Zn Batteries Research Articles

Manganese-based MOF interconnected carbon nanotubes as a high-performance cathode for rechargeable aqueous zinc-ion batteries

Aqueous zinc-ion batteries (ZIBs) have attracted extensive attention due to their low cost, environmental friendliness, and high volumetric specific capacity. However, the design of cathode materials with high performance for ZIBs is quite limited. In this paper, a kind of manganese-based metal-organic framework/carbon nanotubes (Mn-MOF/CNT) composite is prepared as the cathode material for ZIBs via a one-pot in situ solvothermal method. Particularly, the assembled Mn-MOF/CNT//Zn battery exhibits high specific capacity (260 mAh g−1 at 50 mA g−1) and excellent capacity retention (approximately 100 %) after 900 cycles at 1000 mA g−1. This significant electrochemical performance is attributed to the high porosity and the high conductivity of Mn-MOF/CNT, as well as the Mn2+ electrolyte additive. This work renders a new sight to design high-performance MOF-based cathode materials for aqueous ZIBs.

Customizing Hydrophilic Terminations for V2CTx MXene Toward Superior Hybrid‐Ion Storage in Aqueous Zinc Batteries

AbstractV2CTx MXene is a “rising star” cathode material for aqueous zinc‐based batteries (AZBs) owing to its large/flexible interlayer spacing, rich redox chemistry of V, and high electronic conductivity. Nevertheless, the plentiful F surface terminations generated during the common preparation (fluorine‐containing acid etching process) of V2CTx generally result in high hydrophobicity, poor Zn affinity, and sluggish ion‐diffusion kinetics. Herein, a novel OH‐termination‐rich V2CTx material with interlayer “K+‐pillars” (alk‐V2CTx) is fabricated via a facile one‐step alkalization method, which features excellent hydrophilicity, expanded ion‐transport channels, and robust layered structure. Impressively, the tailored alk‐V2CTx cathode enables highly reversible and rapid Li+/Zn2+ co‐insertion/extraction electrochemistry in the formulated 15 m LiTSFI + 1 m Zn(CF3SO3)2 aqueous electrolyte, meanwhile, the “self‐exfoliation” phenomenon of MXenes upon cycling significantly increases the active sites, rendering the superior rate performance (498.2/195.1 mAh g−1 at 0.1/30 A g−1, respectively) and exceptional cycling life (96.2% capacity retention over 20 000 cycles). Systematic in situ/ex situ analyses and theoretical computations elucidate the above hybrid‐ion storage mechanisms. Finally, flexible quasi‐solid‐state rechargeable Zn batteries employing the alk‐V2CTx cathode exhibit inspiring energy output even under severe deformation conditions and low temperatures. This study provides new perspectives for designing high‐performance MXene‐based cathodes for AZBs by modulating surface terminations.

Synergistically regulating the separator pore structure and surface property toward dendrite-free and high-performance aqueous zinc-ion batteries

As an emerging electrochemical device, aqueous zinc-ion batteries (ZIBs) present promising potential in safe and large-scale energy storage. However, the large pores of commercial glass fiber (GF) separators result in uneven Zn2+ ion flux, leading to severe dendrite growth issues of Zn metal anodes. Herein, we integrated a multifunctional layer on the GF separator that can synergistically regulate the pore feature and surface property of commercial GF separators. Such modification layer, composed of nanocellulose and SiO2 nanoparticles, exhibited uniform nanoporous structure and abundant negatively charged polar functional groups. These features allow regulating the distribution of Zn2+ ions at the separator-anode interface, facilitating stable and uniform Zn nucleation and growth. Moreover, the electrostatic interaction between the negatively charged functional groups and Zn2+ ions enhanced the Zn2+ ion transport kinetics, preventing the Zn dendrites formation and adverse reactions. Consequently, the modified electrolyte-filled GF separator showed an increased Zn2+ ion transference number of 0.65. The symmetric Zn//Zn batteries utilizing such a separator achieved an impressive cycling life of 500 h at a high current density/capacity of 10 mA cm−2/4 mAh cm−2, nearly nine times longer than the battery using the unmodified GF separator (<55 h). The superior electrochemical performance was verified in both Zn//AC and Zn//LiMn2O4 full battery evaluations. This work presents a novel synergistic modification strategy for developing advanced separators for aqueous ZIBs.

