High‐Capacity and High‐Rate Discharging of a Coenzyme Q10‐Catalyzed Li–O2 Battery

Discharging of the aprotic Li–O₂ battery relies on O₂ reduction to insulating solid Li₂O₂, which can either deposit as thin films on the cathode surface or precipitate as large particles in the electrolyte solution. Toward realizing Li–O₂ batteries with high capacity and high rate capability, it is crucially important to discharge Li₂O₂ in the electrolyte solution rather than on the cathode surface. Here, a soluble electrocatalyst of coenzyme Q₁₀ (CoQ₁₀) that can efficaciously drive solution phase formation of Li₂O₂ in current benchmark ether‐based Li–O₂ batteries is reported, which would otherwise lead to Li₂O₂ surface‐film growth and premature cell death. In the range of current densities of 0.1–0.5 mA cm^?2_areal, the CoQ₁₀‐catalyzed Li–O₂ battery can deliver a discharge capacity that is ≈40–100 times what the pristine Li–O₂ battery could achieve. The drastically enhanced electrochemical performance is attributed to the CoQ₁₀ that not only efficiently mediates the electron transfer from the cathode to dissolve O₂ but also strongly interacts with the newly formed Li₂O₂ in solution retarding its precipitation on the cathode surface. The mediated oxygen reduction reaction and the bonding mechanism between CoQ₁₀ and Li₂O₂ are understood with density functional theory calculations.     

Textile Inspired Lithium–Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways

The lithium–air (Li–O₂) battery has been deemed one of the most promising next‐generation energy‐storage devices due to its ultrahigh energy density. However, in conventional porous carbon–air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile‐based air cathode is developed with a triple‐phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile‐based Li–O₂ cathode exhibits a high discharge capacity of 8.6 mAh cm^?2, a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile‐based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li–O₂ batteries.     

Developing a “Water‐Defendable” and “Dendrite‐Free” Lithium‐Metal Anode Using a Simple and Promising GeCl4 Pretreatment Method

Lithium metal is an ultimate anode in “next‐generation” rechargeable batteries, such as Li–sulfur batteries and Li–air (Li–O₂) batteries. However, uncontrollable dendritic Li growth and water attack have prevented its practical applications, especially for open‐system Li–O₂ batteries. Here, it is reported that the issues can be addressed via the facile process of immersing the Li metal in organic GeCl₄–THF steam for several minutes before battery assembly. This creates a 1.5 µm thick protection layer composed of Ge, GeO_x, Li₂CO₃, LiOH, LiCl, and Li₂O on Li surface that allows stable cycling of Li electrodes both in Li‐symmetrical cells and Li–O₂ cells, especially in “moist” electrolytes (with 1000–10 000 ppm H₂O) and humid O₂ atmosphere (relative humidity (RH) of 45%). This work illustrates a simple and effective way for the unfettered development of Li‐metal‐based batteries.     

Flexible,Flame‐Resistant,and Dendrite‐Impermeable Gel‐Polymer Electrolyte for Li–O2/Air Batteries Workable Under Hurdle Conditions

Gel‐polymer electrolytes are considered as a promising candidate for replacing the liquid electrolytes to address the safety concerns in Li–O₂/air batteries. In this work, by taking advantage of the hydrogen bond between thermoplastic polyurethane and aerogel SiO₂ in gel polymer, a highly crosslinked quasi‐solid electrolyte (FST‐GPE) with multifeatures of high ionic conductivity, high mechanical flexibility, favorable flame resistance, and excellent Li dendrite impermeability is developed. The resulting gel‐polymer Li–O₂/air batteries possess high reaction kinetics and stabilities due to the unique electrode–electrolyte interface and fast O₂ diffusion in cathode, which can achieve up to 250 discharge–charge cycles (over 1000 h) in oxygen gas. Under ambient air atmosphere, excellent performances are observed for coin‐type cells over 20 days and for prototype cells working under extreme bending conditions. Moreover, the FST‐GPE electrolyte also exhibits durability to protect against fire, dendritic Li, and H₂O attack, demonstrating great potential for the design of practical Li–O₂/air batteries.     

