High-Voltage Zinc-Ion Batteries: Design Strategies and Challenges

Rechargeable zinc-ion batteries (ZIBs) have recently attracted attention for applications in energy storage systems owing to their intrinsic safety, low cost, environmental compatibility, and competitive gravimetric energy density. To enable the practical applications of ZIBs, their energy density must be equivalent to the existing commercial lithium-ion batteries. To acquire high-energy density, increasing the operating voltage of the battery is undoubtedly an effective method, which demands cathode material to exhibit a high voltage versus Zn²⁺/Zn, while matching a highly reversible anode and an electrolyte with a sufficiently wide electrochemical stability window. This review focuses on the design strategies and challenges towards high-voltage ZIBs. First, the basic electrochemistry of ZIBs and the recent progress in various high-voltage cathode materials for ZIBs, including Prussian blue analogs, polyanionic compounds, and metal-based oxides are introduced. The challenges and corresponding countermeasures of these materials are discussed, while strategies to further improve the cathode operating voltage, influence factors of voltage in the redox reaction, and energy storage mechanism are also illustrated. The following section describes the strategies towards high-performance Zn anode, and summarizes the electrolytes that can help increase the battery voltage. The final section outlines the potential development in ZIBs.     

Tungsten‐Based Materials for Lithium‐Ion Batteries

Lithium‐ion batteries are widely used as reliable electrochemical energy storage devices due to their high energy density and excellent cycling performance. The search for anode materials with excellent electrochemical performances remains critical to the further development of lithium‐ion batteries. Tungsten‐based materials are receiving considerable attention as promising anode materials for lithium‐ion batteries owing to their high intrinsic density and rich framework diversity. This review describes the advances of exploratory research on tungsten‐based materials (tungsten oxide, tungsten sulfide, tungsten diselenide, and their composites) in lithium‐ion batteries, including synthesis methods, microstructures, and electrochemical performance. Some personal prospects for the further development of this field are also proposed.     

An Energy‐Dense Solvent‐Free Dual‐Ion Battery

Ever‐increasing energy demands call for alternative energy storage technologies with balanced performance and cost characteristics to meet current and emerging applications. Dual‐ion batteries (DIBs) are considered particularly attractive owing to the potentially high specific energy, a rich variety of charge carrier combinations, and the applicability of metal‐free cathode and earth‐abundant anode materials. However, their performance falls far below expectations because of a large excess of solvent needed to dissolve electroactive species that induces side reactions and contributes parasitic weight, which penalizes the reversible capacity and cell‐level energy density. Herein, a solvent‐free DIB utilizing a binary alkali metal molten salt based on bis(fluorosulfonyl)amide as the electrolyte to solve these issues is demonstrated. The cell (NaK‐DIB) operates in a temperature range of 90–120 °C and exhibits high theoretical energy densities of 246 Wh kg^?1 and 533 Wh L^?1 based on active materials and capacity‐matched electrolyte, far surpassing those of reported DIBs. Further improvements could realize affordable grid‐scale energy storage.     

A Dilute Fluorinated Phosphate Electrolyte Enables 4.9 V-Class Potassium Ion Full Batteries

Potassium ion batteries using graphite anode and high-voltage cathodes are considered to be optimizing candidates for large-scale energy storage. However, the lack of suitable electrolytes significantly hinders the development of high-voltage potassium ion batteries. Herein, a dilute (0.8 m ) fluorinated phosphate electrolyte is proposed, which exhibits extraordinary compatibility with both graphite anode and high-voltage cathodes. The phosphate solvent, tris(2,2,2-trifluoroethyl) phosphate (TFP), has weak solvating ability, which not only allows the formation of robust anion-derived solid electrolyte interphase on graphite anode but also effectively suppresses the corrosion of Al current collector at high voltage. Meanwhile, the high oxidative stability of fluorinated TFP solvent enables stable ultrahigh-voltage (4.95 V) cycling of a potassium vanadium fluorophosphate (KVPO₄F) cathode. Using TFP-based electrolyte, the 4.9 V-class potassium ion full cell based on graphite anode and KVPO₄F cathode shows rather remarkable cycling performance with a high capacity retention of 87.2% after 200 cycles. This study provides a route to develop dilute electrolytes for high-voltage potassium ion batteries, by utilizing solvents with both weak solvating ability and high oxidative stability.     

