Active Salt/Silica‐Templated 2D Mesoporous FeCo‐Nx‐Carbon as Bifunctional Oxygen Electrodes for Zinc–Air Batteries

Two types of templates, an active metal salt and silica nanoparticles, are used concurrently to achieve the facile synthesis of hierarchical meso/microporous FeCo‐N_x‐carbon nanosheets (meso/micro‐FeCo‐N_x‐CN) with highly dispersed metal sites. The resulting meso/micro‐FeCo‐N_x‐CN shows high and reversible oxygen electrocatalytic performances for both ORR and OER, thus having potential for applications in rechargeable Zn–air battery. Our approach creates a new pathway to fabricate 2D meso/microporous structured carbon architectures for bifunctional oxygen electrodes in rechargeable Zn–air battery as well as opens avenues to the scale‐up production of rationally designed heteroatom‐doped catalytic materials for a broad range of applications.     

A Biodegradable Polydopamine‐Derived Electrode Material for High‐Capacity and Long‐Life Lithium‐Ion and Sodium‐Ion Batteries

Polydopamine (PDA), which is biodegradable and is derived from naturally occurring products, can be employed as an electrode material, wherein controllable partial oxidization plays a key role in balancing the proportion of redox‐active carbonyl groups and the structural stability and conductivity. Unexpectedly, the optimized PDA derivative endows lithium‐ion batteries (LIBs) or sodium‐ion batteries (SIBs) with superior electrochemical performances, including high capacities (1818 mAh g^?1 for LIBs and 500 mAh g^?1 for SIBs) and good stable cyclabilities (93 % capacity retention after 580 cycles for LIBs; 100 % capacity retention after 1024 cycles for SIBs), which are much better than those of their counterparts with conventional binders.     

An All‐Solid‐State Fiber‐Shaped Aluminum–Air Battery with Flexibility,Stretchability, and High Electrochemical Performance

Owing to the high theoretical energy density of metal–air batteries, the aluminum–air battery has been proposed as a promising long‐term power supply for electronics. However, the available energy density from the aluminum–air battery is far from that anticipated and is limited by current electrode materials. Herein we described the creation of a new family of all‐solid‐state fiber‐shaped aluminum–air batteries with a specific capacity of 935 mAh g^?1 and an energy density of 1168 Wh kg^?1. The synthesis of an electrode composed of cross‐stacked aligned carbon‐nanotube/silver‐nanoparticle sheets contributes to the remarkable electrochemical performance. The fiber shape also provides the aluminum–air batteries with unique advantages; for example, they are flexible and stretchable and can be woven into a variety of textiles for large‐scale applications.     

From K‐O2 to K‐Air Batteries: Realizing Superoxide Batteries on the Basis of Dry Ambient Air

Although using an air cathode is the goal for superoxide‐based potassium‐oxygen (K‐O₂) batteries, prior studies were limited to pure oxygen. Now, the first K‐air (dry) battery based on reversible superoxide electrochemistry is presented. Spectroscopic and gas chromatography analyses are applied to evaluate the reactivity of KO₂ in ambient air. Although KO₂ reacts with water vapor and CO₂ to form KHCO₃, it is highly stable in dry air. With this knowledge, rechargeable K‐air (dry) batteries were successfully demonstrated by employing dry air cathode. The reduced partial pressure of oxygen plays a critical role in boosting battery lifespan. With a more stable environment for the K anode, a K‐air (dry) battery delivers over 100 cycles (>500 h) with low round‐trip overpotentials and high coulombic efficiencies as opposed to traditional K‐O₂ battery that fails early. This work sheds light on the benefits and restrictions of employing the air cathode in superoxide‐based batteries.     

From Solid‐Solution Electrodes and the Rocking‐Chair Concept to Today's Batteries

Lithium‐ion batteries (LIBs) have become ubiquitous power sources for small electronic devices, electric vehicles, and stationary energy storage systems. Despite the success of LIBs which is acknowledged by their increasing commodity market, the historical evolution of the chemistry behind the LIB technologies is laden with obstacles and yet to be unambiguously documented. This Viewpoint outlines chronologically the most essential findings related to today's LIBs, including commercial electrode and electrolyte materials, but furthermore also depicts how the today popular and widely emerging solid‐state batteries were instrumental at very early stages in the development of LIBs.     

