Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

As an electrochemical energy‐storage technology with the highest theoretical capacity, lithium–oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round‐trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium–oxygen batteries for high‐performance operations and how to eventually materialize the full potentials of this promising technology.     

Singlet Oxygen during Cycling of the Aprotic Sodium–O2 Battery

Aprotic sodium–O₂ batteries require the reversible formation/dissolution of sodium superoxide (NaO₂) on cycling. Poor cycle life has been associated with parasitic chemistry caused by the reactivity of electrolyte and electrode with NaO₂, a strong nucleophile and base. Its reactivity can, however, not consistently explain the side reactions and irreversibility. Herein we show that singlet oxygen (¹O₂) forms at all stages of cycling and that it is a main driver for parasitic chemistry. It was detected in‐ and ex‐situ via a ¹O₂ trap that selectively and rapidly forms a stable adduct with ¹O₂. The ¹O₂ formation mechanism involves proton‐mediated superoxide disproportionation on discharge, rest, and charge below ca. 3.3 V, and direct electrochemical ¹O₂ evolution above ca. 3.3 V. Trace water, which is needed for high capacities also drives parasitic chemistry. Controlling the highly reactive singlet oxygen is thus crucial for achieving highly reversible cell operation.     

Enzyme‐Inspired Room‐Temperature Lithium–Oxygen Chemistry via Reversible Cleavage and Formation of Dioxygen Bonds

Li‐O₂ batteries are promising energy storage systems due to their ultra‐high theoretical capacity. However, most Li‐O₂ batteries are based on the reduction/oxidation of Li₂O₂ and involve highly reactive superoxide and peroxide species that would cause serious degradation of cathodes, especially carbon‐based materials. It is important to explore lithium‐oxygen reactions and find new Li‐O₂ chemistry which can restrict or even avoid the negative influence of superoxide/peroxide species. Here, inspired by enzyme‐catalyzed oxygen reduction/oxidation reactions, we introduce a copper(I) complex 3 N‐Cu^I (3 N=1,4,7‐trimethyl‐1,4,7‐triazacyclononane) to Li‐O₂ batteries and successfully modulate the reaction pathway to a moderate one on reversible cleavage/formation of O?O bonds. This work demonstrates that the reaction pathways of Li‐O₂ batteries could be modulated by introducing an appropriate soluble catalyst, which is another powerful choice to construct better Li‐O₂ batteries.     

Mesoporous MnCo2O4 with a Flake‐Like Structure as Advanced Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A mesoporous flake‐like manganese‐cobalt composite oxide (MnCo₂O₄) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller methods. The flake‐like MnCo₂O₄ is evaluated as the anode material for lithium‐ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g^?1, good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake‐like MnCo₂O₄ also demonstrates a high supercapacitance of 1487 F g^?1 at a current density of 1 A g^?1, and an exceptional cycling performance over 2000 charge/discharge cycles.     

Experimental and Computational Analysis of the Solvent‐Dependent O2/Li+‐O2− Redox Couple: Standard Potentials,Coupling Strength,and Implications for Lithium–Oxygen Batteries

Understanding and controlling the kinetics of O₂ reduction in the presence of Li⁺‐containing aprotic solvents, to either Li⁺‐O₂^? by one‐electron reduction or Li₂O₂ by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O₂ batteries. Standard potentials of O₂/Li⁺‐O₂^? and O₂/O₂^? were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li⁺ and O₂^? was found to lower the coupling of Li⁺‐O₂^? and the difference between O₂/Li⁺‐O₂^? and O₂/O₂^? potentials. The solvation energy of Li⁺ trended with donor number (DN), and varied greater than that of O₂^? ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li⁺‐O₂^? solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries.     

Free‐Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li‐O2 Batteries

Free‐standing macroporous air electrodes with enhanced interfacial contact, rapid mass transport, and tailored deposition space for large amounts of Li₂O₂ are essential for improving the rate performance of Li‐O₂ batteries. An ordered mesoporous carbon membrane with continuous macroporous channels was prepared by inversely topological transformation from ZnO nanorod array. Utilized as a free‐standing air cathode for Li‐O₂ battery, the hierarchically porous carbon membrane shows superior rate performance. However, the increased cross‐sectional area of the continuous macropores on the cathode surface leads to a kinetic overpotential with large voltage hysteresis and linear voltage variation against Butler–Volmer behavior. The kinetics were investigated based on the rate‐determining step of second electron transfer accompanied by migration of Li⁺ in solid or quasi‐solid intermediates. These discoveries shed light on the design of the air cathode for Li‐O₂ batteries with high‐rate performance.     

