinc deposition and dissolution cycling. In this study, we employed electrochemical quartz crystal microbalance (EQCM) analysis to investigate the potential‐dependent formation and decomposition of surface films on zinc metal anodes in sulfate‐based aqueous electrolytes. Changes in frequency and motional resistance served as complementary descriptors, with motional resistance being a highly selective indicator for probing dynamic surface film formation driven by side reactions at the zinc anode. While the frequency change provided the overall changes in the mass of both zinc metal and surface films, changes in the motional resistance selectively reflected the amount and nature of the visco‐elastic interface that comprise the surface films. The two descriptors provide quantitative and complementary means to discover the complex interfacial processes such as the formation of surface visco‐elastic films, guiding to the development of more stable and efficient zinc‐based electrochemical systems.

Anion Chemistry towards On‐Site Construction of Solid‐Electrolyte Interface for Highly Stable Metallic Zn Anode

Reversibility of metallic Zn anode serves as the corner stone for the development of aqueous Zn metal battery, which motivates scrutinizing the electrolyte‐Zn interface. As the representative organic zinc salt, zinc trifluorosulfonate (Zn(OTf)2) facilitates a broad class of aqueous electrolytes, however, the stability issue of Zn anode remains crucial. The great challenge lies in the lack of Zn anode protection by the pristinely formed surface structure in aqueous Zn(OTf)2 electrolytes. Accordingly, an electrochemical route was developed to grow a uniform zinc trifluorosulfonate hydroxide (ZTH) layer on Zn anode as an artificial SEI, via regulation on metal dissolution and strong coordination ability of zinc ions. Co‐precipitation was proposed to be the formation mechanism for the artificial SEI, where the reduction stability of OTf‾ anion and the low‐symmetry layer structure of ZTH was unmasked. This artificial SEI favors interfacial kinetics, depresses side reactions, and well maintains its integrity during cycling, leading to a prolonged lifespan of Zn stripping/plating with a high DOD of ~85%, and an improved cycling stability of ~92% retention rate for V2O5/Zn cell at 1 A g‐1. The unveiled role of anion on Zn anode drives the contemplation on the surface chemistry for the blooming aqueous rechargeable battery.

Anion Chemistry towards On-Site Construction of Solid-Electrolyte Interface for Highly Stable Metallic Zn Anode.

Reversibility of metallic Zn anode serves as the corner stone for the development of aqueous Zn metal battery, which motivates scrutinizing the electrolyte-Zn interface. As the representative organic zinc salt, zinc trifluorosulfonate (Zn(OTf)2) facilitates a broad class of aqueous electrolytes, however, the stability issue of Zn anode remains crucial. The great challenge lies in the lack of Zn anode protection by the pristinely formed surface structure in aqueous Zn(OTf)2 electrolytes. Accordingly, an electrochemical route was developed to grow a uniform zinc trifluorosulfonate hydroxide (ZTH) layer on Zn anode as an artificial SEI, via regulation on metal dissolution and strong coordination ability of zinc ions. Co-precipitation was proposed to be the formation mechanism for the artificial SEI, where the reduction stability of OTf‾ anion and the low-symmetry layer structure of ZTH was unmasked. This artificial SEI favors interfacial kinetics, depresses side reactions, and well maintains its integrity during cycling, leading to a prolonged lifespan of Zn stripping/plating with a high DOD of ~85%, and an improved cycling stability of ~92% retention rate for V2O5/Zn cell at 1 A g-1. The unveiled role of anion on Zn anode drives the contemplation on the surface chemistry for the blooming aqueous rechargeable battery.

Composite Anode for PEM Water Electrolyzers: Lowering Iridium Loadings and Reducing Material Costs with a Conductive Additive.

To enable the greater installed capacity of proton exchange membrane water electrolysis (PEMWE) for clean hydrogen production, associated costs must be lowered while achieving high current density performance and durability. Scarce and expensive iridium (Ir) required for the oxygen evolution reaction (OER) is a large contributor to the overall cost, yet high loadings of Ir (1-2 mgIr cm-2) are currently needed in commercial systems to maintain sufficient activity, conductivity, and durability. To meet the aggressive targets for low Ir loadings, we introduce a composite anode approach using a conductive additive that is less expensive than Ir to facilitate robust, high-performance operation with low Ir loading by retaining electrode thickness and in-plane electrical conductivity. In this demonstration, we use platinum (Pt) black as the conductive additive given its high electrical conductivity, acid stability, and current price one-fifth that of Ir. Using a high-activity commercial Ir oxide (IrO x ) catalyst, we present a 95% Ir loading reduction and 80% cost reduction of the anode catalyst materials while maintaining equal current density performance at a cell voltage of 1.8 V. Furthermore, we show enhanced stability of a composite anode compared to an IrO x anode with loadings of 0.10 mgIr cm-2 via accelerated stress test (AST) and postmortem imaging. With this approach, we show promising results toward lowering Ir loadings and material costs, addressing a significant barrier to the widespread adoption of PEMWE for clean hydrogen production.

Lithiation Induced Hetero-Superlattice Zn/ZnLi as Stable Anode for Aqueous Zinc-Ion Batteries.

Three dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero-superlattice Zn/ZnLi (HS-Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite-free zinc deposition, which significantly improves the cycling stability of the HS-Zn/ZnLi alloy (over 2800 h without a short-circuit at 2 mA cm-2). More importantly, this strategy can be extended to HS-Zn/ZnNa and HS-Zn/ZnK anodes that are similar to the HS-Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite-free metal anodes with stable cycling performance.

Lithiation Induced Hetero‐Superlattice Zn/ZnLi as Stable Anode for Aqueous Zinc‐Ion Batteries

AbstractThree dimensional (3D) framework structure is one of the most effective ways to achieve uniform zinc deposition and thus inhibit the Zn dendrites growth in working Zn metallic anode. A major challenge facing for the most commonly used 3D zincophilic hosts is that the zincophilic layer tends to peel off during repeatedly cycling, making it less stable. Herein, for the first time, a hetero‐superlattice Zn/ZnLi (HS−Zn/ZnLi) anode containing periodic arrangements of metallic Zn phase and zincophilic ZnLi phase at the nanoscale, is well designed and fabricated via electrochemical lithiation method. Based on binding energy and stripping energy calculation, and the operando optical observation of plating/stripping behaviors, the zincophilic ZnLi sites with a strong Zn adsorption ability in the interior of the 3D ZnLi framework structure can effectively guide uniform Zn nucleation and dendrite‐free zinc deposition, which significantly improves the cycling stability of the HS−Zn/ZnLi alloy (over 2800 h without a short‐circuit at 2 mA cm−2). More importantly, this strategy can be extended to HS−Zn/ZnNa and HS−Zn/ZnK anodes that are similar to the HS−Zn/ZnLi microstructure, also displaying significantly enhanced cycling performances in AZIBs. This study can provide a novel strategy to develop the dendrite‐free metal anodes with stable cycling performance.