Fast Rate and Long Life Potassium‐Ion Based Dual‐Ion Battery through 3D Porous Organic Negative Electrode

Potassium‐based dual ion batteries (K‐DIBs) with potassium cation (K⁺) intercalation graphitic anodes have been investigated for their potential in large‐scale energy storage applications owing to their merits of low cost and environmental friendly. Nonetheless, graphite anodes are plagued by volume expansion from the large K⁺ ions and the co‐intercalation of solvent molecules during the charging. Accordingly, organic materials stand out for the flexible adjustable structures and abundant active sites, which can accommodate cations by multiple functional groups without structural collapse. However, K‐DIBs based on organic anodes have rarely been investigated. Herein, 3D porous dipotassium terephthalate nanosheets are synthesized via a freeze‐dry method as the K‐DIB anode, which can reversibly store K⁺ ions at a fast rate with a high specific capacity and robust stability due to the sufficient redox active sites and diffusion pathways of K⁺ ions in the 3D porous structure. Consequently, a novel K‐DIB configuration combining this fast kinetics organic anode and environmental friendly expanded graphite (EG) cathode is constructed (pK2TP//EG), which exhibits a high specific capacity (68 mAh g^‐1 at 2 C), good rate performance up to 20 C, and long cycling life with a capacity retention ~100% after 2000 cycles, which is the best performance observed among reported K‐DIBs.     

A Rechargeable Battery with an Iron Metal Anode

To date, tremendous efforts of the battery community are devoted to batteries that employ Li⁺, Na⁺, and K⁺ as charge carriers and nonaqueous electrolytes. However, aqueous batteries hold great promise for stationary energy storage due to their inherent low cost and high safety. Among metal batteries that use aqueous electrolytes, zinc metal batteries are the focus of attention. In this study, iron as an anode candidate in aqueous batteries is investigated because iron is undoubtedly the most earth‐abundant and cost‐effective metal anode. Reversible iron plating/stripping in a FeSO₄ electrolyte is demonstrated on the anode side and reversible topotactic (de)insertion of Fe²⁺ in a Prussian blue analogue cathode is showcased. Furthermore, it is revealed that LiFePO₄ can pair up with the iron metal anode in a hybrid cell, delivering stable performance as well.     

High‐Performance Cathode Based on Self‐Templated 3D Porous Microcrystalline Carbon with Improved Anion Adsorption and Intercalation

Dual‐ion batteries (DIBs) have attracted much attention due to their advantages of low cost and especially environmental friendliness. However, the capacities of most DIBs are still unsatisfied (≈100 mAh g^?1) ascribed to the limited capacity of anions intercalation for conventional graphite cathode. In this study, 3D porous microcrystalline carbon (3D‐PMC) was designed and synthesized via a self‐templated growth approach, and when used as cathode for a DIB, it allows both intercalation and adsorption of anions. The microcrystalline carbon is beneficial to obtain capacity originated from anions intercalation, and the 3D porous structure with a certain surface area contributes to anions adsorption capacity. With the synergistic effect, this 3D‐PMC is utilized as cathode and tin as anode for a sodium‐based DIB, which has a high capacity of 168.0 mAh g^?1 at 0.3 A g^?1, among the best values of reported DIBs so far. This cell also exhibits long‐term cycling stability with a capacity retention of ≈70% after 2000 cycles at a high current rate of 1 A g^?1. It is believed that this work will provide a strategy to develop high‐performance cathode materials for DIBs.     