Modified High‐Nickel Cathodes with Stable Surface Chemistry Against Ambient Air for Lithium‐Ion Batteries

High‐Ni layered oxides are promising next‐generation cathodes for lithium‐ion batteries owing to their high capacity and lower cost. However, as the Ni content increases over 70 %, they have a high dynamic affinity towards moisture and CO₂ in ambient air, primarily reacting to form LiOH, Li₂CO₃, and LiHCO₃ on the surface, which is commonly termed “residual lithium”. Air exposure occurs after synthesis as it is common practice to handle and store them under ambient conditions. The air exposure leads to significant performance losses, and hampers the electrode fabrication, impeding their practical viability. Herein, we show that substituting a small amount of Al for Ni in the crystal lattice notably improves the chemical stability against air by limiting the formation of LiOH, Li₂CO₃, LiHCO₃, and NiO in the near‐surface region. The Al‐doped high‐Ni oxides display a high capacity retention with excellent rate capability and cycling stability after being exposed to air for 30 days.     

Flexible,Stretchable, and Rechargeable Fiber‐Shaped Zinc–Air Battery Based on Cross‐Stacked Carbon Nanotube Sheets

The fabrication of flexible, stretchable and rechargeable devices with a high energy density is critical for next‐generation electronics. Herein, fiber‐shaped Zn–air batteries, are realized for the first time by designing aligned, cross‐stacked and porous carbon nanotube sheets simultaneously that behave as a gas diffusion layer, a catalyst layer, and a current collector. The combined remarkable electronic and mechanical properties of the aligned carbon nanotube sheets endow good electrochemical properties. They display excellent discharge and charge performances at a high current density of 2 A g^?1. They are also flexible and stretchable, which is particularly promising to power portable and wearable electronic devices.     

Polyaniline/Pure Carbon Assemblies as Efficient Self‐standing Metal‐free Oxygen Electrodes in Alkaline Media for Zn‐Air Batteries

A facile design and fabrication of self‐standing metal‐free polyaniline (PANI)@carbon nanotubes (CNTs) composite membrane was initially proposed by straightforward noncovalent wrapping the polymer around pure CNTs. Without introduction of extra heteroatoms into CNTs, the optimized PANI@CNTs composite exhibits a much better electrocatalytic performance for oxygen evolution reaction (OER) than pure CNTs via favorable interfacial modification with PANI to largely expose the active sites of on the surface of pure CNTs. Besides, it displays good oxygen reduction reaction (ORR) performance. When directly utilized as bifunctional air electrode without extra additive agents, the composite membrane‐enabled rechargeable Zn‐air batteries not only deliver a high peak power density (201.9 W g^?1) and a large energy density (850.3 Wh kg_Zn^?1), but also present robust cycling performance for 216 cycles with a high energy efficiency of 57.8%.     

Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials

Li‐ and Mn‐rich layered oxides are among the most promising cathode materials for Li‐ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near‐edge structure (FDMNES) code was combined with in situ X‐ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition metals (TMs) in fresh and heavily cycled electrodes. Theoretical modeling reveals a recurring partially reversible LiMn₂O₄‐like sub‐nanodomain formation/dissolution process during each charge/discharge, which accumulates gradually and accounts for the Mn phase transition. From the modeling of spectra and maps of the valence state over large regions of the cathodes, it was found that the phase change is size‐dependent. After prolonged cycling, the TMs displayed different levels of inactivity.     