A facile tip shielding strategy for highly reversible Zn anode

Long-term reversibility and stability of aqueous Zn-ion batteries (AZIBs) at high current density are significantly impeded by uncontrolled Zn dendrites and side reactions on Zn anodes. Herein, a facile tip-shielding strategy was proposed via surface reduction approach aimed at liberating pure Zn sites for interfacial grafting of 5-amino-2-fluoro-pyridine (AFPD) molecular solid-electrolyte interface (SEI), realizing the direct utilization of the selective adsorption procedure in electrolyte optimization to substitute of the non-discriminatory modification process in interfacial engineering. This approach could effectively suppress Zn dendrite growth, hydrogen evolution reaction, and corrosion/passivation. Characterization and simulation results demonstrated that the parallel absorption mode of 5-amino-2-fluoro-pyridine (AFPD), preferential absorption of AFPD on non-Zn(002) facets, and homogeneous electric field distribution synergistically promote the deposition of planar and low-angle Zn lamellas. Consequently, the symmetrical battery assembled by the optimized AFPD-2–4@Zn electrodes achieved a significantly enhanced cycling performance (over 3400 h) in contrast to the bare Zn||bare Zn battery (approximately 370 h) at 5 mA cm−2 and 1 mAh cm−2. AFPD-2–4@Zn||MnO2 full cell also manifested elevated capacity retention of approximately 70.2 % at 1 A/g after 700 cycles. This strategy introduces a facile tip-shielding strategy to construct robust Zn anodes for achieving the practical implementation of AZIBs, especially at high current densities.

Engineering anion defects of ternary V-S-Se layered cathodes for ultrafast zinc ion storage

In this work, a novel stainless-steel (SS) supported lattice-mismatched V-S-Se layered compound (VSySe2−x-SS) with high selenium (Se) vacancy was synthesized by tailoring the molar ratio of S to Se. The difference between the radii of Se and S results in lattice mismatches for a large number of Se vacancies, and the highest vacancy with the ultrafast zinc (Zn) storage performance are achieved by tuning a molar ratio of sulfur (S) to Se. More interestingly, with the introduction of Se vacancies, additional redox peaks of S appear, and creates more mass-transport channels as well as active sites for Zn2+ toward fast reaction kinetics. Density functional theory (DFT) calculations confirm that the Se defects can also effectively reduce the adsorption energy of Zn2+ ions on VS0.5Se2−x-SS for more reversible adsorption/desorption process of Zn2+ ions. Consequently, the specific capacity of the VS0.5Se2−x-SS electrode is as high as 188.1 mAh g−1 after 70 cycles at 0.6 A g−1, while accomplishing an excellent rate capability and satisfactory cycle stability. In addition, an assembled flexible quasi-solid state VS0.5Se2−x-SS//Zn battery also display good cycle stability, excellent electrochemical performance, and good environmental adaptability under different malignant environments including bending, soaking, hammering, weighing, washing and cutting. This work demonstrates a facile approach for electrode modifications used in Zn2+ ion batteries, holding great promise for practical applications and shedding lights on fundamentals of defects effects on battery performance.

Controlled synthesis of spindle-like CoNi2S4 as electrode material for aqueous energy storage application

Rational structural design is an important method to control conductivity and enhance the electrochemical performance. In this work, a spindle-like CoNi2S4 is prepared by a simple hydrothermal technique. XRD and SEM tests indicate the spindle shape of CoNi2S4. TEM measurement further implies the hollow structure, which can effectively shorten electron/ion transfer distance and improve conductivity. Electrochemical analysis demonstrates that the CoNi2S4 exhibits a specific capacitance of 1326.2 F g−1 at 1 A g−1; the CoNi2S4//AC also shows high specific capacitance (96.48 F g−1 at 0.2 A g−1) and cycling durability with nearly no capacitance retention after 10,000 cycles. Furthermore, in Ni–Zn battery application field, the CoNi2S4//Zn also displays satisfying specific capacity (156.7 mAh g−1 at 0.5 A g−1) and cycle durability (∼60.3 % capacity retention after 1500 cycles). The above results imply that CoNi2S4 is a promising electrode candidate in energy storage field.

Guiding Zn Uniform Deposition with Polymer Additives for Long-lasting and Highly Utilized Zn Metal Anodes.