An Ultrastable Aqueous Iodine-Hydrogen Gas Battery

Rechargeable hydrogen gas batteries are highly desirable for large-scale energy storage because of their long life cycle, high round trip efficiency, fast reaction kinetics, and hydrogen gas profusion. Coupling advanced cathode chemistries with hydrogen gas anode is an emerging and exciting area of research. Here, a novel high-performance aqueous iodine-hydrogen gas (I₂-H₂) battery using iodine as cathode and hydrogen gas as the electrocatalytic anode in environmentally benign aqueous electrolytes is reported. The working chemistry of the battery involves I₂/I⁻ solid-liquid reactions occurring over the cathode along with H₂/H₂O gas-liquid reactions at the anode, achieving a high rate performance of 100 C and long-lasting stability of over 60 000 cycles. Additionally, the static aqueous I₂-H₂ battery displays a volumetric capacity of 15.5 Ah L⁻¹ along with good self-healing capability towards cell overcharge. The current battery design exhibits robust electrochemical performance irrespective of acidic, neutral, and alkaline electrolyte systems. This study paves the way towards the industrialization of economically effective, high-power density, and long-term I₂-H₂ batteries for large-scale energy storage applications.     

Progress of Phosphate-based Polyanion Cathodes for Aqueous Rechargeable Zinc Batteries

Aqueous rechargeable zinc batteries (ARZBs) are recently prevailing devices that utilize the abundant Zn resources and the merits of aqueous electrolytes to become a competitive alternative for large-scale energy storage. Benefiting from the unique inductive effect and flexible structure, the past five years have experienced a diversiform of phosphate-based polyanion materials that are used as cathodes in ARZBs. In this review, the most recent advances in the Zn²⁺ storage mechanisms and electrolyte optimization of the phosphate-based cathodes of ARZBs, which mainly focus on vanadium/iron-based phosphates and their derivatives are presented. Furthermore, in addition to significant progress on polyanion phosphate-based cathode materials, the design strategies both for electrode materials and compatible electrolytes are also elaborated to improve the energy density and extend the cycling life of aqueous Zn/polyanion batteries.     

A High‐Potential Anion‐Insertion Carbon Cathode for Aqueous Zinc Dual‐Ion Battery

Aqueous dual‐ion batteries (DIBs) are promising for large‐scale energy storage due to low cost and inherent safety. However, DIBs are limited by low capacity and poor cycling of cathode materials and the challenge of electrolyte decomposition. In this study, a new cathode material of nitrogen‐doped microcrystalline graphene‐like carbon is investigated in a water‐in‐salt electrolyte of 30 m ZnCl₂, where this carbon cathode stores anions reversibly via both electrical double layer adsorption and ion insertion. The (de)insertion of anions in carbon lattice delivers a high‐potential plateau at 1.85 V versus Zn²⁺/Zn, contributing nearly 1/3 of the capacity of 134 mAh g^?1 and half of the stored energy. This study shows that both the unique carbon structure and concentrated ZnCl₂ electrolyte play critical roles in allowing anion storage in carbon cathode for this aqueous DIB.     

A Universal Strategy Toward Low-Cost Aqueous Sulfur–Iodine Batteries

Rechargeable aqueous batteries with non-toxic and non-flammable features are promising candidates for large-scale energy storage. However, their practical applications are impeded by the insufficient electrochemical stability windows of aqueous electrolytes and intrinsic drawbacks of current electrodes. Herein, an aqueous sulfur–iodine chemistry that can be deployed in aqueous battery systems by employing water-in-bisalt (WiBS) electrolyte, sulfur composite anode, and iodine composite cathode is demonstrated. The freestanding iodine/carbon cloth cathode and halide-containing WiBS electrolyte can support the continuous I⁺/I⁰ reaction by forming interhalogen. Meanwhile, the highly-concentrated electrolyte and inorganic-based solid electrolyte interphase can effectively suppress the dissolution/diffusion of polysulfides, thus realizing S/S_x²⁻ conversion reactions on the anode. Therefore, the as-assembled aqueous sulfur–iodine batteries based on S/S_x²⁻ and I⁺/I⁰ redox couples can deliver a high energy density of 158.7 Wh kg⁻¹ with a considerable cycling performance and safety. Furthermore, this chemistry can be further extended to multivalent ion-based battery systems. As demonstration models, Ca-based and Al-based aqueous sulfur–iodine batteries are also fabricated, which provide a new avenue towards the development of aqueous batteries for low-cost and highly safe energy storage.     

