Interfacial Super‐Assembled Porous CeO2/C Frameworks Featuring Efficient and Sensitive Decomposing Li2O2 for Smart Li–O2 Batteries

The Li–O₂ battery (LOB) represents a promising candidate for future electric vehicles owing to its outstanding energy density. However, the practical application of LOB cells is largely blocked by the poor cycling performance of cathode materials. Herein, an ultralong 440‐cycle life of an LOB cell is achieved using CeO₂ nanocubes super‐assembled on an inverse opal carbon matrix as the cathode material without any additives. CeO₂ is proved to be effective for the complete and sensitive decomposition of loosely stacked Li₂O₂ films during the oxygen evolution reaction process and full accommodation of volume changes caused by the fast growth of Li₂O₂ films during the oxygen reduction reaction process. The super‐assembled porous CeO₂/C frameworks satisfy critical requirements including controlled size, morphology, high Ce³⁺/Ce⁴⁺ ratio, and efficient volume change accommodation, which dramatically increase the cycle life of LOB cell to 440 cycles. This study reveals the design strategy for high performance CeO₂ catalyst cathodes for LOB cells and the generation mechanisms of Li₂O₂ films during the discharge process by using density functional theory calculations, showing new avenues for improving the future smart design of CeO₂‐based cathode catalysts for Li–O₂ batteries.     

Critical Challenges in Rechargeable Aprotic Li–O2 Batteries

Rechargeable aprotic Li–O₂ batteries are one of the most promising next‐generation battery technologies that can deliver extremely high energy density. In the past decades, this technology has attracted worldwide attention, and considerable progress has been achieved. However, numerous critical scientific challenges remain to be solved for practical applications. A specific discussion of recent progress from the perspective of the stable aprotic Li–O₂ system with high energy efficiency is presented. The discussion is highlighted on the reaction mechanisms on air cathode, stability of cell components in semi‐open surroundings, and improvement of battery performance by catalyst design. Challenges and perspectives are also presented. This study provides an intensive understanding of aprotic Li–O₂ batteries and offers an important guideline for developing reversible and high‐efficiency Li–O₂ batteries.     

Fundamental Understanding and Material Challenges in Rechargeable Nonaqueous Li–O2 Batteries: Recent Progress and Perspective

Energy storage challenges have triggered growing interest in various battery technologies and electrocatalysis. As a particularly promising variety, the Li–O₂ battery with an extremely high energy density is of great significance, offering tremendous opportunities to improve cell performance via understanding catalytic mechanisms and the exploration of new materials. Furthermore, focus on nonaqueous electrolyte‐based Li–O₂ batteries has markedly intensified since there could be a higher probability of commercialization, compared to that of solid‐state or aqueous electrolytes. The recent advancements of the nonaqueous Li–O₂ battery in terms of fundamental understanding and material challenges, including electrolyte stability, water effect, and noncarbon cathode materials are summarized in this review. Further, the current status of water impact on discharge products, possible mechanisms, and parasitic reactions in nonaqueous electrolytes are reviewed for the first time. The key challenges of noncarbon oxygen electrode materials, such as noble metals and metal oxides‐based cathodes, transition metals, transition metal compounds (carbides, oxides) based cathodes as well as noncarbon supported catalysts are discussed. This review concludes with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

Recent Advances in Non‐Aqueous Electrolyte for Rechargeable Li–O2 Batteries

The rechargeable Li–O₂ battery has attracted much attention over the past decades owing to its overwhelming advantage in theoretical specific energy density compared to state‐of‐the‐art Li‐ion batteries. Practical application requires non‐aqueous Li–O₂ batteries to stably obtain high reversible capacity, which highly depends on a suitable electrolyte system. Up to now, some critical challenges remain in developing desirable non‐aqueous electrolytes for Li–O₂ batteries. Herein, we will review the current status and challenges in non‐aqueous liquid electrolytes, ionic liquid electrolytes and solid‐state electrolytes of Li–O₂ batteries, as well as the perspectives on these issues and future development.     