Strategies towards Low‐Cost Dual‐Ion Batteries with High Performance

Rocking‐chair based lithium‐ion batteries (LIBs) have extensively applied to consumer electronics and electric vehicles (EVs) for solving the present worldwide issues of fossil fuel exhaustion and environmental pollution. However, due to the growing unprecedented demand of LIBs for commercialization in EVs and grid‐scale energy storage stations, and a shortage of lithium and cobalt, the increasing cost gives impetus to exploit low‐cost rechargeable battery systems. Dual‐ion batteries (DIBs), in which both cations and anions are involved in the electrochemical redox reaction, are one of the most promising candidates to meet the low‐cost requirements of commercial applications, because of their high working voltage, excellent safety, and environmental friendliness compared to conventional rocking‐chair based LIBs. However, DIB technologies are only at the stage of fundamental research and considerable effort is required to improve the energy density and cycle life further. We review the development history and current situation, and discuss the reaction kinetics involved in DIBs, including various anionic intercalation mechanism of cathodes, and the reactions at the anodes including intercalation and alloying to explore promising strategies towards low‐cost DIBs with high performance.     

A Sodiophilic Interphase‐Mediated,Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

Despite efforts to stabilize sodium metal anodes and prevent dendrite formation, achieving long cycle life with high areal capacities remains difficult owing to a combination of complex failure modes that involve retardant uneven sodium nucleation and subsequent dendrite formation. Now, a sodiophilic interphase based on oxygen‐functionalized carbon nanotube networks is presented, which concurrently facilitates a homogeneous sodium nucleation and a dendrite‐free, lateral growth behavior upon recurring sodium plating/stripping processes. This sodiophilic interphase renders sodium anodes with an ultrahigh capacity of 1078 mAh g^?1 (areal capacity of 10 mAh cm^?2), approaching the theoretical capacity of 1166 mAh g^?1 of pure sodium, as well as a long cycle life up to 3000 cycles. Implementation of this anode allows for the construction of a sodium–air battery with largely enhanced cycling performance owing to the oxygen functionalization‐mediated, dendrite‐free sodium morphology.     

Advanced High‐Voltage Aqueous Lithium‐Ion Battery Enabled by “Water‐in‐Bisalt” Electrolyte

A new super‐concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra‐high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO₂ as the anode material, and a 2.5 V aqueous Li‐ion cell based on LiMn₂O₄ and carbon‐coated TiO₂ delivered the unprecedented energy density of 100 Wh kg^?1 for rechargeable aqueous Li‐ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the “water‐in‐salt” electrolyte further pushed the energy densities of aqueous Li‐ion cells closer to those of the state‐of‐the‐art Li‐ion batteries.     

Generation of Nanoparticle,Atomic‐Cluster,and Single‐Atom Cobalt Catalysts from Zeolitic Imidazole Frameworks by Spatial Isolation and Their Use in Zinc–Air Batteries

The size effect of transition‐metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo‐ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N‐doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Ångström dimensions. Single‐atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn–air batteries compared with the other derivatives and noble‐metal Pt/C+RuO₂, which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.     

Photo‐excited Oxygen Reduction and Oxygen Evolution Reactions Enable a High‐Performance Zn–Air Battery

The storage of solar energy in battery systems is pivotal for a sustainable society, which faces many challenges. Herein, a Zn–air battery is constructed with two cathodes of poly(1,4‐di(2‐thienyl))benzene (PDTB) and TiO₂ grown on carbon papers to sandwich a Zn anode. The PDTB cathode is illuminated in a discharging process, in which photoelectrons are excited into the conduction band of PDTB to promote oxygen reduction reaction (ORR) and raise the output voltage. In a reverse process, holes in the valence band of the illuminated TiO₂ cathode are driven for the oxygen evolution reaction (OER) by an applied voltage. A record‐high discharge voltage of 1.90 V and an unprecedented low charge voltage of 0.59 V are achieved in the photo‐involved Zn–air battery, regardless of the equilibrium voltage. This work offers an innovative pathway for photo‐energy utilization in rechargeable batteries.     

