Li-air Research Articles

Constructed Mott–Schottky Heterostructure Catalyst to Trigger Interface Disturbance and Manipulate Redox Kinetics in Li-O2 Battery

HighlightsA carbon free self supported Mott-Schottky heterostructure was constructed as an efficient cathode catalyst for lithium oxygen batteries, achieving homogeneous contact between the two materials for strong interfacial interactions.The heterostructure triggered interfacial perturbations and band structure changes, which accelerated oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics, resulting in an extremely long cycle life of 800 cycles and an extremely low overpotential of 0.73 V.Combined with advanced characterization techniques and density functional theory calculations, the underlying mechanism behind the boosted ORR/OER activities and the electrocatalytic mechanism were revealed.

Minireview: Design of Cathode Structures for Solid-State Lithium–Air Batteries─Learning from Solid Oxide Fuel Cells

Minireview: Design of Cathode Structures for Solid-State Lithium–Air Batteries─Learning from Solid Oxide Fuel Cells

2D MXene/MBene Superlattice with Narrow Bandgap as Superior Electrocatalyst for High-Performance Lithium-Oxygen Battery.

Lithium-oxygen (Li-O2) battery with large theoretical energy density (≈3500Whkg-1) is one of the most promising energy storage and conversion systems. However, the slow kinetics of oxygen electrode reactions inhibit the practical application of Li-O2 battery. Thus, designing efficient electrocatalysts is crucial to improve battery performance. Here, Ti3C2 MXene/Mo4/3B2-x MBene superlattice is fabricated its electrocatalytic activity toward oxygen redox reactions in Li-O2 battery is studied. It is found that the built-in electric field formed by a large work function difference between Ti3C2 and Mo4/3B2-x will power the charge transfer at the interface from titanium (Ti)site in Ti3C2 to molybdenum (Mo) site in Mo4/3B2-x. This charge transfer increases the electron density in 4d orbital of Mo site and decreases the d-band center of Mo site, thus optimizing the adsorption of intermediate product LiO2 at Mo site and accelerating the kinetics of oxygen electrode reactions. Meanwhile, the formed film-like discharge products (Li2O2) improve the contact with electrode and facilitate the decomposition of Li2O2. Based on the above advantages, the Ti3C2 MXene/Mo4/3B2-x MBene superlattice-based Li-O2 battery exhibits large discharge specific capacity (17167 mAhg-1), low overpotential (1.16V), and superior cycling performance (475 cycles).

Solution-plasma treatment for synthesizing Ketjenblack-supported Pt (1 1 1) nanocatalysts with ultra-low overpotential for Li-O2 batteries

Reducing the loading of noble metals to achieve high catalytic activity is key to enhancing the performance and reducing the cost of lithium-oxygen (Li-O2) batteries. In this study, a highly dispersed platinum (111) catalyst supported on Ketjenblack (p-Pt/KBs) is synthesized using a novel approach that involves the interaction between solution and nonthermal plasma (SNP). The influence of different glow discharge voltages on morphology and performance of catalytic materials is investigated. The results show that the electrocatalyst prepared at 400 V has uniform Pt (111) nanocrystals embedded on Ketjenblack, achieved through plasma-induced decomposition of H2PtCl6 followed by nucleation and growth. The designed catalyst, when used as the cathode catalyst in Li-O2 batteries, demonstrates lower polarization losses with an overall overpotential of only 0.24 V compared to commercial platinum on carbon (Pt/C). The plasma effect results in significantly increased defects and grafted oxygen-containing functional groups on the support surface, providing abundant active sites conducive to anchoring of Pt nanoparticles (NPs) onto the scaffold and promoting their electronic coupling. Moreover, dominant mesopores offer ample triple-phase active zones that facilitates lithium-ion transport and rapid oxygen diffusion, further lowering energy barrier for Li2O2 decomposition and reducing the charge overpotential.