The parasitic side reaction on Zn anode is the key issue which hinders the development of aqueous Zn-based energy storage systems on power-grid applications. Here, a polymer additive (PMCNA) engineered by copolymerizing 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-acryloyl glycinamide (NAGA) was employed to regulate the Zn deposition environment for satisfying side reaction inhibition performance during long-term cycling with high Zn utilization. The PMCNA can preferentially adsorb on Zn metal surface to form a uniform protective layer for effective water molecule repelling and side reaction resistance. In addition, the PMCNA can guide Zn nucleation and deposition along 002 plane for further side reaction and dendrite suppression. Consequently, the PMCNA additive can enable the Zn//Zn battery with an ultrahigh depth of discharge (DOD) of 90.0% for over 420 h, the Zn//active carbon (AC) capacitor with long cycling lifespan, and the Zn//PANI battery with Zn utilization of 51.3% at low N/P ratio of 2.6.

Guiding Zn Uniform Deposition with Polymer Additives for Long‐lasting and Highly Utilized Zn Metal Anodes

AbstractThe parasitic side reaction on Zn anode is the key issue which hinders the development of aqueous Zn‐based energy storage systems on power‐grid applications. Here, a polymer additive (PMCNA) engineered by copolymerizing 2‐methacryloyloxyethyl phosphorylcholine (MPC) and N‐acryloyl glycinamide (NAGA) was employed to regulate the Zn deposition environment for satisfying side reaction inhibition performance during long‐term cycling with high Zn utilization. The PMCNA can preferentially adsorb on Zn metal surface to form a uniform protective layer for effective water molecule repelling and side reaction resistance. In addition, the PMCNA can guide Zn nucleation and deposition along 002 plane for further side reaction and dendrite suppression. Consequently, the PMCNA additive can enable the Zn//Zn battery with an ultrahigh depth of discharge (DOD) of 90.0 % for over 420 h, the Zn//active carbon (AC) capacitor with long cycling lifespan, and the Zn//PANI battery with Zn utilization of 51.3 % at low N/P ratio of 2.6.

Activating Organic Electrode via Trace Dissolved Organic Molecules.

Organic electrode materials have gained attention for their tunable structures and sustainability, but their low electronic conductivity requires the use of large amounts of carbon additives (30 wt %) and low mass loadings (<2 mg cm-2) in electrodes. Here, we synthesize dibenzo[b,i]phenazine-5,7,12,14-tetrone (DPT) as a cathode active material for an aqueous Zn battery and find that Zn2+ storage dominates the cathode reaction. This battery demonstrates high capacity (367 mAh g-1), high-rate performance, and superlong life (12000 cycles). Remarkably, despite DPT's insulative nature, even with a high mass loading (10 mg cm-2) and only 10 wt % carbon additives, the DPT-based cathode exhibits promising performance due to trace dissolved discharge product (DPTx-). During discharge, the DPT is reduced to trace amounts of dissolved DPTx- at the cathode surface, which in turn reduces the remaining solid DPT as a redox mediator. Furthermore, dissolution-redeposition results in the reduction of DPT size and the formation of pores, further activating the electrode.

Chemisorption Effect Enables High-Loading Zinc-Iodine Batteries

Rechargeable Zn-I2 batteries featuring intrinsic safety and high energy density demonstrate promising energy storage prospects. However, the poor interface stability of the Zn anode and the undesirable shuttle effect severely hinder the device stability due to the diffusive characteristics of the soluble polyiodides in aqueous media. Here, a synergetic physicochemical strategy that combines physical constraints and chemical absorption was proposed by developing a composite host matrix with a core/porous-sheath structure, which can effectively confine iodine species. Initial I− ions bind securely with carboxylated multi-walled carbon nanotubes (c-MCNTs) to form the C–I bonds through chemical interactions. Furthermore, the pore structure of microporous carbon (MPC) not only restricts the iodine species in the pores through physisorption (secondary adsorption) but also facilitates the diffusion of Zn2+. The as-prepared carbon nanotubes coated with microporous carbon (glucose as the carbon source, and its ratio to CNT is 12:1) can serve as a host material (CNT@MPC12), and adsorb iodide ions to derive CNT@MPC12-I−. As a result, the developed aqueous Zn battery with CNT@MPC12-I− cathode delivers superior reversible rate capacity (0.35mAh cm–2 at 20mAcm–2) and remarkable cycling performance (12000 cycles at 10mAcm–2). Notably, such cathode can also exhibit an impressive capacity retention of 97% after 8600 cycles, even at an ultrahigh loading mass of 16.05mgcm–2. As such, our strategy can be extended to design other metal I2 batteries with high loading and long-life expectancy.

Conversion-type Cathode Materials for Aqueous Zn Metal Batteries in Non-Alkaline Aqueous Electrolytes: Progress, Challenges, And Solutions.