A High‐Performance Li–O2 Battery with a Strongly Solvating Hexamethylphosphoramide Electrolyte and a LiPON‐Protected Lithium Anode

The aprotic Li–O₂ battery has attracted a great deal of interest because theoretically it can store more energy than today's Li‐ion batteries. However, current Li–O₂ batteries suffer from passivation/clogging of the cathode by discharged Li₂O₂, high charging voltage for its subsequent oxidation, and accumulation of side reaction products (particularly Li₂CO₃ and LiOH) upon cycling. Here, an advanced Li–O₂ battery with a hexamethylphosphoramide (HMPA) electrolyte is reported that can dissolve Li₂O₂, Li₂CO₃, and LiOH up to 0.35, 0.36, and 1.11 × 10^?3m , respectively, and a LiPON‐protected lithium anode that can be reversibly cycled in the HMPA electrolyte. Compared to the benchmark of ether‐based Li–O₂ batteries, improved capacity, rate capability, voltaic efficiency, and cycle life are achieved for the HMPA‐based Li–O₂ cells. More importantly, a combination of advanced research techniques provide compelling evidence that operation of the HMPA‐based Li–O₂ battery is backed by nearly reversible formation/decomposition of Li₂O₂ with negligible side reactions.     

In Situ Construction of Stable Tissue‐Directed/Reinforced Bifunctional Separator/Protection Film on Lithium Anode for Lithium–Oxygen Batteries

To achieve a high reversibility and long cycle life for Li–O₂ battery system, the stable tissue‐directed/reinforced bifunctional separator/protection film (TBF) is in situ fabricated on the surface of metallic lithium anode. It is shown that a Li–O₂ cell composed of the TBF‐modified lithium anodes exhibits an excellent anodic reversibility (300 cycles) and effectively improved cathodic long lifetime (106 cycles). The improvement is attributed to the ability of the TBF, which has chemical, electrochemical, and mechanical stability, to effectively prevent direct contact between the surface of the lithium anode and the highly reactive reduced oxygen species (Li₂O₂ or its intermediate LiO₂) in cell. It is believed that the protection strategy describes here can be easily extended to other next‐generation high energy density batteries using metal as anode including Li–S and Na–O₂ batteries.     

High‐Performance Integrated Self‐Package Flexible Li–O2 Battery Based on Stable Composite Anode and Flexible Gas Diffusion Layer

With the rising development of flexible and wearable electronics, corresponding flexible energy storage devices with high energy density are required to provide a sustainable energy supply. Theoretically, rechargeable flexible Li–O₂ batteries can provide high specific energy density; however, there are only a few reports on the construction of flexible Li–O₂ batteries. Conventional flexible Li–O₂ batteries possess a loose battery structure, which prevents flexibility and stability. The low mechanical strength of the gas diffusion layer and anode also lead to a flexible Li–O₂ battery with poor mechanical properties. All these attributes limit their practical applications. Herein, the authors develop an integrated flexible Li–O₂ battery based on a high‐fatigue‐resistance anode and a novel flexible stretchable gas diffusion layer. Owing to the synergistic effect of the stable electrocatalytic activity and hierarchical 3D interconnected network structure of the free‐standing cathode, the obtained flexible Li–O₂ batteries exhibit superior electrochemical performance, including a high specific capacity, an excellent rate capability, and exceptional cycle stability. Furthermore, benefitting from the above advantages, the as‐fabricated flexible batteries can realize excellent mechanical and electrochemical stability. Even after a thousand cycles of the bending process, the flexible Li–O₂ battery can still possess a stable open‐circuit voltage, a high specific capacity, and a durable cycle performance.     