Wide Working Temperature Range Rechargeable Lithium–Sulfur Batteries: A Critical Review

At the technological forefront of energy storage, there is still a continuous upsurge in demand for high energy and power density batteries that can operate at a wide range of temperature. Rechargeable lithium sulfur batteries stand out among other advanced cell concepts owing to their ultrahigh theoretical gravimetric energy density characteristic as well as merits of low cost and environmental friendliness. Although achieving good operability of ambient lithium sulfur batteries, extending their workability to both higher and lower temperatures is also of paramount importance especially for future task-specific applications. As a first attempt, this review presents a comprehensive understanding on the advances, challenges, and future research directions on lithium sulfur batteries operating at both low and high temperature extremes. From a material perspective, the workability of sulfur-containing cathode materials, advanced electrolytes (from conventional liquid to quasi- and all-solid-state electrolytes), lithium metal anodes and the electrochemically inert components (separators and interlayer materials) at extreme temperatures are thoroughly analyzed. The insurmountable challenges and mechanistic understandings caused by thermal changes are critically reviewed. Finally, potential future research directions and prospects for lithium sulfur batteries operated at a wide range of temperature are also proposed.     

A High‐Performance Sodium‐Ion Hybrid Capacitor Constructed by Metal–Organic Framework–Derived Anode and Cathode Materials

Sodium‐ion hybrid capacitors (SIHCs) can potentially combine the virtues of high‐energy density of batteries and high‐power output as well as long cycle life of capacitors in one device. The key point of constructing a high‐performance SIHC is to couple appropriate anode and cathode materials, which can well match in capacity and kinetics behavior simultaneously. In this work, a novel SIHC, coupling a titanium dioxide/carbon nanocomposite (TiO₂/C) anode with a 3D nanoporous carbon cathode, which are both prepared from metal–organic frameworks (MOFs, MIL‐125 (Ti) and ZIF‐8, respectively), is designed and fabricated. The robust architecture and extrinsic pseudocapacitance of TiO₂/C nanocomposite contribute to the excellent cyclic stability and rate capability in half‐cell. Hierarchical 3D nanoporous carbon displays superior capacity and rate performance. Benefiting from the merits of structures and performances of anode and cathode materials, the as‐built SIHC achieves a high energy density of 142.7 W h kg^?1 and a high power output of 25 kW kg^?1 within 1–4 V, as well as an outstanding life span of 10 000 cycles with over 90% of the capacity retention. The results make it competitive in high energy and power–required electricity storage applications.     

Progress and Perspectives of Lithium Aluminum Germanium Phosphate-Based Solid Electrolytes for Lithium Batteries

Solid-state lithium batteries are considered promising energy storage devices due to their superior safety and higher energy density than conventional liquid electrolyte-based batteries. Lithium aluminum germanium phosphate (LAGP), with excellent stability in air and good ionic conductivity, has gained tremendous attention over the past decades. However, the poor interface compatibility with Li anode, slow Li-ion conduction in thick pellets, and high-temperature sintering procedure limit the further development of LAGP solid electrolytes in practical applications. This review comprehensively summarizes the crystal structure, Li-ion conducting mechanism, and various synthesis methods, especially the latest thin-film preparation approach. The underlying reason for Li/LAGP interfacial instability is identified, followed by several advanced interface engineering strategies, for example, introducing a functional interlayer. The integration design of LAGP-based solid electrolytes and cathode is also highlighted to enable high-loading cathodes. Additionally, recent progress of lithium-oxygen and lithium-sulfur batteries with LAGP-based solid electrolytes is discussed. Moreover, the different Li-ion migration pathways, preparation procedures, and electrochemical performance of polymer-LAGP composite solid electrolytes in Li-ion batteries are introduced. Lastly, the remaining challenges and opportunities are proposed to encourage more efforts in this field. This review aims to provide fundamental insights and promising directions toward practical LAGP-based solid-state batteries.     

