Electrical-Conductive/Insulating Bi-Functional Layers for Stable Zn Metal Anode

Zinc-ion batteries are regarded as an extremely promising candidate for large-scale energy storage equipment due to the inexpensive ingredients and high safety. However, dendrite growth and side reactions occur in the Zn anode, which lead to exceedingly low coulombic efficiency (CE) and poor cycling stability. In this work, we propose a strategy of a conductive/insulating bi-functional coating layer (CIBL) for stable Zn metal anodes. Porous Ag nanowires (NWs) coating as a conductive layer effectively reduces the nuclear barrier and contains Zn²⁺ deposition in a certain space. Polyimide (PI) coatings as insulating layer implement a shunting effect on Zn²⁺, which could reduce the differential concentration on the Zn surface and induce uniform deposition of Zn²⁺. Therefore, the CIBL−Zn//CIBL−Zn battery achieves stable plating/stripping of over 1300 h at 1 mA cm⁻². The CE of CIBL−Zn//CIBL−Zn battery maintains at 99.2 % even after 1000 cycles. Moreover, the CIBL−Zn//V₂O₅ battery exhibits a capacity of nearly 289.2 mA h g⁻¹ at 5 A g⁻¹ after 3000 cycles and no sign of capacity degradation is found, which further demonstrate the feasibility of this strategy in practical application.     

Monolithic Phosphate Interphase for Highly Reversible and Stable Zn Metal Anode

Zinc metal battery (ZMB) is promising as the next generation of energy storage system, but challenges relating to dendrites and corrosion of the zinc anode are restricting its practical application. Here, to stabilize Zn anode, we report a controlled electrolytic method for a monolithic solid-electrolyte interphase (SEI) via a high dipole moment solvent dimethyl methylphosphonate (DMMP). The DMMP-based electrolytes can generate a homogeneous and robust phosphate SEI (Zn₃(PO₄)₂ and ZnP₂O₆). Benefiting from the protecting impact of this in situ monolithic SEI, the zinc electrode exhibits long-term cycling of 4700 h and a high Coulombic efficiency 99.89 % in Zn|Zn and Zn|Cu cell, respectively. The full V₂O₅|Zn battery with DMMP-H₂O hybrid electrolyte exhibits a high capacity retention of 82.2 % following 4000 cycles under 5 A g⁻¹. The first success in constructing the monolithic phosphate SEI will open a new avenue in electrolyte design for highly reversible and stable Zn metal anodes.     

Graphene-Enabled Electric-Field Regulation and Ionic Redistribution Around Lithiophilic Aurum Nanoparticles Toward a Dendrite-Free and 2000-Cycle-Life Lithium Metal Battery

Lithium metal batteries (LMBs) have attracted extensive attention owing to their high energy density. However, the uncontrolled volume changes and serious dendrite growth of the Li metal anode have hindered their commercialization. Herein, a three-dimensional Cu foam decorated with Au nanoparticles and conformal graphene layer was designed to tune the Li plating/stripping behaviors. The 3D−Cu conductive host anchored by lithiophilic Au nanoparticles can effectively alleviate the volume expansion caused by the continuous plating/stripping of Li and reduce the nucleation energy barrier. Notably, the conductive graphene not only facilitates the transfer of electrons, but also acts as an ionic rectifier, thereby avoiding the aggregation of local current density and Li⁺ ions around Au nanoparticles and enabling the uniform Li⁺ flux. As a result, the G−Au@3D−Cu/Li anode ensures the non-dendritic and homogeneous Li⁺ plating/stripping. Electrochemical results show that the symmetric G−Au@3D−Cu/Li cell delivers a low voltage hysteresis of 110 mV after 1000 h at 1 mA cm⁻². Matched with a layered LiNi_0.6Co_0.2Mn_0.2O₂ cathode, the NCM622||G−Au@3D−Cu/Li full cell exhibits a long cycle life of 2000 cycles and an ultra-low capacity decay rate (0.01 % per cycle).     