Aqueous Zn metal batteries are attractive as safe and low-cost energy storage systems. At present, due to the narrow window of the aqueous electrolyte and the strong reliance of the Zn2+ ion intercalated reaction on the host structure, the current intercalated cathode materials exhibit restricted energy densities. In contrast, cathode materials with conversion reactions can promise higher energy densities. Especially, the recently reported conversion-type cathode materials that function in non-alkaline electrolytes have garnered increasing attention. This is because the use of non-alkaline electrolytes can prevent the occurrence of side reactions encountered in alkaline electrolytes and thereby enhance cycling stability. However, there is a lack of comprehensive review on the reaction mechanisms, progress, challenges, and solutions to these cathode materials. In this review, four kinds of conversion-type cathode materials including MnO2 , halogen materials (Br2 and I2 ), chalcogenide materials (O2 , S, Se, and Te), and Cu-based compounds (CuI, Cu2 O, Cu2 S, CuO, CuS, and CuSe) are reviewed. First, the reaction mechanisms and battery structures of these materials are introduced. Second, the fundamental problems and their corresponding solutions are discussed in detail in each material. Finally, future directions and efforts for the development of conversion-type cathode materials for aqueous Zn batteries are proposed. This article is protected by copyright. All rights reserved.

A systematic study on the metallophilicity of ordered five-atomic-layer MXenes using high-throughput automated workflow and machine learning

Dendrite growth is an important issue hindering practical applications of various kinds of metal (e.g. Li, Na, K, Mg, Ca, Fe, Zn, and Al) batteries. To tackle this problem, an effective method is to introduce metallophilic materials as hosts for metal anodes. Due to its high electrical conductivity, ease of assembly, and large compositional space, MXene is an excellent choice for anode host materials. However, how do MXenes’ compositions influence their metallophilicity to different kinds of metals, and how do we find MXenes with the strongest metallophilicity to different kinds of metals? To answer these questions, a density functional theory (DFT) based high-throughput automated workflow (HTAW) is designed and a machine learning (ML) study is performed focusing on the metallophilicity of ordered five-atomic-layer MXenes. For the first time, the metallophilicity of ordered five-atomic-layer MXenes from their entire compositional space to a total of eight kinds of metal anodes is studied. The metallophilicity of ∼10 % of the compositional space is investigated by the HTAW and serves as the dataset for ML study, and the remaining ∼90 % is predicted by the trained ML model. Based on the predictions, a ‘cooperation with neighbor’ mechanism governing MXenes’ metallophilicity is summarized, MXenes with the strongest metallophilicity to the eight kinds of metals are discovered, and the already synthesized -O terminated Cr2TiC2 is found to be a member of them, which represents a readily available subject for further experimental verifications and practical applications.

Surface Adsorption and Proton Chemistry of Ultra-Stabilized Aqueous Zinc-Manganese Dioxide Batteries.

Aqueous rechargeable Zinc (Zn) batteries incorporating MnO2 cathodes possess favorable sustainability properties and are being considered for low-cost, high-safety energy storage. However, unstable electrode structures and unclear charge storage mechanisms limit their development. Here, advanced transmission electron microscopy, electrochemical analysis, and theoretical calculations are utilized to study the working mechanisms of a Zn/MnO2 battery with a Co2+ -stabilized, tunnel-structured α-MnO2 cathode (Cox MnO2 ). It is shown that Co2+ can be pre-intercalated into α-MnO2 and occupy the (2×2) tunnel structure, which improves the structural stability of MnO2 , facilitates the proton diffusion and Zn2+ adsorption on the MnO2 surface upon battery cycling. It is further revealed that for the MnO2 cathode, the charge storage reaction proceeds mainly by proton intercalation with the formation of α-Hy Cox MnO2 , and that the anode design (with or without Zn metal) affects the surface adsorption of by-product Zn4 SO4 (OH)6 ·nH2 O on MnO2 surface. This work advances the fundamental understanding of rechargeable Zn batteries and also sheds light on efficient electrode modifications toward performance enhancement.