A Quasi‐Solid‐State Flexible Fiber‐Shaped Li–CO2 Battery with Low Overpotential and High Energy Efficiency

The rapid development of wearable electronics requires a revolution of power accessories regarding flexibility and energy density. The Li–CO₂ battery was recently proposed as a novel and promising candidate for next‐generation energy‐storage systems. However, the current Li–CO₂ batteries usually suffer from the difficulties of poor stability, low energy efficiency, and leakage of liquid electrolyte, and few flexible Li–CO₂ batteries for wearable electronics have been reported so far. Herein, a quasi‐solid‐state flexible fiber‐shaped Li–CO₂ battery with low overpotential and high energy efficiency, by employing ultrafine Mo₂C nanoparticles anchored on a carbon nanotube (CNT) cloth freestanding hybrid film as the cathode, is demonstrated. Due to the synergistic effects of the CNT substrate and Mo₂C catalyst, it achieves a low charge potential below 3.4 V, a high energy efficiency of ≈80%, and can be reversibly discharged and charged for 40 cycles. Experimental results and theoretical simulation show that the intermediate discharge product Li₂C₂O₄ stabilized by Mo₂C via coordinative electrons transfer should be responsible for the reduction of overpotential. The as‐fabricated quasi‐solid‐state flexible fiber‐shaped Li–CO₂ battery can also keep working normally even under various deformation conditions, giving it great potential of becoming an advanced energy accessory for wearable electronics.     

Redox Mediators for Li–O2 Batteries: Status and Perspectives

Li–O₂ batteries have received much attention due to their extremely large theoretical energy density. However, the high overpotentials required for charging Li–O₂ batteries lower their energy efficiency and degrade the electrolytes and carbon electrodes. This problem is one of the main obstacles in developing practical Li–O₂ batteries. To solve this problem, it is important to facilitate the oxidation of Li₂O₂ upon charging by using effective electrocatalysis. Using solid catalysts is not too effective for oxidizing the electronically isolating Li‐peroxide layers. In turn, for soluble catalysts, red‐ox mediators (RMs) are homogeneously dissolved in the electrolyte solutions and can effectively oxidize all of the Li₂O₂ precipitated during discharge. RMs can decompose solid Li₂O₂ species no matter their size, morphology, or thickness and thus dramatically increase energy efficiency. However, some negative side effects, such as the shuttle reactions of RMs and deterioration of the Li‐metal occur. Therefore, it is necessary to study the activity and stability of RMs in Li–O₂ batteries in detail. Herein, recent studies related to redox mediators are reviewed and the mechanisms of redox reactions are illustrated. The development opportunities of RMs for this important battery technology are discussed and future directions are suggested.     

Atomically Thin Mesoporous Co3O4 Layers Strongly Coupled with N‐rGO Nanosheets as High‐Performance Bifunctional Catalysts for 1D Knittable Zinc–Air Batteries

Under development for next‐generation wearable electronics are flexible, knittable, and wearable energy‐storage devices with high energy density that can be integrated into textiles. Herein, knittable fiber‐shaped zinc–air batteries with high volumetric energy density (36.1 mWh cm^?3) are fabricated via a facile and continuous method with low‐cost materials. Furthermore, a high‐yield method is developed to prepare the key component of the fiber‐shaped zinc–air battery, i.e., a bifunctional catalyst composed of atomically thin layer‐by‐layer mesoporous Co₃O₄/nitrogen‐doped reduced graphene oxide (N‐rGO) nanosheets. Benefiting from the high surface area, mesoporous structure, and strong synergetic effect between the Co₃O₄ and N‐rGO nanosheets, the bifunctional catalyst exhibits high activity and superior durability for oxygen reduction and evolution reactions. Compared to a fiber‐shaped zinc–air battery using state‐of‐the‐art Pt/C + RuO₂ catalysts, the battery based on these Co₃O₄/N‐rGO nanosheets demonstrates enhanced and stable electrochemical performance, even under severe deformation. Such batteries, for the first time, can be successfully knitted into clothes without short circuits under external forces and can power various electronic devices and even charge a cellphone.     