Advancements in Lithium–Oxygen Batteries: A Comprehensive Review of Cathode and Anode Materials

As modern society continues to advance, the depletion of non-renewable energy sources (such as natural gas and petroleum) exacerbates environmental and energy issues. The development of green, environmentally friendly energy storage and conversion systems is imperative. The energy density of commercial lithium-ion batteries is approaching its theoretical limit, and even so, it struggles to meet the rapidly growing market demand. Lithium–oxygen batteries have garnered significant attention from researchers due to their exceptionally high theoretical energy density. However, challenges such as poor electrolyte stability, short cycle life, low discharge capacity, and high overpotential arise from the sluggish kinetics of the oxygen reduction reaction (ORR) during discharge and the oxygen evolution reaction (OER) during charging. This article elucidates the fundamental principles of lithium–oxygen batteries, analyzes the primary issues currently faced, and summarizes recent research advancements in air cathodes and anodes. Additionally, it proposes future directions and efforts for the development of lithium–air batteries.

Ordered layered manganese‐based metal–organic frameworks induce 2D growth of discharge products via LiO2 adsorbent for high performance lithium–oxygen batteries

Adjusting the morphology and structure of the catalyst to optimize the structure of the discharge product is an effective strategy for improving the electrocatalytic activity of lithium–oxygen batteries (LOBs). In this paper, a novel high‐orientation layered manganese‐based metal–organic frameworks (Mn‐MOFs) catalyst for the air cathode of a LOB is synthesized via a facile solvothermal method using 2,4‐pyridine dicarboxylic acid combined with the metal Mn2+ ion. The presence of layered structure increases the specific surface area of the catalytic material, and the interlayer spacing can be used as a channel for electron and oxygen transport, thus promoting ion diffusion and catalyzing reactions. Otherwise, the coordination of the N element and metal ion in the organic ligand significantly improves the electrical conductivity and oxygen reduction reaction/oxygen extraction reaction (ORR/OER) performance of LOB. The effective combination of Mn2+ and 2,4‐pyridine dicarboxylic acid improves the overall catalytic capacity of the material, leading to a high LiO2 adsorption capacity so as to induce the formation of film discharge products and extend the cycle life of LOBs. When using Mn‐MOFs at 140°C as the cathode catalyst, the specific discharge capacity of the LOB can achieve 5579 mAh/g with a 0.2 mA/cm2 current density and maintain 140 stable cycles, limiting the specific discharge capacity to 500 mAh/g.

Hydrogen-Bonded Organic Frameworks-based Electrolytes with Controllable Hydrogen Bonding Networks for Solid-State Lithium Batteries.

The lack of stable solid-state electrolytes (SSEs) with high-ionic conductivity and the rational design of electrode/electrolyte interfaces remains challenging for solid-state lithium batteries. Here, for the first time, a high-performance solid-state lithium-oxygen (Li-O2) battery is developed based on the Li-ion-conducted hydrogen-bonded organic framework (LHOF) electrolyte and the HOF-DAT@CNT composite cathode. Benefiting from the abundant dynamic hydrogen bonding network in the backbone of LHOF-DAT SSEs, fast Li+ ion transport (2.2×10-4 S cm-1), a high Li+ transference number (0.88), and a wide electrochemical window of 5.05 V are achieved. Symmetric batteries constructed with LHOF-DAT SSEs exhibit a stably cycled duration of over 1400 h with uniform deposition, which mainly stems from the jumping sites that promote a uniformly high rate of Li+ flux and the hydrogen-bonding network structure that can relieve the structural changes during Li+ transport. LHOF-DAT SSEs-based Li-O2 batteries exhibit high specific capacity (10335 mAh g-1), and stable cycling life up to 150 cycles. Moreover, the solid-state lithium metal battery with LHOF-DAT SSEs endow good rate capability (129.6 mAh g-1 at 0.5 C), long-term discharge/charge stability (210 cycles). The design of LHOF-DAT SSEs opens an avenue for the development of novel SSEs-based solid-state lithium batteries.

Cobalt-Copper-Embedded Nitrogen-Doped Carbon Nanostructures Derived from Zeolite Imidazolate Frameworks as Electrocatalysts for the Oxygen Reduction Reaction.