Li2O:Li–Mn–O Disordered Rock‐Salt Nanocomposites as Cathode Prelithiation Additives for High‐Energy Density Li‐Ion Batteries

The irreversible loss of lithium from the cathode material during the first cycles of rechargeable Li‐ion batteries notably reduces the overall cell capacity. Here, a new family of sacrificial cathode additives based on Li₂O:Li_2/3Mn_1/3O_5/6 composites synthesized by mechanochemical alloying is reported. These nanocomposites display record (but irreversible) capacities within the Li–Mn–O systems studied, of up to 1157 mAh g^?1, which represents an increase of over 300% of the originally reported capacity in Li_2/3Mn_1/3O_5/6 disordered rock salts. Such a high irreversible capacity is achieved by the reaction between Li₂O and Li_2/3Mn_1/3O_5/6 during the first charge, where electrochemically active Li₂O acts as a Li⁺ donor. A 13% increase of the LiFePO₄ and LiCoO₂ first charge gravimetric capacities is demonstrated by the addition of only 2 wt% of the nanosized composite in the cathode mixture. This result shows the great potential of these newly discovered sacrificial additives to counteract initial losses of Li⁺ ions and improve battery performance.     

Stable Li–Organic Batteries with Nafion‐Based Sandwich‐Type Separators

Similar to Li–S batteries, Li–organic batteries have also been plagued by the dissolution of active materials and the resulting shuttle effect for many years. An effective strategy to eliminate the shuttle effect is adopting solid electrolytes or Li–ion permselective separators to prohibit the dissolved electroactive species from migrating to the Li anode. A polypropylene/Nafion/polypropylene (PNP) sandwich‐type separator is reported with many advantages in comparison with previously reported LISICON, polymer electrolyte, and other Nafion utilization forms. The physical and chemical properties of PNP separators are studied in detail by cross‐section scanning electron microscopy (SEM), infrared spectroscopy (IR), and electrochemical impedance spectroscopy. 1,1′‐Iminodianthraquinone (IDAQ), a novel organic cathode, is taken as an example to quantitatively investigate the function of PNP separators. In the presence of PNP5 with the most appropriate Nafion loading of 0.5 mg cm^–2, IDAQ is able to achieve dramatically improved cycling stability with capacity retention of 76% after 400 cycles and Coulombic efficiency above 99.6%, which reaches the highest level for reported soluble organic electrode materials. Besides Li–organic batteries, such kind of Nafion‐based sandwich‐type separators are also promising for Li–S batteries and other new battery designs involving dissolved electroactive species.     

Optimized Bicompartment Two Solution Cells for Effective and Stable Operation of Li–O2 Batteries

Lithium–oxygen batteries are in fact the only rechargeable batteries that can rival internal combustion engines, in terms of high energy density. However, they are still under development due to low‐efficiency and short lifetime issues. There are problems of side reactions on the cathode side, high reactivity of the Li anode with solution species, and consumption of redox mediators via reactions with metallic lithium. Therefore, efforts are made to protect/block the lithium metal anode in these cells, in order to mitigate side reactions. However, new approach is required in order to solve the problems mentioned above, especially the irreversible reactions of the redox mediators which are mandatory to these systems with the Li anode. Here, optimized bicompartment two solution cells are proposed, in which detrimental crossover between the cathode and anode is completely avoided. The Li metal anode is cycled in electrolyte solution containing fluorinated ethylene carbonate, in which its cycling efficiency is excellent. The cathode compartment contains ethereal solution with redox mediator that enables oxidation of Li₂O₂ at low potentials. The electrodes are separated by a solid electrolyte membrane, allowing free transport of Li ions. This approach increases cycle life of lithium oxygen cells and their energy efficiency.     

An Advanced Separator for Li–O2 Batteries: Maximizing the Effect of Redox Mediators

Although Li–O₂ batteries are promising next‐generation energy storage systems with superior theoretical capacities, they have a serious limitation regarding the large overpotential upon charging that results from the low conductivity of the discharge product. Thus, various redox mediators (RMs) have been widely studied to reduce the overpotential in the charging process, which should promote the oxidation of Li₂O₂. However, RMs degrade the Li metal anode through a parasitic reaction between the RM and the Li metal, and a solution for this phenomenon is necessary. In this study, an effective method is proposed to prevent the migration of the RM toward the anode side of the lithium using a separator that is modified with a negatively charged polymer. When DMPZ (5,10‐dihydro‐5,10‐dimethylphenazine) is used as an RM, it is found that the modified separator suppresses the migration of DMPZ toward the counter electrode of the Li metal anode. This is investigated by a visual redox couple diffusion test, a morphological investigation, and an X‐ray diffraction study. This advanced separator effectively maximizes the catalytic activity of the redox mediator. Li–O₂ batteries using both a highly concentrated DMPZ and the modified separator exhibit improved performance and maintained 90% round‐trip efficiency up to the 20th cycle.     