Tuning the Valence of MnOx Cathodes Reveals the Universality of the Proton‐Coupled Electrodissolution/Electrodeposition Mechanism in Rechargeable Aqueous Zn Batteries

AbstractThe charge storage mechanism of manganese oxides (MnOx) in rechargeable mild aqueous Zn batteries is still a matter of debate, with no consensus on mechanism and charge carriers. In this work, this issue is addressed by relying on a quantitative and comparative electrochemical study of low‐valence crystalline MnOx cathodes in a range of aqueous electrolytes, with a primary focus on spinel Mn3O4. The results demonstrate that the oxidation state of Mn in MnOx structures as well as their degree of crystallinity have little impact on the electrochemical reactivity, all MnOx being fully converted into soluble Mn2+ upon discharge. It is further revealed that this electrodissolution mechanism is affected by Mn3O4 dismutation in the most acidic electrolytes. Accordingly, the true thermodynamics and kinetics of Mn3O4 are only accessible at mildly acidic to neutral pHs. In addition, the study confirms the phase transformation of Mn3O4 to Mn5O8 upon galvanostatic oxidation, and demonstrates that this transformation only proceeds in Mn2+‐free electrolytes, since otherwise amorphous MnO2 electrodeposits on top of Mn3O4. Finally, it is concluded that regardless of the starting MnOx material, after the first discharge or a first charge/discharge cycle, subsequent charge/discharge cycles rely on a reversible proton‐coupled electrodeposition of amorphous MnO2.

NiCo2O4 on monolithic 3DGF/CNT for high performance hybrid zinc batteries

Hybrid Zn-Air and Zn-MX (MX refers to metal species with cation redox properties) batteries that combine the merits of both types are attracting increasing interest. However, the low areal capacity of the Zn-MX segment hinders their applications toward power resilience. Increasing the electrochemically active material loading is critical to achieving sufficient capacity but poses a challenge for conventional electrodes to maintain fast gas diffusion, which is necessary for the Zn-air function. Herein, we report an advanced, monolithic, carbon-based current collector by growing carbon nanotubes (CNT) onto a 3D graphene network (3DGF). The porous and highly conductive current collector readily accommodates more electrochemically active material, NiCo2O4 (NCO), thereby improving the Zn-NCO segment’s capacity without sacrificing the Zn-air segment’s performance. The 3DGF/CNT/NCO electrode was fabricated into a hybrid Zn battery which achieved a superior areal specific capacity of 2.87 mAh cm−2 at 5 mA cm−2, almost threefold of previously reported values, and an impressive rate capability and cycling stability with 98% of original capacity retained after 1000 cycles at 20 mA cm−2 charging/discharging current density. This work showcases 3DGF/CNT as an advanced current collector architecture for new and novel batteries.

Revealing the missing puzzle piece of concentration in regulating Zn electrodeposition.

Despite achievements in suppressing dendrites and regulating Zn crystal growth, secondary aqueous Zn batteries are still rare in the market. Existing strategies mainly focus on electrode modification and electrolyte optimization, while the essential role of ion concentration in liquid-to-solid electrodeposition is neglected for a long time. Herein, the mechanism of concentration regulation in Zn electrodeposition is investigated in depth by combining electrochemical tests, post hoc characterization, and multiscale simulations. First, initial Zn electrodeposition is thermodynamically controlled epitaxial growth, whereas with the rapid depletion of ions, the concentration overpotential transcends the thermodynamic influence to kinetic control. Then, the evolution of the morphology from 2D sheets to 1D whiskers due to the concentration change is insightfully revealed by the morphological characterization and phase-field modeling. Furthermore, the depth of discharge (DOD) results in large concentration differences at the electrode-electrolyte interface, with a mild concentration distribution at lower DOD generating (002) crystal plane 2D sheets and a heavily varied concentration distribution at higher DOD yielding arbitrarily oriented 3D blocks. As a proof of concept, relaxation is introduced into two systems to homogenize the concentration distribution, revalidating the essential role of concentration in regulating electrodeposition, and two vital factors affecting the relaxation time, i.e., current density and electrode distance, are deeply investigated, demonstrating that the relaxation time is positively related to both and is more sensitive to the electrode distance. This work contributes to reacquainting aqueous batteries undergoing phase transitions and reveals a missing piece of the puzzle in regulating Zn electrodeposition.

Corn Husk‐Derived Activated Carbon as High‐Performance Anode Constituent for Rechargeable Aqueous Zn/α‐MnO2 Batteries

Zinc (Zn) aqueous batteries have gained significant research interest for large‐scale electrochemical energy storage applications due to their rich abundance of raw materials, high energy density, environmental friendliness, low capital, and maintenance expenditure. However, the progress of metallic Zn anode in the aqueous Zn battery chemistry is hindered by several critical challenges, including low Coulombic efficiency and the formation of Zn dendrites, irrespective of the pH of the electrolyte. Herein, the application of porous activated carbon (AC) derived from waste corn husk as Zn anode constituent to improve the cyclability of the aqueous Zn battery is reported. In the full cell study, it is observed that the battery containing 15 wt% of AC as anode coupled with α‐MnO2 nanorods cathode shows excellent capacity retention of 86.42% (initial discharge capacity = 211.67 mAh g−1) after 125 charge/discharge cycles at current rate of 100 mA g−1. Moreover, herein, insights into converting waste to energy by utilizing the biowaste precursor to develop stable and durable rechargeable aqueous Zn‐based batteries are provided.