In recent years, researchers have focused on developing zeolite imidazolate frameworks (ZIFs) as an alternative to Pt electrocatalysts for various applications, including water splitting, lithium-air batteries, zinc-air batteries, and fuel cells. In this study, we synthesized CoCu-ZIF to be used as a precursor in the development of cathode catalysts for the oxygen reduction reaction (ORR) in fuel cells. Hydrazine played a crucial role in maintaining uniformity in the development and particle size of the ZIF-67 structures. Moreover, it facilitated the rapid formation of the ZIF-67 structures at higher temperatures. A unique pseudorhombic dodecahedral morphology was obtained at a Co/Cu molar ratio of 7:3. Among all the synthesized N-doped carbon nanostructures embedded with Co and Cu nanoparticles, CoCu@NC-750, pyrolyzed at 750 °C, showed superior ORR catalytic performance. This catalyst exhibited a notably higher half-wave potential of 0.816 V and demonstrated a clear 4-electron transfer mechanism. The overpotential of CoCu@NC-750 shifted by only 11 mV over 10,000 cyclic voltammetry cycles, whereas a 55 mV shift was observed for Pt/C. CoCu@NC-750 exhibited a ∼0.8% decrease in current density during a 12-h ORR, in contrast to the 8.3% decline shown by Pt/C. This superior catalytic activity and stability can be attributed to factors such as higher oxygen adsorption induced by the N-doped carbon layer due to the localized changes in electron density and the enhanced stability of the bimetallic core. Our findings suggest that CoCu@NC-750 is a promising alternative to Pt/C in fuel cell cathodes.

MOFs-derived CoMn-layered double hydroxide array anchored to Ti3C2Tx MXene nanosheets as efficent catalysts for rechargeable lithium-oxygen batteries

Rechargeable lithium-oxygen batteries (LOBs) are acknowledged as potential candidates for advanced energy storage devices as a result of their considerable theoretical energy densities. Nevertheless, they encounter significant challenges throughout discharging and recharging phases, including the difficult decomposition of Li2O2 products, sluggish reaction kinetics, and limited cycle stability. In this study, an efficient catalyst was synthesized by in situ growth of metal–organic frameworks (MOFs)-derived cobalt manganese layered double hydroxide (CoMn-LDH) array on Ti3C2Tx MXene nanosheets (CoMn-LDH@Ti3C2Tx). The LOBs with CoMn-LDH@Ti3C2Tx cathode demonstrated high discharge specific capacity of 27.61 Ah g−1 at 100 mA g−1 and an extended cycle stability of over 224 cycles at 500 mA g−1. Density functional theory (DFT) computations showed that CoMn-LDH@Ti3C2Tx facilitates electron redistribution, optimising the adsorption energy of intermediates, thereby lowering the energy barriers for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). Consequently, this work presents a multi-level nanostructured catalyst preparation strategy derived from MOFs, offering new insights for the fabrication of efficient electrocatalytic materials.

Mass Transfer Analysis for Achieving High-Rate Lithium-Air Batteries.

Lithium-air batteries (LABs) have aroused worldwide interest due to their high energy density as a promising next-generation battery technology. From a practical standpoint, one of the most pressing issues currently in LABs is their poor rate performance. Accelerating the mass transfer rate within LABs is a crucial aspect for enhancing their rate capability. In this Perspective, we have meticulously analyzed the ion and oxygen transport processes to provide readers with a comprehensive understanding of the mass transfer within LABs. Following this, we have discussed potential misconceptions in the existing literature and propose our recommendations for improving the rate performance of LABs. This Perspective provides a deep insight into the mass transfer process in LABs and offers promising strategies for developing other high-rate metal-O2 batteries.

Modeling of the multi-cycle deep charge and discharge attenuation mechanism of non-aqueous Li–O2 batteries

Due to the high energy density, non-aqueous lithium-oxygen (Li–O2) batteries attract significant attention. However, batteries' high capacity attenuation rate under deep charge and discharge conditions remains a significant challenge. This paper presents a multi-cycle deep charge and discharge model for non-aqueous lithium-oxygen batteries, which predicts the performance of the battery during multiple deep charge and discharge cycles at high and low discharge-specific capacities. The parameter states during different discharge stages in different discharge cycles are investigated by analyzing the battery's cathode porosity, product volume fraction, and oxygen concentration changes. The study shows that as the number of cycles increases, the deposition of a small number of discharge products in the cathode altered the distribution of the newly generated products, thereby affecting the cathode structure and oxygen transport in the subsequent discharge. Moreover, depositing a small amount of discharge products can result in significant capacity attenuation in the battery. This model can accurately evaluate the deep charge and discharge performance attenuation process of non-aqueous Li–O2 batteries, which helps improve the understanding of the deep discharge attenuation mechanism of non-aqueous Li–O2 batteries.

