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.     

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.     

Lithiation/Delithiation Synthesis of Few Layer Silicene Nanosheets for Rechargeable Li–O2 Batteries

Silicene has recently received increasing interest due to its unique properties. However, the synthesis of silicene remains challenging, which limits its wide applications. In this work, a top‐down lithiation and delithiation process is developed to prepare few layer silicene‐like nanosheets from ball‐milled silicon nanopowders. It is found that delithiation solvent plays a critical role in the structure evolution of the final products. The use of isopropyl alcohol renders 2D silicene‐like products 30–100 nm in length and ≈2.4 nm in thickness. The electrochemical characterization analysis suggests that the product shows high performance for rechargeable Li–O₂ batteries with 73% energy efficiency and high stability. The top‐down synthesis strategy proposed in this work not only provides a new solution to the challenging preparation issue of few layer silicene but also demonstrates the feasibility of producing 2D materials from nonlayered starting structures.     

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.     

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.     

Component‐Interaction Reinforced Quasi‐Solid Electrolyte with Multifunctionality for Flexible Li–O2 Battery with Superior Safety under Extreme Conditions

High‐performance flexible lithium–oxygen (Li–O₂) batteries with excellent safety and stability are urgently required due to the rapid development of flexible and wearable devices. Herein, based on an integrated solid‐state design by taking advantage of component‐interaction between poly(vinylidene fluoride‐co‐hexafluoropropylene) and nanofumed silica in polymer matrix, a stable quasi‐solid‐state electrolyte (PS‐QSE) for the Li–O₂ battery is proposed. The as‐assembled Li–O₂ battery containing the PS‐QSE exhibits effectively improved anodic reversibility (over 200 cycles, 850 h) and cycling stability of the battery (89 cycles, nearly 900 h). The improvement is attributed to the stability of the PS‐QSE (including electrochemical, chemical, and mechanical stability), as well as the effective protection of lithium anode from aggressive soluble intermediates generated in cathode. Furthermore, it is demonstrated that the interaction among the components plays a pivotal role in modulating the Li‐ion conducting mechanism in the as‐prepared PS‐QSE. Moreover, the pouch‐type PS‐QSE based Li–O₂ battery also shows wonderful flexibility, tolerating various deformations thanks to its integrated solid‐state design. Furthermore, holes can be punched through the Li–O₂ battery, and it can even be cut into any desired shape, demonstrating exceptional safety. Thus, this type of battery has the potential to meet the demands of tailorability and comformability in flexible and wearable electronics.     

Covalent‐Organic‐Framework‐Based Li–CO2 Batteries

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials constructed from designer molecular building blocks that are linked and extended periodically via covalent bonds. Their high stability, open channels, and ease of functionalization suggest that they can function as a useful cathode material in reversible lithium batteries. Here, a COF constructed from hydrazone/hydrazide‐containing molecular units, which shows good CO₂ sequestration properties, is reported. The COF is hybridized to Ru‐nanoparticle‐coated carbon nanotubes, and the composite is found to function as highly efficient cathode in a Li–CO₂ battery. The robust 1D channels in the COF serve as CO₂^– and lithium‐ion‐diffusion channels and improve the kinetics of electrochemical reactions. The COF‐based Li–CO₂ battery exhibits an ultrahigh capacity of 27 348 mAh g^?1 at a current density of 200 mA g^?1, and a low cut‐off overpotential of 1.24 V within a limiting capacity of 1000 mAh g^?1. The rate performance of the battery is improved considerably with the use of the COF at the cathode, where the battery shows a slow decay of discharge voltage from a current density of 0.1 to 4 A g^?1. The COF‐based battery runs for 200 cycles when discharged/charged at a high current density of 1 A g^?1.     