Strategies Toward Stable Nonaqueous Alkali Metal–O2 Batteries

Alkali metal–O₂ batteries, by coupling high‐capacity alkali metal anodes with gaseous oxygen, possess extremely high gravimetric energy density that is comparable to gasoline and are potential energy storage technologies beyond lithium–ion batteries. The development of alkali metal–O₂ batteries has achieved great progress in recent years, from materials to prototype devices and on fundamental mechanisms. The stability of alkali metal–O₂ batteries is still poor, however, leading to a huge gap between laboratory research and commercial applications. A series of parasitic reactions result in the instability, which occur during electrochemical discharging and charging. The ubiquitous active oxygen species attack both the organic electrolyte and the carbon cathode, triggering various parasitic reactions. Meanwhile, dendrite growth and volume expansion upon repeated plating/stripping and O₂ crossover severely limit the reversibility of alkali metal anodes. Here, an overview of the strategies against these issues is given to improve the stability of nonaqueous alkali metal–O₂ batteries, which is discussed from three aspects: air cathodes, alkali metal anodes, and aprotic electrolytes. Furthermore, perspectives for future research of stable alkali metal–O₂ batteries are outlined.     

Nature‐Inspired Tri‐Pathway Design Enabling High‐Performance Flexible Li–O2 Batteries

Trees have an abundant network of channels for the multiphase transport of water, ions, and nutrients. Recent studies have revealed that multiphase transport of ions, oxygen (O₂) gas, and electrons also plays a fundamental role in lithium–oxygen (Li–O₂) batteries. The similarity in transport behavior of both systems is the inspiration for the development of Li–O₂ batteries from natural wood featuring noncompetitive and continuous individual pathways for ions, O₂, and electrons. Using a delignification treatment and a subsequent carbon nanotube/Ru nanoparticle coating process, one is able to convert a rigid and electrically insulating wood membrane into a flexible and electrically conductive material. The resulting cell walls are comprised of cellulose nanofibers with abundant nanopores, which are ideal for Li⁺ ion transport, whereas the unperturbed wood lumina act as a pathway for O₂ gas transport. The noncompetitive triple pathway design endows the wood‐based cathode with a low overpotential of 0.85 V at 100 mA g^?1, a record‐high areal capacity of 67.2 mAh cm^?2, a long cycling life of 220 cycles, and superior electrochemical and mechanical stability. The integration of such excellent electrochemical performance, outstanding mechanical flexibility, and renewable yet cost‐effective starting materials via a nature‐inspired design opens new opportunities for developing portable energy storage devices.     

High‐Fluorinated Electrolytes for Li–S Batteries

Rechargeable Li–S batteries are regarded as one of the most promising next‐generation energy‐storage systems. However, the inevitable formation of Li dendrites and the shuttle effect of lithium polysulfides significantly weakens electrochemical performance, preventing its practical application. Herein, a new class of localized high‐concentration electrolyte (LHCE) enabled by adding inert fluoroalkyl ether of 1H,1H,5H‐octafluoropentyl‐1,1,2,2‐tetrafluoroethyl ether into highly‐concentrated electrolytes (HCE) lithium bis(fluorosulfonyl) imide/dimethoxyether (DME) system is reported to suppress Li dendrite formation and minimize the solubility of the high‐order polysulfides in electrolytes, thus reducing the amount of electrolyte in cells. Such a unique LHCE can achieve a high coulombic efficiency of Li plating/stripping up to 99.3% and completely suppressing the shuttling effect, thus maintaining a S cathode capacity of 775 mAh g^?1 for 150 cycles with a lean electrolyte of 4.56 g A^?1 h^?1. The LHCE reduces the solubility of lithium polysulfides, allowing the Li/S cell to achieve super performance in a lean electrolyte. This conception of using inert diluents in a highly concentrated electrolyte can accelerate commercialization of Li–S battery technology.     