Understanding the Reaction Chemistry during Charging in Aprotic Lithium–Oxygen Batteries: Existing Problems and Solutions

The aprotic lithium–oxygen (Li–O₂) battery has excited huge interest due to it having the highest theoretical energy density among the different types of rechargeable battery. The facile achievement of a practical Li–O₂ battery has been proven unrealistic, however. The most significant barrier to progress is the limited understanding of the reaction processes occurring in the battery, especially during the charging process on the positive electrode. Thus, understanding the charging mechanism is of crucial importance to enhance the Li–O₂ battery performance and lifetime. Here, recent progress in understanding the electrochemistry and chemistry related to charging in Li–O₂ batteries is reviewed along with the strategies to address the issues that exist in the charging process at the present stage. The properties of Li₂O₂ and the mechanisms of Li₂O₂ oxidation to O₂ on charge are discussed comprehensively, as are the accompanied parasitic chemistries, which are considered as the underlying issues hindering the reversibility of Li–O₂ batteries. Based on the detailed discussion of the charging mechanism, innovative strategies for addressing the issues for the charging process are discussed in detail. This review has profound implications for both a better understanding of charging chemistry and the development of reliable rechargeable Li–O₂ batteries in the future.     

Water-Trapping Single-Atom Co-N4/Graphene Triggering Direct 4e− LiOH Chemistry for Rechargeable Aprotic Li–O2 Batteries

Lithium–oxygen (Li–O₂) batteries have received extensive attention owing to ultrahigh theoretical energy density. Compared to typical discharge product Li₂O₂, LiOH has attracted much attention for its better chemical and electrochemical stability. Large-scale applications of Li–O₂ batteries with LiOH chemistry are hampered by the serious internal shuttling of the water additives with the desired 4e⁻ electrochemical reactions. Here, a metal organic framework-derived “water-trapping” single-atom-Co-N₄/graphene catalyst (Co-SA-rGO) is provided that successfully mitigates the water shuttling and enables the direct 4e⁻ catalytic reaction of LiOH in the aprotic Li–O₂ battery. The Co-N₄ center is more active toward proton-coupled electron transfer, benefiting - direction 4e⁻ formation of LiOH. 3D interlinked networks also provide large surface area and mesoporous structures to trap ≈12 wt% H₂O molecules and offer rapid tunnels for O₂ diffusion and Li⁺ transportation. With these unique features, the Co-SA-rGO based Li–O₂ battery delivers a high discharge platform of 2.83 V and a large discharge capacity of 12 760.8 mAh g⁻¹. Also, the battery can withstand corrosion in the air and maintain a stable discharge platform for 220 cycles. This work points out the direction of enhanced electron/proton transfer for the single-atom catalyst design in Li–O₂ batteries.     

High Capacity Li2S–Li2O–LiI Positive Electrodes with Nanoscale Ion-Conduction Pathways for All-Solid-State Li/S Batteries

All-solid-state lithium–sulfur (Li/S) batteries are promising next-generation energy-storage devices owing to their high capacities and long cycle lives. The Li₂S active material used in the positive electrode has a high theoretical capacity; consequently, nanocomposites composed of Li₂S, solid electrolytes, and conductive carbon can be used to fabricate high-energy-density batteries. Moreover, the active material should be constructed with both micro- and nanoscale ion-conduction pathways to ensure high power. Herein, a Li₂S–Li₂O–LiI positive electrode is developed in which the active material is dispersed in an amorphous matrix. Li₂S–Li₂O–LiI exhibits high charge–discharge capacities and a high specific capacity of 998 mAh g⁻¹ at a 2 C rate and 25 °C. X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy observation suggest that Li₂O–LiI provides nanoscale ion-conduction pathways during cycling that activate Li₂S and deliver large capacities; it also exhibits an appropriate onset oxidation voltage for high capacity. Furthermore, a cell with a high areal capacity of 10.6 mAh cm^–2 is demonstrated to successfully operate at 25 °C using a Li₂S–Li₂O–LiI positive electrode. This study represents a major step toward the commercialization of all-solid-state Li/S batteries.     