Nanoengineering of Cathode Catalysts for Li-O2 Batteries.

Lithium-oxygen (Li-O2) batteries have obtained widespread attention as next-generation energy storage systems due to their extremely high energy density. However, the high charge overpotential, attributed to the insulating property of Li2O2, significantly limits the energy efficiency and triggers solvent degradation. The high electrochemical activities of oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) on the cathode are crucial for alleviating the high charging polarizations and enhancing the lifetime of Li-O2 batteries, which are also top challenges of state-of-art research. In this review, the scientific challenges and the proposed solutions in the development of cathode catalysts have been summarized. The recent research advancements on the nanoengineering of cathode catalysts for Li-O2 batteries have been comprehensively discussed, and the perspectives on the structure optimization are presented. Meanwhile, we have elucidated the structure-performance relationship between the electronic state and performance of the cathode catalysts at the nanoscale level. This review intends to provide guidelines for the design and construction of cathode catalysts in advanced Li-O2 batteries.

Synthesis of High-Entropy Perovskite Hydroxides as Bifunctional Electrocatalysts for Oxygen Evolution Reaction and Oxygen Reduction Reaction.

Oxygen reduction reaction (ORR) and oxygen evolutionc reaction (OER) are important chemical reactions for a rechargeable lithium-oxygen battery (LOB). Recently, high-entropy alloys and oxides have attracted much attention because they showed good electrocatalytic performance for oxygen evolution reaction (OER) and/or oxygen reduction reaction (ORR). In this study, we aimed to synthesize and characterize CoSn(OH)6 and two types of high-entropy perovskite hydroxides, that is, (Co0.2Cu0.2Fe0.2Mn0.2Mg0.2)Sn(OH)6 (CCFMMSOH) and (Co0.2Cu0.2Fe0.2Mn0.2Ni0.2)Sn(OH)6 (CCFMNSOH). TEM observation and XRD measurements revealed that the high-entropy hydroxides CCFMMSOH and CCFMNSOH had cubic crystals with sides of approximately 150-200 nm and crystal structures similar to those of perovskite-type CSOH. LSV measurement results showed that the high-entropy hydroxides CCFMMSOH and CCFMNSOH showed bifunctional catalytic functions for the ORR and OER. CCFMNSOH showed better catalytic performance than CCFMMSOH.

Constructing an Interlaced Catalytic Surface via Fluorine-Doped Bimetallic Oxides for Oxygen Electrode Processes in Li-O2 Batteries.

Lithium-oxygen (Li-O2) batteries, renowned for their high theoretical energy density, have garnered significant interest as prime candidates for future electric device development. However, their actual capacity is often unsatisfactory due to the passivation of active sites by solid-phase discharge products. Optimizing the growth and storage of these products is a crucial step in advancing Li-O2 batteries. Here, a fluorine-doped bimetallic cobalt-nickel oxide (CoNiO2- xFx/CC) with an interlaced catalytic surface (ICS) and a corncob-like structure is proposed as an oxygen electrode. Unlike conventional oxide electrodes with a "single adsorption catalytic mechanism," the ICS of CoNiO2- xFx/CC offers a "competitive adsorption catalytic mechanism," where oxygen sites facilitate oxygen conversion while fluorine sites contribute to the growth of Li2O2. This results in a change in Li2O2 morphology from a surface film to toroidal particles, effectively preventingthe burial of active sites. Additionally, the unique open architecture aids in the capture and release of oxygen and the formation of well-contacted Li2O2/electrode interfaces, which benefits the complete decomposition of Li2O2 products. Consequently, the Li-O2 battery with a CoNiO2- xFx/CC cathode demonstrates a high specific capacity of up to 30923 mAh g-1 and a lifespan exceeding 580 cycles, surpassing most reported metal oxide-based cathodes.