Stabilization of Li Metal Anode in DMSO‐Based Electrolytes via Optimization of Salt–Solvent Coordination for Li–O2 Batteries

The conventional electrolyte of 1 m lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl sulfoxide (DMSO) is unstable against the Li metal anode and therefore cannot be used directly in practical Li–O₂ batteries. Here, we demonstrate that a highly concentrated electrolyte based on LiTFSI in DMSO (with a molar ratio of 1:3) can greatly improve the stability of the Li metal anode against DMSO and significantly improve the cycling stability of Li–O₂ batteries. This highly concentrated electrolyte contains no free DMSO solvent molecules, but only complexes of (TFSI^?)_a ? Li⁺? (DMSO)_b (where a + b = 4), and thus enhances their stability with Li metal anodes. In addition, such salt–solvent complexes have higher Gibbs activation energy barriers than the free DMSO solvent molecules, indicating improved stability of the electrolyte against the attack of superoxide radical anions. Therefore, the stability of this highly concentrated electrolyte at both Li metal anodes and carbon‐based air electrodes has been greatly enhanced, resulting in improved cycling performance of Li–O₂ batteries. The fundamental stability of the electrolyte in the absence of free‐solvent against the chemical and electrochemical reactions can also be used to enhance the stability of other electrochemical systems.     

Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries

The critical challenges of Li‐O₂ batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo₂S₄@NiO core–shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li‐O₂ batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built‐in interfacial potential between NiCo₂S₄ and NiO can drastically enhance interfacial charge transfer kinetics. According to density functional theory calculations, intrinsic LiO₂‐affinity characteristics of NiCo₂S₄ and NiO play an importantly synergistic role in promoting the formation of large peasecod‐like Li₂O₂, conducive to construct a low‐impedance Li₂O₂/cathode contact interface. As expected, Li‐O₂ cells based on NiCo₂S₄@NiO electrode exhibit an improved overpotential of 0.88 V, a high discharge capacity of 10 050 mAh g^?1 at 200 mA g^?1, an excellent rate capability of 6150 mAh g^?1 at 1.0 A g^?1, and a long‐term cycle stability under a restricted capacity of 1000 mAh g^?1 at 200 mA g^?1. Notably, the reported strategy about heterostructure accouplement may pave a new avenue for the effective electrocatalyst design for Li‐O₂ batteries.     

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials,Construction, and Challenges

Nonaqueous Li–air and Li–S batteries are attracting considerable interest because of their outstanding theoretical capacities and energy densities. However, despite the substantial progress in their development, safety remains an issue because of the flammability of their organic electrolytes. Moreover, the electrolyte volatilization of Li–air batteries and “shuttle effect” in Li–S batteries seriously hinder their development. The use of solid‐state Li–air and Li–S batteries is one of the best solutions. Nevertheless, many challenges remain in solid electrolytes, electrodes, and interfaces. In this review, a comprehensive discussion on the development of solid‐state Li–air and Li–S batteries is provided. The discussion begins with introduction of the progress in solid electrolytes, including their ionic conductivities and chemical stabilities. It then moves on to the cathodes of both batteries and the interface between electrolytes and electrodes. The reaction process inside the cathode is also presented. Suggestions for the optimization of composite cathodes and modification of the electrode–electrolyte interface are provided in the end. Intensive effort is required for the development of solid‐state Li–air and Li–S batteries in the future.     

Spinel‐Layered Core‐Shell Cathode Materials for Li‐Ion Batteries

In an attempt to overcome the problems associated with LiNiO₂, the solid solution series of lithium nickel‐metal oxides, Li[Ni_1–xM_x]O₂ (with M = Co, Mn, Al, Ti, Mg, etc.), have been investigated as favorable cathode materials for high‐energy and high‐power lithium‐ion batteries. However, along with the improvement in the electrochemical properties in Ni‐based cathode materials, the thermal stability has been a great concern, and thus violent reaction of the cathode with the electrolyte needs to be avoided. Here, we report a heterostructured Li[Ni_0.54Co_0.12Mn_0.34]O₂ cathode material which possesses both high energy and safety. The core of the particle is Li[Ni_0.54Co_0.12Mn_0.34]O₂ with a layered phase (R3‐m) and the shell, with a thickness of < 0.5 μm, is a highly stable Li_1+x[CoNi_xMn_2–x]₂O₄ spinel phase (Fd‐3m). The material demonstrates reversible capacity of 200 mAhg‐1 and retains 95% capacity retention under the most severe test condition of 60 °C. In addition, the amount of oxygen evolution from the lattice in the cathode with two heterostructures is reduced by 70%, compared to the reference sample. All these results suggest that the bulk Li[Ni_0.54Co_0.12Mn_0.34]O₂ consisting of two heterostructures satisfy the requirements for hybrid electric vehicles, power tools, and mobile electronics.