Strategies toward High‐Performance Cathode Materials for Lithium–Oxygen Batteries

Rechargeable aprotic lithium (Li)–O₂ batteries with high theoretical energy densities are regarded as promising next‐generation energy storage devices and have attracted considerable interest recently. However, these batteries still suffer from many critical issues, such as low capacity, poor cycle life, and low round‐trip efficiency, rendering the practical application of these batteries rather sluggish. Cathode catalysts with high oxygen reduction reaction (ORR) and evolution reaction activities are of particular importance for addressing these issues and consequently promoting the application of Li–O₂ batteries. Thus, the rational design and preparation of the catalysts with high ORR activity, good electronic conductivity, and decent chemical/electrochemical stability are still challenging. In this Review, the strategies are outlined including the rational selection of catalytic species, the introduction of a 3D porous structure, the formation of functional composites, and the heteroatom doping which succeeded in the design of high‐performance cathode catalysts for stable Li–O₂ batteries. Perspectives on enhancing the overall electrochemical performance of Li–O₂ batteries based on the optimization of the properties and reliability of each part of the battery are also made. This Review sheds some new light on the design of highly active cathode catalysts and the development of high‐performance lithium–O₂ batteries.     

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal?air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm^?2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm^?2, a high energy density of 938 Wh kg_Zn^?1, and can be steadily cycled over 130 h at 10 mA cm^?2, demonstrating great application potential in rechargeable metal–air batteries.     

Fundamental Understanding of Water‐Induced Mechanisms in Li–O2 Batteries: Recent Developments and Perspectives

Modern sustainability challenges in recent years have warranted the development of new energy storage technologies. Practical realization of the lithium–O₂ battery holds great promise for revolutionizing energy storage as it holds the highest theoretical specific energy of any rechargeable battery yet discovered. However, the complete realization of Li–O₂ batteries necessitates ambient air operations, which presents quite a few challenges, as carbon dioxide (CO₂) and water (H₂O) contaminants introduce unwanted byproducts from side reactions that greatly affect battery performance. Although current research has thoroughly explored the beneficial incorporation of CO₂, much mystery remains over the inconsistent effects of H₂O. The presence of water in both the cathode and electrolyte has been observed to alter reaction mechanisms differently, resulting in a diverse range of effects on voltage, capacity, and cyclability. Moreover, recent preliminary research with catalysts and redox mediators has attempted to utilize the presence of water to the battery's benefit. Here, the key mechanism discrepancies of water‐afflicted Li–O₂ batteries are presented, concluding with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

Crosslinked Carbon Nanotube Aerogel Films Decorated with Cobalt Oxides for Flexible Rechargeable Zn–Air Batteries

Air electrodes with high catalytic activity are of great importance for rechargeable zinc–air batteries. Herein, a flexible, binder‐free composite air electrode for zinc–air batteries is reported, which utilizes a lightweight, conductive, and crosslinked aerogel film of carbon nanotubes (CNTs) functioned as a 3D catalyst‐supporting scaffold for bifunctional cobalt (II/III) oxides and as a current collector. The composite electrode shows high catalytic activities for both oxygen reduction reaction and oxygen evolution reaction, resulting from the synergistic effect of nitrogen‐doped CNTs and spinel Co₃O₄ nanoparticles. Solid‐state Zn–air batteries assembled using such free‐standing air electrodes (without the need of additional current collectors) are bendable and show low resistances, low charge/discharge overpotentials, and a high cyclic stability.     