Integrated Configuration Design Strategy Via Cathode-Gel Electrolyte With Forged Solid Electrolyte Interface Toward Advanced Lithium-Sulfurized Polyacrylonitrile Batteries

Li-SPAN batteries are a promising energy storage system, providing remarkable energy density and high Coulomb efficiency. However, the inherent sluggishness of the cathode's electrochemical kinetics and the instability of the Li anode hamper their cycle lifespan. In this study, a novel design of integrated configuration between cathode and electrolyte that addresses the challenges and promises to reshape the landscape of Li-SPAN, significantly enhancing the cycling stability, is presented. An artificial solid electrolyte interface (ASEI) is forged to simultaneously stabilize the Li anode and improve the interfacial compatibility, enabling an all-in-one battery system. A vertically aligned cathode structure is achieved using directional ice templating, enabling efficient Li-ion diffusion and enhancing electrochemical kinetics. The Li metal anode is coated with a MOF-on-COF ASEI, ensuring uniform Li⁺ deposition and high Li-ion transference number (0.86). Dual surface engineering further enhances the Li-SPAN cell, exhibiting a low capacity decay rate of 0.037% per cycle after 1000 cycles and superior C-rate performance. This study introduces promising strategies for effectively overcoming the challenges associated with the SPAN cathode and Li anode and paves the way for the design of high-performance Li-SPAN batteries, unlocking their full potential in the field of advanced energy storage systems.     

Anode/Cathode Dual-Purpose Aluminum Current Collectors for Aqueous Zinc-Ion Batteries

Rechargeable aqueous zinc (Zn)-ion batteries (RAZIBs), which use non-flammable aqueous electrolytes and low-cost electrode materials, show great potential to boost the development of safe, cost-effective, and highly efficient energy storage systems. The adoption of lightweight and inexpensive aluminum (Al) as current collectors seems to be a good vision, but Al exhibits an easily-corroded nature and a high impedance in aqueous electrolytes, making it a challenge to realize the utilization of Al current collector in RAZIBs. In this study, through the direct current magnetron sputtering, niobium (Nb) coated Al (Al-Nb) foils are prepared, which shows superior corrosion-resistance in an aqueous solution, while maintaining a satisfying electronic conductivity. Moreover, the Al-Nb foils can be adopted to both anode and cathode current collectors while exhibiting high coulombic efficiency and good cycling stability even when they are tested under a condition that can meet the real-world application demands, e.g., the Zn||Al-Nb half-cell shows an average coulombic efficiency of 99.17% in 320 cycles under a current density of 25 mA cm⁻² and a galvanizing capacity of 6.25 mAh cm⁻². The superior performance of the modified Al current collectors may mark a significant step toward the development of high-energy-density aqueous batteries.     

Stabilizing Solid Electrolyte Interphases on Both Anode and Cathode for High Areal Capacity,High‐Voltage Lithium Metal Batteries with High Li Utilization and Lean Electrolyte

High‐energy‐density lithium metal batteries are considered the most promising candidates for the next‐generation energy storage systems. However, conventional electrolytes used in lithium‐ion batteries can hardly meet the demand of the lithium metal batteries due to their intrinsic instability for Li metal anodes and high‐voltage cathodes. Herein, an ester‐based electrolyte with tris(trimethylsilyl)phosphate additive that can form stable solid electrolyte interphases on the anode and cathode is reported. The additive decomposes before the ester solvent and enables the formation of P‐ and Si‐rich interphases on both electrodes that are ion conductive and robust. Thus, lithium metal batteries with a high‐specific‐energy of 373 Wh kg^?1 can exhibit a long lifespan of over 80 cycles under practical conditions, including a low negative/positive capacity ratio of 2.3, high areal capacity of 4.5 mAh cm^?2 for cathode, high‐voltage of 4.5 V, and lean electrolyte of 2.8 µL mAh^?1. A 4.5 V pouch cell is further assembled to demonstrate the practical application of the tris(trimethylsilyl)phosphate additive with an areal capacity of 10.2 and 9.4 mAh cm^?2 for the anode and cathode, respectively. This work is expected to provide an effective electrolyte optimizing strategy compatible with current lithium ion battery manufacturing systems and pave the way for the next‐generation Li metal batteries with high specific energy and energy density.     