Homogeneous In‐Plane Lattice Strain Enabling d‐Band Center Modulation and Efficient d–π Interaction for an Ag2Mo2O7 Cathode Catalyst With Ultralong Cycle Life in Li‐O2 Batteries

AbstractAlthough lithium–oxygen batteries (LOBs) hold great promise as future energy storage systems, they are impeded by insulated discharge product Li2O2 and sluggish oxygen reduction reaction/oxygen evolution revolution (ORR/OER) kinetics. The application of a highly efficient cathode catalyst determines the LOBs performance. The d‐band modulation and catalytic kinetics promotion are important concept guidelines for the performance enhancement of cathode catalysts. In this work, the homogeneous in‐plane distortion‐derived synergistic catalytic capability of an Ag2Mo2O7 catalyst with modulated d‐band centers and promoted ORR/OER kinetics is demontrated. The uniform elongation of Ag─O bonds and compression of Mo─O bonds in (020) plane leads to d‐band splitting and d‐band center optimization and delivers improved adsorption behavior for high ORR/OER capability. Furthermore, the spatial and energy overlap of Ag dxz and O2 anti‐bonding π* orbitals facilitate electron injection during ORR process and reduce the energy barrier for charge transfer and O2 desorption during OER process, accelerating the ORR/OER kinetics. As a result, the (020) plane‐exposed Ag2Mo2O7 cathode exhibits ultralong cycle stability of 817 cycles at 500 mA g−1 and large specific discharge/charge capacities of 15898/15180 mAh g−1. This work provides facile concept guidance for optimizing catalytic capability through controlled lattice distortion in cathode catalysts for LOBs.

Crown Ether Electrolyte Induced Li2O2 Amorphization for Low Polarization and Long Lifespan Li-O2 Batteries.

Lithium-oxygen batteries possess an extremely high theoretical energy density, rendering them a prime candidate for next-generation secondary batteries. However, they still face multiple problems such as huge charge polarization and poor life, which lay a significant gap between laboratory research and commercial applications. In this work, we adopt 15-crown-5 ether (C15) as solvent to regulate the generation of discharge products in lithium-oxygen batteries. The coronal structure endows C15 with strong affinity to Li+, firmly stabilizes the intermediate LiO2 and discharge product Li2O2. Thus, the crystalline Li2O2 is amorphized into easily decomposable amorphous products. The lithium-oxygen batteries assembled with 0.5 M C15 electrolyte show an increased discharge capacity from 4.0 mAh cm-2 to 5.7 mAh cm-2 and a low charge overpotential of 0.88 V during the whole lifespan at 0.05 mA cm-2. The batteries with 1 M C15 electrolyte can cycle stably for 140 cycles. Furthermore, the amorphous characteristic of Li2O2 product is preserved when matched with redox mediators such as LiI, with the charge polarization further decreasing to 0.74 V over a cycle life of 190 cycles. This provides new possibilities for electrolyte design to promote Li2O2 amorphization and reduce charge overpotential in lithium-oxygen batteries.

Promoted Reaction Reversibility by Dual-Effect 15-Crown-5 Ether Additive for High-Performance Li-O2 Batteries.

The practical application of lithium-oxygen batteries (LOBs) with ultrahigh theoretical energy density faces the problems of poor kinetics and deficient reversibility. The electrolyte is of vital significance to the electrochemical stability and reaction pathway of LOBs due to the formation of soluble products. Here, a 15-crown-5 ether (15C5) is employed to regulate the solvation structure of Li+ and manipulate the reaction mechanism through regulating the binding ability toward Li+. The promoted dissociation of LiNO3 by 15C5 increases the catalytical active anions in the electrolyte and stabilizes the Li-containing reduced oxygen species to promote the solution pathway of discharge product growth. Besides, 15C5 also facilitates the kinetics of the electrochemical decomposition of Li2O2 and prolongs the cycle life to 178 cycles. This work inspires a novel approach to improve the battery performance through electrolyte component design.