Designing a Multifunctional Separator for High‐Performance Li–S Batteries at Elevated Temperature

The practical applications of lithium–sulfur (Li–S) batteries are seriously limited by the undesirable polysulfide shuttling and lithium dendrite growth. Herein, a multifunctional membrane is designed and prepared by coating a lithiated Nafion (Li@Nafion) layer and an Al₂O₃ layer on the two sides of a routine polymer membrane (polypropylene/polyethylene/polypropylene, PEP). The Li@Nafion layer faced to the sulfur cathode builds a “polysulfide‐phobic” surface to restrain the shuttle effect via Coulomb repulsion, while the Al₂O₃ layer with a uniform porous structure aids in regulating homogeneous Li⁺ fluxes to achieve stable Li electrodeposition. As a result, the Li//Li symmetric cell with a Li@Nafion/PEP/Al₂O₃ (LNPA) separator realizes stable Li plating/striping even after 1000 h at a high current density (5 mA cm^?2). Moreover, the Li–S batteries incorporating LNPA separators not only can achieve excellent outstanding cyclic stability at an ultrahigh sulfur loading (7.6 mg cm^?2), but also exhibit impressive electrochemical performance at an elevated temperature (60 °C). The rational design of the LNPA separator presents new insights to develop high‐performance Li–S batteries.     

Intrinsically Optimizing Charge Transfer via Tuning Charge/Discharge Mode for Lithium–Oxygen Batteries

Lithium–oxygen batteries have an ultrahigh theoretical energy density, almost ten times higher than lithium‐ion batteries. The poor conductivity of the discharge product Li₂O₂, however, severely raises the charge overpotential and pulls down the cyclability. Here, a simple and effective strategy is presented for regular formation of lithium vacancies in the discharge product via tuning charge/discharge mode, and their effects on the charge transfer behavior. The effects of the discharge current density on the lithium vacancies, ionic conductivity, and electronic conductivity of the discharge product Li₂O₂ are systematically investigated via electron spin resonance, spin‐alignment echo nuclear magnetic resonance, and tungsten nanomanipulators, respectively. The study by density functional theory indicates that the lithium vacancies in Li₂O₂ generated during the discharge process are highly dependent on the current density. High current can induce a high vacancy density, which enhances the electronic conductivity and reduces the overpotential. Meanwhile, with increasing discharge current, the morphology of the Li₂O₂ changes from microtoroids to thin nanoplatelets, effectively shortening the charge transfer distance and improving the cycling performance. The Li₂O₂ grown in fast discharge mode is more easily decomposed in the following charging process. The lithium–oxygen battery cycling in fast‐discharge/slow‐charge mode exhibits low overpotential and long cycle life.     

Strongly Coupled Carbon Nanosheets/Molybdenum Carbide Nanocluster Hollow Nanospheres for High‐Performance Aprotic Li–O2 Battery

A highly efficient oxygen electrode is indispensable for achieving high‐performance aprotic lithium–O₂ batteries. Herein, it is demonstrated that strongly coupled carbon nanosheets/molybdenum carbide (α‐MoC_1?x) nanocluster hierarchical hybrid hollow spheres (denoted as MoC_1?x/HSC) can work well as cathode for boosting the performance of lithium–O₂ batteries. The important feature of MoC_1?x/HSC is that the α‐MoC_1?x nanoclusters, uniformly incorporated into carbon nanosheets, can not only effectively prevent the nanoclusters from agglomeration, but also help enhance the interaction between the nanoclusters and the conductive substrate during the charge and discharge process. As a consequence, the MoC_1?x/HSC shows significantly improved electrocatalytic performance in an aprotic Li–O₂ battery with greatly reduced charge and discharge overpotentials and long cycle stability. The ex situ scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy studies reveal that the mechanism for the high‐performance Li–O₂ battery using MoC_1?x/HSC as cathode is that the incorporated molybdenum carbide nanoclusters can make oxygen reduction on their surfaces easy, and finally form amorphous film‐like Li‐deficient Li₂O₂ with the ability to decompose at a low potential. To the best of knowledge, the MoC_1?x/HSC of this paper is among the best cathode materials for lithium–O₂ batteries reported to date.