Regulating Lithium Plating and Stripping by Using Vertically Aligned Graphene/CNT Channels Decorated with ZnO Particles

Lithium (Li) metal is regarded as the ultimate anode material for use in Li batteries due to its high theoretical capacity (3860 mA h g⁻¹). However, the Li dendrites that are generated during iterative Li plating/stripping cycles cause poor cycling stability and even present safety risks, and thus severely handicap the commercial utility of Li metal anodes. Herein, we describe a graphene and carbon nanotube (CNT)-based Li host material that features vertically aligned channels with attached ZnO particles (designated ZnO@G-CNT-C) and show that the material effectively regulates Li plating and stripping. ZnO@G-CNT-C is prepared from an aqueous suspension of Zn(OAc)₂, CNTs, and graphene oxide by using ice to template channel growth. ZnO@G-CNT-C was found to be mechanically robust and capable of guiding Li deposition on the inner walls of the channels without the formation of Li dendrites. When used as an electrode, the material exhibits relatively low polarization for Li plating, fast Li-ion diffusion, and high Coulombic efficiency, even over hundreds of Li plating/stripping cycles. Moreover, full cells prepared with ZnO@G-CNT-C as Li host and LiFePO₄ as cathode exhibit outstanding performance in terms of specific capacity (155.9 mA h g⁻¹ at 0.5 C), rate performance (91.8 mA h g⁻¹ at 4 C), cycling stability (109.4 mA h g⁻¹ at 0.5 C after 800 cycles). The methodology described can be readily adapted to enable the use of carbon-based electrodes with well-defined channels in a wide range of contemporary applications that pertain to energy storage and delivery.     

Polycation-Regulated Electrolyte and Interfacial Electric Fields for Stable Zinc Metal Batteries

Zn metal as one of promising anode materials for aqueous batteries but suffers from disreputable dendrite growth, grievous hydrogen evolution and corrosion. Here, a polycation additive, polydiallyl dimethylammonium chloride (PDD), is introduced to achieve long-term and highly reversible Zn plating/stripping. Specifically, the PDD can simultaneously regulate the electric fields of electrolyte and Zn/electrolyte interface to improve Zn²⁺ migration behaviors and guide dominant Zn (002) deposition, which is veritably detected by Zeta potential, Kelvin probe force microscopy and scanning electrochemical microscopy. Moreover, PDD also creates a positive charge-rich protective outer layer and a N-rich hybrid inner layer, which accelerates the Zn²⁺ desolvation during plating process and blocks the direct contact between water molecules and Zn anode. Thereby, the reversibility and long-term stability of Zn anodes are substantially improved, as certified by a higher average coulombic efficiency of 99.7 % for Zn||Cu cells and 22 times longer life for Zn||Zn cells compared with that of PDD-free electrolyte.     

Dendrite-free and anti-corrosion Zn metal anode enabled by an artificial layer for high-performance Zn ion capacitor

Aqueous zinc energy storage devices, holding various merits such as high specific capacity and low costs, have attracted extensive attention in recent years. Nevertheless, Zn metal anodes still suffer from a short lifespan and low Coulombic efficiency due to corrosion and side reactions in aqueous electrolytes. In this paper, we construct an artificial Sn inorganic layer on Zn metal anode through a facile strategy of atom exchange. The Sn layer suppresses Zn dendrite growth by facilitating homogeneous Zn plating and stripping during charge and discharge processes. Meanwhile, the Sn protective layer also serves as a physical barrier to decrease Zn corrosion and hydrogen generation. As a result, The Sn-coated anode (Sn|Zn) exhibits a low polarization voltage (～34 mV at 0.5 mAh/cm²) after 800 testing hours and displays a smooth and an even surface without corrosion. Moreover, the zinc ion capacitor (Sn|Zn||activated carbon) is assembled with an enhanced capacity of 42 mAh/g and a capacity retention of 95% after 10,000 cycles at 5 A/g. This work demonstrates a feasible approach for the commercialization of aqueous Zn-based energy storage devices.     