Electrochemical Properties and Sodium‐Storage Mechanism of Ag2Mo2O7 as the Anode Material for Sodium‐Ion Batteries

Silver molybdate, Ag₂Mo₂O₇, has been prepared by a conventional solid‐state reaction. Its electrochemical properties as an anode material for sodium‐ion batteries (SIBs) have been comprehensively examined by means of galvanostatic charge–discharge cycling, cyclic voltammetry, and rate performance measurements. At operating voltages between 3.0 and 0.01 V, the electrode delivered a reversible capacity of nearly 190 mA h g^?1 at a current density of 20 mA g^?1 after 70 cycles. Ag₂Mo₂O₇ also demonstrated a good rate capability and long‐term cycle stability, the capacity reaching almost 100 mA h g^?1 at a current density of 500 mA g^?1, with a capacity retention of 55 % over 1000 cycles. Moreover, the sodium storage process of Ag₂Mo₂O₇ has been investigated by means of ex situ XRD, Raman spectroscopy, and HRTEM. Interestingly, the anode decomposes into Ag metal and Na₂MoO₄ during the initial discharge process, and then Na⁺ ions are considered to be inserted into/extracted from the Na₂MoO₄ lattice in the subsequent cycles governed by an intercalation/deintercalation mechanism. Ex situ HRTEM images revealed that Ag metal not only remains unchanged during the sodiation/desodiation processes, but is well dispersed throughout the amorphous matrix, thereby greatly improving the electronic conductivity of the working electrode. The “in situ” decomposition behavior of Ag₂Mo₂O₇ is distinct from that of chemically synthesized, metal‐nanoparticle‐coated electrode materials, and provides strong supplementary insight into the mechanism of such new anode materials for SIBs and may set a precedent for the design of further materials.     

A Microwave Synthesis of Mesoporous NiCo2O4 Nanosheets as Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A facile microwave method was employed to synthesize NiCo₂O₄ nanosheets as electrode materials for lithium‐ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. Owing to the porous nanosheet structure, the NiCo₂O₄ electrodes exhibited a high reversible capacity of 891 mA h g^?1 at a current density of 100 mA g^?1, good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo₂O₄ nanosheets demonstrated a specific capacitance of 400 F g^?1 at a current density of 20 A g^?1 and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode–electrolyte contact area and facilitate rapid ion transport.     

The Relationship between the Relative Solvating Power of Electrolytes and Shuttling Effect of Lithium Polysulfides in Lithium–Sulfur Batteries

Relative solvating power, that is, the ratio of the coordination ratios between a solvent and the reference solvent, was used to probe the quantitative structure–activity relationship of electrolyte solvents and the lithium polysulfide (LiPS) dissolution in lithium–sulfur batteries. Internally referenced diffusion‐ordered nuclear magnetic resonance spectroscopy (IR‐DOSY) was used to determine the diffusion coefficient and coordination ratio, from which the relative solvating power can be easily measured. The higher the relative solvating power of an ethereal solvent, the more severe will be the LiPS dissolution and the lower the coulombic efficiency of the lithium–sulfur battery. A linear relationship was established between the logarithm of relative solvating power of a solvent and the degree of LiPS dissolution, rendering relative solvating power an important parameter in choosing the electrolyte solvent for lithium–sulfur batteries.     

Synthesis of Single‐Crystalline Spinel LiMn2O4 Nanorods for Lithium‐Ion Batteries with High Rate Capability and Long Cycle Life

The long‐standing challenge associated with capacity fading of spinel LiMn₂O₄ cathode material for lithium‐ion batteries is investigated. Single‐crystalline spinel LiMn₂O₄ nanorods were successfully synthesized by a template‐engaged method. Porous Mn₃O₄ nanorods were used as self‐sacrificial templates, into which LiOH was infiltrated by a vacuum‐assisted impregnation route. When used as cathode materials for lithium‐ion batteries, the spinel LiMn₂O₄ nanorods exhibited superior long cycle life owing to the one‐dimensional nanorod structure, single‐crystallinity, and Li‐rich effect. LiMn₂O₄ nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn₂O₄ was well‐preserved after a long‐term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn₂O₄ nanorods. This result shows the promising applications of single‐crystalline spinel LiMn₂O₄ nanorods as cathode materials for lithium‐ion batteries with high rate capability and long cycle life.     

Raman and Photoluminescence Spectroscopic Detection of Surface‐Bound Li+O2− Defect Sites in Li‐Doped ZnO Nanocrystals Derived from Molecular Precursors

We present a detailed study of Raman spectroscopy and photoluminescence measurements on Li‐doped ZnO nanocrystals with varying lithium concentrations. The samples were prepared starting from molecular precursors at low temperature. The Raman spectra revealed several sharp lines in the range of 100–200 cm^?1, which are attributed to acoustical phonons. In the high‐energy range two peaks were observed at 735 cm^?1 and 1090 cm^?1. Excitation‐dependent Raman spectroscopy of the 1090 cm^?1 mode revealed resonance enhancement at excitation energies around 2.2 eV. This energy coincides with an emission band in the photoluminescence spectra. The emission is attributed to the deep lithium acceptor and intrinsic point defects such as oxygen vacancies. Based on the combined Raman and PL results, we introduce a model of surface‐bound LiO₂ defect sites, that is, the presence of Li⁺O₂^? superoxide. Accordingly, the observed Raman peaks at 735 cm^?1 and 1090 cm^?1 are assigned to Li? O and O? O vibrations of LiO₂.     

Direct Visualization of the Chemical Mechanism in SERRS of 4‐Aminothiophenol/Metal Complexes and Metal/4‐Aminothiophenol/Metal Junctions

Direct visualization of photoinduced tunneling charge transfer (TCT) in an Au₅/para‐aminothiophenol (PATP)/Ag₆ junction in which Au and Ag clusters form the first and second layer, respectively, is provided by the charge difference density (see picture; green and red stand for holes and electrons, respectively).