Lithium Tritelluride as an Electrolyte Additive for Stabilizing Lithium Deposition and Enhancing Sulfur Utilization in Anode-Free Lithium–Sulfur Batteries

Despite the potential to become the next-generation energy storage technology, practical lithium–sulfur (Li–S) batteries are still plagued by the poor cyclability of the lithium-metal anode and sluggish conversion kinetics of S species. In this study, lithium tritelluride (LiTe₃), synthesized with a simple one-step process, is introduced as a novel electrolyte additive for Li–S batteries. LiTe₃ quickly reacts with lithium polysulfides and functions as a redox mediator to greatly improve the cathode kinetics and the utilization of active materials in the cathode. Moreover, the formation of a Li₂TeS₃/Li₂Te-enriched interphase layer on the anode surface enhances ionic transport and stabilizes Li deposition. By regulating the chemistry on both the anode and cathode sides, this additive enables a stable operation of anode-free Li–S batteries with only 0.1 m concentration in conventional ether-based electrolytes. The cell with the LiTe₃ additive retains 71% of the initial capacity after 100 cycles, while the control cell retains only 23%. More importantly, with high utilization of Te, the additive enables significantly better cyclability of anode-free pouch full-cells under lean electrolyte conditions.     

Graphene Oxide‐Template Controlled Cuboid‐Shaped High‐Capacity VS4 Nanoparticles as Anode for Sodium‐Ion Batteries

Room‐temperature sodium‐ion batteries have attracted great attentions for large‐scale energy storage applications in renewable energy. However, exploring suitable anode materials with high reversible capacity and cyclic stability is still a challenge. The VS₄, with parallel quasi‐1D chains structure of V⁴⁺(S₂^2?)₂, which provides large interchain distance of 5.83 Å and high capacity, has showed great potential for sodium storage. Here, the uniform cuboid‐shaped VS₄ nanoparticles are prepared as anode for sodium‐ion batteries by the controllable of graphene oxide (GO)‐template contents. It exhibits superb electrochemical performances of high‐specific charge capacity (≈580 mAh·g^?1 at 0.1 A·g^?1), long‐cycle‐life (≈98% retain at 0.5 A·g?¹ after 300 cycles), and high rates (up to 20 A·g^?1). In addition, electrolytes are optimized to understand the sodium storage mechanism. It is thus demonstrated that the findings have great potentials for the applications in high‐performance sodium‐ion batteries.     

Pre-Protonated Vanadium Hexacyanoferrate for High Energy-Power and Anti-Freezing Proton Batteries

Proton batteries have been considered as an innovative energy storage technology owing to their high safety and cost-effectiveness. However, the development of fast-charging proton batteries with high energy/power density is greatly limited by feasible material selection. Here, the pre-protonated vanadium hexacyanoferrate (H-VHCF) is developed as a proton cathode material to alleviate the capacity loss of proton-free electrode materials during electrochemical tests. The pre-protonation process realizes fast and long-distance transport of protons by shortening diffusion path and reducing migration barriers. Benefitting from the enhanced hydrogen bonding network combined with dual redox reactions of V and Fe in protonated H-VHCF cathode, a high energy density of 74 Wh kg⁻¹ at 1.1 kW kg⁻¹, and a maximum power density of 54 kW kg⁻¹ at 65 Wh kg⁻¹ is achieved for the asymmetric proton batteries coupling with MoO₃/MXene anode. Proton transport and double oxidation-reduction center are verified by theoretical calculations and ex situ experimental measurements. Considering the anti-freezing availability of proton batteries, 82.5% of its initial capacity is maintained after 10000 cycles under −40 °C at 0.5 A g⁻¹. As a proof-of-concept, flexible device fabricated by optimized electrodes and hydrogel electrolytes can power up a light-emitting diode even under a bent state.