Highly Reversible Zinc Metal Anode in a Dilute Aqueous Electrolyte Enabled by a pH Buffer Additive

Aqueous zinc-ion batteries have drawn increasing attention due to the intrinsic safety, cost-effectiveness and high energy density. However, parasitic reactions and non-uniform dendrite growth on the Zn anode side impede their application. Herein, a multifunctional additive, ammonium dihydrogen phosphate (NHP), is introduced to regulate uniform zinc deposition and to suppress side reactions. The results show that the NH₄⁺ tends to be preferably absorbed on the Zn surface to form a “shielding effect” and blocks the direct contact of water with Zn. Moreover, NH₄⁺ and (H₂PO₄)⁻ jointly maintain pH values of the electrode-electrolyte interface. Consequently, the NHP additive enables highly reversible Zn plating/stripping behaviors in Zn//Zn and Zn//Cu cells. Furthermore, the electrochemical performances of Zn//MnO₂ full cells and Zn//active carbon (AC) capacitors are improved. This work provides an efficient and general strategy for modifying Zn plating/stripping behaviors and suppressing side reactions in mild aqueous electrolyte.     

Facile synthesized Cu-SnO2 anode materials with three-dimensional metal cluster conducting architecture for high performance lithium-ion batteries

A novel Cu-SnO₂ anode material derived from Cu₆Sn₅ alloy, retaining high conductivity of Cu and high theoretical capacity of SnO₂ with a facile synthesizing process by oxidation and reduction method. The novel Cu structure penetrates in the composite particles inducing high conductivity and spaceconfined SnO₂, which restrict the pulverization of SnO₂ during lithiation/delithiation process.     

多孔纳米立方FeSe2/石墨烯复合材料的可控构建及在钠离子电池中的应用

设计具有较高比容量和循环稳定性的负极材料对于钠离子电池的发展至关重要。过渡金属硒化物因其具有较高的理论容量而成为潜在的负极材料。但是,硒化物电导率低下且在钠离子嵌入/脱出的过程中会发生较大程度的体积膨胀,导致比容量快速下降。因此,结构调控显得尤为重要。通过常规水热法在二维还原氧化石墨烯（rGO）上原位生长多孔纳米立方体FeSe₂,制备了具有更多活性位点和结构更加稳定的FeSe₂/rGO复合材料。当用作钠离子电池的负极时,复合材料FeSe₂/rGO在0.2 A/g时比容量为694.6 mA?h/g,在2.0 A/g电流密度下,循环300圈后比容量为300 mA?h/g。     

An Organic Coordination Manganese Complex as Cathode for High-Voltage Aqueous Zinc-metal Battery

Aqueous Zn−Mn battery has been considered as the most promising scalable energy-storage system due to its intrinsic safety and especially ultralow cost. However, the traditional Zn−Mn battery mainly using manganese oxides as cathode shows low voltage and suffers from dissolution/disproportionation of the cathode during cycling. Herein, for the first time, a high-voltage and long-cycle Zn−Mn battery based on a highly reversible organic coordination manganese complex cathode (Manganese polyacrylate, PAL−Mn) was constructed. Benefiting from the insoluble carboxylate ligand of PAL−Mn that can suppress shuttle effect and disproportionationation reaction of Mn³⁺ in a mild electrolyte, Mn³⁺/Mn²⁺ reaction in coordination state is realized, which not only offers a high discharge voltage of 1.67 V but also exhibits excellent cyclability (100 % capacity retention, after 4000 cycles). High voltage reaction endows the Zn−Mn battery high specific energy (600 Wh kg⁻¹ at 0.2 A g⁻¹), indicating a bright application prospect. The strategy of introducing carboxylate ligands in Zn−Mn battery to harness high-voltage reaction of Mn³⁺/Mn²⁺ well broadens the research of high-voltage Zn−Mn batteries under mild electrolyte conditions.     