Coordination environment modulation to optimize d-orbit arrangement of Mn-based MOF electrocatalyst for lithium-oxygen battery

Nowadays lithium-oxygen (Li-O2) batteries with metal-organic frameworks (MOFs) based oxygen electrodes have suffered from the sluggish kinetics and irreversible behavior of Li2O2 formation/decomposition, which originates from weak orbit coupling with oxygen species caused by narrow orbit arrangement of metal sites in MOFs. Modulation of coordination environment of metal sites has been regarded as the vital strategy to tune 3d orbit arrangement and electron distribution of metal sites, which is favorable for altering electron transfer pathway and oxygen electrode reaction kinetics. Herein, electron-rich ferrocene acid (FcA), as grafted ligand, is introduced on Mn sites of Mn-MOF-74 (named as Mn-MOF-74-FcA) for facilitating the oxygen electrode reactions in Li-O2 batteries. In details, due to the strong electron delocalization on electron-rich FcA ligand, the resulted metal-ligand interaction between FcA and Mn sites distorts [MnOx] coordination sphere, which induces 3d orbits rearrangement of Mn sites from (dx2-y2/dxy, dz2, dxz/dyz) to (dx2-y2, dz2, dxz, dyz, dxy) and electron transfer from electron-rich FcA to Mn sites. And the strong orbit overlapping between LiO2 intermediate and widened Mn d-band ensures the electron exchange with each other and thus reduces the energy barrier of oxygen electrode reactions. Moreover, electron transfer from FcA ligand to Mn sites also leads to the decreased energy gap between valence band (VB) and conduction band (CB). As expected, Li-O2 battery with Mn-MOF-74-FcA exhibits low overpotential of 0.82 V and long lifespan of 276 cycles at the current density of 200 mA g−1.

Recent Progress of Electrolyte Materials for Solid‐State Lithium–Oxygen (Air) Batteries

AbstractSolid‐state lithium–air batteries (SSLABs) have become the focus of next‐generation advanced batteries due to their safety and high energy densities. Current research on SSLABs is mainly centered on solid‐state electrolytes (SSEs). Although SSEs exhibit excellent properties, such as good stability, high safety, and great mechanical strength, they also display several distinct weaknesses of low ionic conductivities, poor stabilities in air, and high interfacial impedances, which will require sustained attentions for further investigations. This review first overviews the development history of SSEs achieved in terms of Li–air batteries. Subsequently, the fundamental properties, preparation methods, merits and drawbacks of different SSEs, along with their use in SSLABs, and the optimization strategy, especially for the inorganic solid electrolytes, polymer electrolytes, and hybrid electrolytes are comprehensively summarized. Finally, the research progresses made with SSEs are outlined, and critical insights and approaches for the remaining challenges of electrolytes and commercial application of SSLABs are proposed, which include advanced characterization, combining experiments and artificial intelligence such as theoretical calculations, and constructing selective permeability membranes. It is expected that this timely review will provide researchers with an integrated, systematic, and in‐depth understanding of SSEs and guidelines for future research, thus further promoting the commercial application of SSLABs.

Reducing Overpotential of Lithium-Oxygen Batteries by Diatomic Metal Catalyst Orbital Matching Strategy.

Aprotic Li-O2 batteries have sparked attention in recent years due to their ultrahigh theoretical energy density. Nevertheless, their practical implementation is impeded by the sluggish reaction kinetics at the cathode. Comprehending the catalytic mechanisms is pivotal to developing efficient cathode catalysts for high-performance Li-O2 batteries. Herein, the intrinsic activity map of Li-O2 batteries is established based on the specific adsorption mode of O2 induced by diatomic catalyst orbital matching and the transfer-acceptance-backdonation mechanism, and the four-step screening strategy based on the intrinsic activity map is proposed. Guided by the strategy, FeNi@NC and FeCu@NC promising durable stability with a low overpotential are screened out from 27 Fe-Metal diatomic catalysts. Our research not only provides insights into the fundamental understanding of the reaction mechanism of Li-O2 batteries but also accelerates the rational design of efficient Li-O2 batteries based on the structure-activity relationship.