Molecular engineering of self-assembled monolayers for highly utilized Zn anodes

Stabilizing the Zn anode under high utilization rates is highly applauded yet very challenging in aqueous Zn batteries. Here, we rationally design a zincophilic short-chain aromatic molecule, 4-mercaptopyridine (4Mpy), to construct self-assembled monolayers (SAMs) on a copper substrate to achieve highly utilized Zn anodes. We reveal that 4Mpy could be firmly bound on the Cu substrate via Cu–S bond to form compact and uniform SAMs, which could effectively isolate the water on the electrode surface and thus eliminate the water-related side reactions. In addition, the short-chain aromatic ring structure of 4Mpy could not only ensure the ordered arrangement of zincophilic pyridine N but also facilitate charge transfer, thus enabling uniform and rapid Zn deposition. Consequently, the Zn/4Mpy/Cu electrode not only enables the symmetric cell to stably cycle for over 180 ​h at 10 ​mA ​cm−2 under a high depth-of-discharge of 90%, but also allows the MnO2-paired pouch cell to survive for 100 cycles under a high Zn utilization rate of 78.8%. An anode-free 4Mpy/Cu||graphite cell also operates for 150 cycles without obvious capacity fading at 0.1 ​A ​g−1. This control of interfacial chemistry via SAMs to achieve high utilization rates of metal anodes provides a new paradigm for developing high-energy metal-based batteries.

High Energy Density Aqueous Zinc–Chalcogen (S, Se, Te) Batteries: Recent Progress, Challenges, and Perspective

AbstractZinc‐ion batteries with chalcogen‐based (S, Se, Te) cathodes have emerged as a promising candidate for utility‐scale energy storage systems and portable electronics, which have attracted rapid attention and offer tremendous opportunities owing to their excellent energy density, on top of the advantages of aqueous Zn batteries including cost‐effectiveness, inherent safety, and eco‐friendliness. Here, a comprehensive overview on the basic mechanism of zinc–chalcogen batteries with their great advantages and intrinsic issues is provided. More detailed recent progress is summarized and the existing challenges with promising strategies are provided as well. First, four specific types of batteries are presented, including: zinc–sulfur, zinc–selenium, zinc–selenium sulfide, and zinc–tellurium batteries. Second, the remaining challenges within chalcogen‐based cathodes in the material preparation, physicochemical properties, and battery performance are summarized and discussed. Meanwhile, a series of constructive strategies are comprehensively put forward for optimizing electrochemical performance. Finally, the future research perspectives of zinc–chalcogen batteries are proposed for the exploration and innovation of next‐generation green zinc storage applications.

Reversible Zn electrodeposition enabled by interfacial chemistry manipulation for high-energy anode-free Zn batteries

Aqueous Zn batteries have attracted intensive interest in terms of the high safety and sustainable raw materials with low cost. However, the excess use of Zn anode greatly limits the practical energy density of batteries and arouses a threat to their real-life application. Here, a robust heterointerface composed of 0D metal nanodots and 2D metal carbide nanosheets with triple synergistic effects is designed to manipulate interfacial chemistry for anode-free Zn batteries. An interface of in situ anchoring ultrafine Sn nanodots on Na+ decorated MXene nanosheets is used as a model. The 2D Na-MXene promotes the Zn plating/stripping kinetics and homogenizes the distributions of electric field and ion flux. The high-affinity Zn binding sites of 0D Sn nanodots reduce the plating energy barrier and consequently manipulate the uniform Zn nucleation/growth. The in situ formed ZnF2 layer during Zn plating allows Zn ions to diffuse and shields side reactions. Consequently, the stable Zn plating/stripping with a high accumulated areal capacity of 5,000 mAh cm−2 is realized at high current density and plating capacity (10 mA cm−2∼20 mAh cm−2). Benefitting from triply synergistic effects derived from built cooperative interfaces, an anode-free Zn cell is constructed, proving ameliorative cyclic stability.