Sn Anodes Protected by Intermetallic FeSn2 Layers for Long-lifespan Sodium-ion Batteries with High Initial Coulombic Efficiency of 93.8 %

With a theoretical capacity of 847 mAh g⁻¹, Sn has emerged as promising anode material for sodium-ion batteries (SIBs). However, enormous volume expansion and agglomeration of nano Sn lead to low Coulombic efficiency and poor cycling stability. Herein, an intermetallic FeSn₂ layer is designed via thermal reduction of polymer-Fe₂O₃ coated hollow SnO₂ spheres to construct a yolk-shell structured Sn/FeSn₂@C. The FeSn₂ layer can relieve internal stress, avoid the agglomeration of Sn to accelerate the Na⁺ transport, and enable fast electronic conduction, which endows quick electrochemical dynamics and long-term stability. As a result, the Sn/FeSn₂@C anode exhibits high initial Coulombic efficiency (ICE=93.8 %) and a high reversible capacity of 409 mAh g⁻¹ at 1 A g⁻¹ after 1500 cycles, corresponding to an 80 % capacity retention. In addition, NVP//Sn/FeSn₂@C sodium-ion full cell shows outstanding cycle stability (capacity retaining rate of 89.7 % after 200 cycles at 1 C).     

Bio-Inspired Polyanionic Electrolytes for Highly Stable Zinc-Ion Batteries

For zinc-ion batteries (ZIBs), the non-uniform Zn plating/stripping results in a high polarization and low Coulombic efficiency (CE), hindering the large-scale application of ZIBs. Here, inspired by biomass seaweed plants, an anionic polyelectrolyte alginate acid (SA) was used to initiate the in situ formation of the high-performance solid electrolyte interphase (SEI) layer on the Zn anode. Attribute to the anionic groups of −COO⁻, the affinity of Zn²⁺ ions to alginate acid induces a well-aligned accelerating channel for uniform plating. This SEI regulates the desolvation structure of Zn²⁺ and facilitates the formation of compact Zn (002) crystal planes. Even under high depth of discharge conditions (DOD), the SA-coated Zn anode still maintains a stable Zn stripping/plating behavior with a low potential difference (0.114 V). According to the classical nucleation theory, the nucleation energy for SA-coated Zn is 97 % less than that of bare Zn, resulting in a faster nucleation rate. The Zn||Cu cell assembled with the SA-coated electrode exhibits an outstanding average CE of 99.8 % over 1,400 cycles. The design is successfully demonstrated in pouch cells, where the SA-coated Zn exhibits capacity retention of 96.9 % compared to 59.1 % for bare Zn anode, even under the high cathode mass loading (>10 mg/cm²).     

Boosting Zn Anode Utilization by Trace Iodine Ions in Organic-Water Hybrid Electrolytes through Formation of Anion-rich Adsorbing Layers

Aqueous Zn batteries are attracting extensive attentions, but their application is still hindered by H₂O-induced Zn-corrosion and hydrogen evolution reactions. Addition of organic solvents into aqueous electrolytes to limit the H₂O activity is a promising solution, but at the cost of greatly reduced Zn anode kinetics. Here we propose a simple strategy for this challenge by adding 50 mM iodine ions into an organic-water (1,2-dimethoxyethane (DME)+water) hybrid electrolyte, which enables the electrolyte simultaneously owns the advantages of low H₂O activity and accelerated Zn kinetics. We demonstrate that the DME breaks the H₂O hydrogen-bond network and exclude H₂O from Zn²⁺ solvation shell. And the I⁻ is firmly adsorbed on the Zn anode, reducing the Zn²⁺ de-solvation barrier from 74.33 kJ mol⁻¹ to 32.26 kJ mol⁻¹ and inducing homogeneous nucleation behavior. With such electrolyte, the Zn//Zn symmetric cell exhibits a record high cycling lifetime (14.5 months) and achieves high Zn anode utilization (75.5 %). In particular, the Zn//VS₂@SS full cell with the optimized electrolyte stably cycles for 170 cycles at a low N : P ratio (3.64). Even with the cathode mass-loading of 16.7 mg cm⁻², the full cell maintains the areal capacity of 0.96 mAh cm⁻² after 1600 cycles.     