Protecting the Li‐Metal Anode in a Li–O2 Battery by using Boric Acid as an SEI‐Forming Additive

The Li–O₂ battery (LOB) is considered as a promising next‐generation energy storage device because of its high theoretic specific energy. To make a practical rechargeable LOB, it is necessary to ensure the stability of the Li anode in an oxygen atmosphere, which is extremely challenging. In this work, an effective Li‐anode protection strategy is reported by using boric acid (BA) as a solid electrolyte interface (SEI) forming additive. With the assistance of BA, a continuous and compact SEI film is formed on the Li‐metal surface in an oxygen atmosphere, which can significantly reduce unwanted side reactions and suppress the growth of Li dendrites. Such an SEI film mainly consists of nanocrystalline lithium borates connected with amorphous borates, carbonates, fluorides, and some organic compounds. It is ionically conductive and mechanically stronger than conventional SEI layer in common Li‐metal‐based batteries. With these benefits, the cycle life of LOB is elongated more than sixfold.     

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.     

Rationalizing the Effect of Oxygen Vacancy on Oxygen Electrocatalysis in Li–O2 Battery

Albeit the effectiveness of surface oxygen vacancy in improving oxygen redox reactions in Li–O₂ battery, the underpinning reason behind this improvement remains ambiguous. Herein, the concentration of oxygen vacancy in spinel NiCo₂O₄ is first regulated via magnetron sputtering and its relationship with catalytic activity is comprehensively studied in Li–O₂ battery based on experiment and density functional theory (DFT) calculation. The positive effect posed by oxygen vacancy originates from the up shifted antibond orbital relative to Fermi level (E_f), which provides extra electronic state around E_f, eventually enhancing oxygen adsorption and charge transfer during oxygen redox reactions. However, with excessive oxygen vacancy, the negative effect emerges because the metal ions are mostly reduced to low valence based on the electrical neutral principle, which not only destabilizes the crystal structure but also weakens the ability to capture electrons from the antibond orbit of Li₂O₂, leading to poor catalytic activity for oxygen evolution reaction (OER).     

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.     

Bending‐Tolerant Anodes for Lithium‐Metal Batteries

Bendable energy‐storage systems with high energy density are demanded for conformal electronics. Lithium‐metal batteries including lithium–sulfur and lithium–oxygen cells have much higher theoretical energy density than lithium‐ion batteries. Reckoned as the ideal anode, however, Li has many challenges when directly used, especially its tendency to form dendrite. Under bending conditions, the Li‐dendrite growth can be further aggravated due to bending‐induced local plastic deformation and Li‐filaments pulverization. Here, the Li‐metal anodes are made bending tolerant by integrating Li into bendable scaffolds such as reduced graphene oxide (r‐GO) films. In the composites, the bending stress is largely dissipated by the scaffolds. The scaffolds have increased available surface for homogeneous Li plating and minimize volume fluctuation of Li electrodes during cycling. Significantly improved cycling performance under bending conditions is achieved. With the bending‐tolerant r‐GO/Li‐metal anode, bendable lithium–sulfur and lithium–oxygen batteries with long cycling stability are realized. A bendable integrated solar cell–battery system charged by light with stable output and a series connected bendable battery pack with higher voltage is also demonstrated. It is anticipated that this bending‐tolerant anode can be combined with further electrolytes and cathodes to develop new bendable energy systems.     

Conjugated Cobalt Polyphthalocyanine as the Elastic and Reprocessable Catalyst for Flexible Li–CO2 Batteries

Li–CO₂ batteries represent an attractive solution for electrochemical energy storage by utilizing atmospheric CO₂ as the energy carrier. However, their practical viability critically depends on the development of efficient and low‐cost cathode catalysts for the reversible formation and decomposition of Li₂CO₃. Here, the great potential of a structurally engineered polymer is demonstrated as the cathode catalyst for rechargeable Li–CO₂ batteries. Conjugated cobalt polyphthalocyanine is prepared via a facile microwave heating method. Due to the crosslinked network, it is intrinsically elastic and has improved chemical, physical, and mechanical stability. Electrochemical measurements show that cobalt polyphthalocyanine facilitates the reversible formation and decomposition of Li₂CO₃, and therefore enables high‐performance Li–CO₂ batteries with large areal capacity and impressive cycling performance. In addition, the elastic and reprocessable property of the polymeric catalyst renders it possible to fabricate flexible batteries.