Sulfur‐Based Electrodes that Function via Multielectron Reactions for Room‐Temperature Sodium‐Ion Storage

Emerging rechargeable sodium‐ion storage systems—sodium‐ion and room‐temperature sodium–sulfur (RT‐NaS) batteries—are gaining extensive research interest as low‐cost options for large‐scale energy‐storage applications. Owing to their abundance, easy accessibility, and unique physical and chemical properties, sulfur‐based materials, in particular metal sulfides (MS_x) and elemental sulfur (S), are currently regarded as promising electrode candidates for Na‐storage technologies with high capacity and excellent redox reversibility based on multielectron conversion reactions. Here, we present current understanding of Na‐storage mechanisms of the S‐based electrode materials. Recent progress and strategies for improving electronic conductivity and tolerating volume variations of the MS_x anodes in Na‐ion batteries are reviewed. In addition, current advances on S cathodes in RT‐NaS batteries are presented. We outline a novel emerging concept of integrating MS_x electrocatalysts into conventional carbonaceous matrices as effective polarized S hosts in RT‐NaS batteries as well. This comprehensive progress report could provide guidance for research toward the development of S‐based materials for the future Na‐storage techniques.     

A Surface‐Oxide‐Rich Activation Layer (SOAL) on Ni2Mo3N for a Rapid and Durable Oxygen Evolution Reaction

The oxygen evolution reaction (OER) is key to renewable energy technologies such as water electrolysis and metal–air batteries. However, the multiple steps associated with proton‐coupled electron transfer result in sluggish OER kinetics and catalysts are required. Here we demonstrate that a novel nitride, Ni₂Mo₃N, is a highly active OER catalyst that outperforms the benchmark material RuO₂. Ni₂Mo₃N exhibits a current density of 10 mA cm^?2 at a nominal overpotential of 270 mV in 0.1 m KOH with outstanding catalytic cyclability and durability. Structural characterization and computational studies reveal that the excellent activity stems from the formation of a surface‐oxide‐rich activation layer (SOAL). Secondary Mo atoms on the surface act as electron pumps that stabilize oxygen‐containing species and facilitate the continuity of the reactions. This discovery will stimulate the further development of ternary nitrides with oxide surface layers as efficient OER catalysts for electrochemical energy devices.     

A Deep‐Cycle Aqueous Zinc‐Ion Battery Containing an Oxygen‐Deficient Vanadium Oxide Cathode

Rechargeable aqueous zinc‐ion batteries are attractive because of their inherent safety, low cost, and high energy density. However, viable cathode materials (such as vanadium oxides) suffer from strong Coulombic ion–lattice interactions with divalent Zn²⁺, thereby limiting stability when cycled at a high charge/discharge depth with high capacity. A synthetic strategy is reported for an oxygen‐deficient vanadium oxide cathode in which facilitated Zn²⁺ reaction kinetic enhance capacity and Zn²⁺ pathways for high reversibility. The benefits for the robust cathode are evident in its performance metrics; the aqueous Zn battery shows an unprecedented stability over 200 cycles with a high specific capacity of approximately 400 mAh g^?1, achieving 95 % utilization of its theoretical capacity, and a long cycle life up to 2 000 cycles at a high cathode utilization efficiency of 67 %. This work opens up a new avenue for synthesis of novel cathode materials with an oxygen‐deficient structure for use in advanced batteries.     

From Lithium‐Ion to Sodium‐Ion Batteries: Advantages,Challenges, and Surprises

Mobile and stationary energy storage by rechargeable batteries is a topic of broad societal and economical relevance. Lithium‐ion battery (LIB) technology is at the forefront of the development, but a massively growing market will likely put severe pressure on resources and supply chains. Recently, sodium‐ion batteries (SIBs) have been reconsidered with the aim of providing a lower‐cost alternative that is less susceptible to resource and supply risks. On paper, the replacement of lithium by sodium in a battery seems straightforward at first, but unpredictable surprises are often found in practice. What happens when replacing lithium by sodium in electrode reactions? This review provides a state‐of‐the art overview on the redox behavior of materials when used as electrodes in lithium‐ion and sodium‐ion batteries, respectively. Advantages and challenges related to the use of sodium instead of lithium are discussed.     

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi‐electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single‐electron transfer, which are not ideal for multivalent‐ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope‐like voltage profiles with insertion/extraction redox of less than one electron. Taking VS₄ as a model material, reversible two‐electron redox with cationic–anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g^?1 at a current density of 100 mA g^?1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg^?1 for RMBs and >500 Wh kg^?1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg²⁺ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS₄.