A ZIF-8 Host for Dendrite-Free Zinc Anodes and N,O Dual-doped Carbon Cathodes for High-Performance Zinc-Ion Hybrid Capacitors

Zn is a promising anode for aqueous energy storage owing to it intrinsic superior properties such as large capacity, abundant reserves, low potential and safety. But, the growth of dendrites during charge and discharge leads to a decrease in reversibility. In addition, further development of zinc-ion hybrid capacitors (ZICs) is seriously challenging because of the lack of an exceptional cathode. Herein, we use ZIF-8 annealed at 500 °C (annealed ZIF-8) as a host material for stable and dendrite-free Zn anodes. Utilization of annealed ZIF-8 results in dendrite-free Zn deposition and stripping as a result of its porous construction, which contains trace Zn. Furthermore, we firstly proposed innovative N,O dual-doped carbon which was designed by the derived ZIF-8 (ZIF-8 derived C) as cathode for high-energy and power-density ZICs. The new ZIC assembled by Zn@annealed ZIF-8 anode and ZIF-8 derived C cathode provides a capacity of 135.5 mAh g⁻¹ and an energy density of 108.4 Wh kg⁻¹ with a power density of 800 W kg⁻¹ at 1.0 A g⁻¹. In addition, it shows outstanding cycling stability of 91% capacity retention after 6000 cycles at 5.0 A g⁻¹. Moreover, the solid-state ZICs can drive LEDs and smart watches. This ZIC holds promise for the practical application of supercapacitors.     

Zincophilic Electrode Interphase with Appended Proton Reservoir Ability Stabilizes Zn Metal Anodes

The rampant dendrites and hydrogen evolution reaction (HER) resulting from the turbulent interfacial evolution at the anode/electrolyte are the main culprits of short lifespan and low Coulombic efficiency of Zn metal batteries. In this work, a versatile protective coating with excellent zincophilic and amphoteric features is constructed on the surface of Zn metal (ZP@Zn) as dendrite-free anodes. This kind of protective coating possesses the advantages of reversible proton storage and rapid desolvation kinetics, thereby mitigating the HER and facilitating homogeneous nucleation concomitantly. Furthermore, the space charge polarization effect promotes charge redistribution to achieve uniform Zn deposition. Accordingly, the ZP@Zn symmetric cell manifests excellent reversibility at an ultrahigh cumulative plating capacity of 4700 mAh cm⁻² and stable cycling at 80 % depth of discharge (DOD). The ZP@Zn//V₆O₁₃ pouch cell also reveals superior cycling stability with a high capacity of 326.6 mAh g⁻¹.     

Regulated Ion/Electron-Conducting Interphase Enables Stable Zinc-Metal Anodes for Aqueous Zinc-Ions Batteries

Metallic Zinc (Zn) is considered as a remarkably promising anode for aqueous Zn-ion batteries due to its high volumetric capacity and low redox potential. Unfortunately, dendritic growth and severe side reactions destabilizes the electrode/electrolyte interface, and ultimately reduce the electrochemical performance. Here, an artificial protective layer (APL) with a regulated ion and electron-conducting interphase is constructed on the Zn-metal anode to provide excellent interfacial stability in high-rate cycling. The superior ionic and moderate electronic conductivity of the APL derives from the co-embedding of MXene and Zn(CF₃SO₃)₂ salts into the polyvinyl alcohol hydrogel, which enables a synergistic effect of local current density reduction during plating and ion transport acceleration during stripping for Zn anode. Furthermore, the high Young's modulus of the protective layer and dendrite-free deposition morphology during cycling suppresses hydrogen evolution reactions (2.5 mmol h⁻¹ cm⁻²) and passivation. As a result, in symmetrical cell tests, the modified battery presents a stable life of over 2000 cycles at ultra-high current density of 20 mA cm⁻². This research presents a new insight into the formation and regulation of stable electrode-electrolyte interface for the Zn-metal anode.     

Tetraphenylporphyrin-based Chelating Ligand Additive as a Molecular Sieving Interfacial Barrier toward Durable Aqueous Zinc Metal Batteries

The sustained water consumption and uncontrollable dendrite growth strongly hamper the practical applications of rechargeable zinc (Zn) metal batteries (ZMBs). Herein, for the first time, we demonstrate that trace amount of chelate ligand additive can serve as a “molecular sieve-like” interfacial barrier and achieve highly efficient Zn plating/stripping. As verified by theoretical modeling and experimental investigations, the benzenesulfonic acid groups on the additive molecular not only facilitates its water solubility and selective adsorption on the Zn anode, but also effectively accelerates the de-solvation kinetics of Zn²⁺. Meanwhile, the central porphyrin ring on the chelate ligand effectively expels free water molecules from Zn²⁺ via chemical binding against hydrogen evolution, and reversibly releases the captured Zn²⁺ to endow a dendrite-free Zn deposition. By virtue of this non-consumable additive, high average Zn plating/stripping efficiency of 99.7 % over 2100 cycles together with extended lifespan and suppressed water decomposition in the Zn||MnO₂ full battery were achieved, thus opening a new avenue for developing highly durable ZMBs.     

Localized Anion-Cation Aggregated Aqueous Electrolytes with Accelerated Kinetics for Low-Temperature Zinc Metal Batteries

Aqueous zinc metal batteries hold great promise for large-scale energy storage because of their high safety, rich material resources and low cost. However, the freeze of aqueous electrolytes hinders low-temperature operation of the batteries. Here, aqueous localized anion-cation aggregated electrolytes composed of Zn(BF₄)₂ as the salt and tetrahydrofuran (THF) as the diluent, are developed to improve the low-temperature performance of the Zn anode. THF promotes the inclusion of BF₄⁻ in the solvation sheath of Zn²⁺, facilitating the formation of ZnF₂-rich solid-electrolyte-interphase. THF also affects the hydrogen bonding between neighboring H₂O molecules, effectively lowering the freezing point. Therefore, the full cells of Zn||polyaniline (PANI) exhibit an ultralong cycle life of 8000 cycles with an average Coulombic efficiency of 99.99 % at −40 °C. Impressively, the pouch cells display a high capacity retention of 86.2 % after 500 cycles at −40 °C, which demonstrates the great prospect of such electrolytes in cold regions. This work provides new insights for the design of low-temperature aqueous electrolytes.     

Bifunctional Interphase with Target-Distributed Desolvation Sites and Directionally Depositional Ion Flux for Sustainable Zinc Anode

Aqueous zinc batteries (AZBs) feature high safety and low cost, but intricate anodic side reactions and dendrite growth severely restrict their commercialization. Herein, ethylenediaminetetraacetic acid (EDTA) grafted metal organic framework (MOF-E) is proposed as a dually-functional anodic interphase for sustainable Zn anode. Specifically, the target-distributed EDTA serves as an ion-trapped tentacle to accelerate the desolvation and ionic transport by powerful chemical coordination, while the MOFs offer suitable ionic channels to induce oriented deposition. As a result, MOF-E interphase fundamentally suppresses side reactions and guides horizontally arranged Zn deposition with (002) preferred orientations. The Zn|MOF-E@Cu cell exhibits a markedly improved Coulombic efficiency of 99.7 % over 2500 cycles, and the MOF-E@Zn|KVOH (KV₁₂O_30-y ⋅ nH₂O) cell yields a steady circulation of 5000 cycles@90.47 % at 8 A g⁻¹.     

Fast Polysulfide Conversion Catalysis and Reversible Anode Operation by A Single Cathode Modifier in Li-Metal Anode-Free Lithium-Sulfur Batteries

The two major issues confronting the commercialization of rechargeable lithium-sulfur (Li−S) batteries are the sluggish kinetics of the sulfur electrochemical reactions on the cathode and inadequate lithium deposition/stripping reversibility on the anode. They are commonly mitigated with additives designed specifically for the anode and the cathode individually. Here, we report the use of a single cathode modifier, In₂Se₃, which can effectively catalyse the polysulfide reactions on the cathode, and also improve the reversibility of Li deposition and removal on the anode through a LiInS₂/LiInSe₂ containing solid electrolyte interface formed in situ by the Se and In ions dissolved in the electrolyte. The amounts of dissolved Se and In are small relative to the amount of In₂Se₃ administered. The benefits of using this single modification approach were verified in Li-metal anode-free Li−S batteries with a Li₂S loading of 4 mg cm⁻² and a low electrolyte/Li₂S ratio of 7.5 μL mg⁻¹. The resulting battery showed 60 % capacity retention after 160 cycles at the 0.2 C rate and an average Coulombic efficiency of 98.27 %, comparing very well with recent studies using separate electrode modifiers.