Discharge Product Li2O2 Research Articles

N, F Co-Doped Carbon Material Self-Supporting Cathode for High-Performance Lithium-Oxygen Batteries.

The Li-O2 battery has emerged as a promising energy storage system due to its exceptionally high theoretical energy density of 3500 Wh kg-1. However, the sluggish kinetics associated with the formation and decomposition of discharge product Li2O2 poses several challenges in Li-O2 batteries, including excessive over-potential, limited rate performance, and reduced actual specific energy. Consequently, the development of cost-effective cathode catalysts with enhanced catalytic activity and long-term stability represents a viable approach to address these challenges. In this study, commercial melamine foam is utilized as a precursor material which was subjected to pyrolysis at elevated temperatures with PVDF to synthesize N, F co-doped self-supporting carbon cathode (NF-NSC). Remarkably, thanks to the synergistic effects of N, F heteroatomic in conjunction with the inherent three-dimensional reticular porous structure, NF-NSC exhibited enhanced electrochemical performance when utilized in Li-O2 batteries. Specifically, the NF-NSC cathode demonstrated an impressive discharge specific capacity of up to 35204 mAh g-1 alongside a low over-potential (0.86 V) and excellent cycling stability (146 cycles).

A‐Site Defect Engineering Regulates Bimetallic Exsolution in Perovskite Oxide Boosting the Performance of Li–O2 Batteries

AbstractThe application life of Lithium–oxygen (Li–O2) batteries can be significantly affected by the formation and full decomposition of the discharge product Li2O2. After exsolution, the catalyst is designed to control the morphology and crystallinity of Li2O2 enhanced reversibility. In the perovskite exsolution system, the large amount of A‐site defects are introduced to induce the activation of lattice oxygen and the formation of oxygen vacancy, and promote the bimetallic exsolution from LaxFe0.8Cu0.1Co0.1O3. When x = 0.70, the distribution density of CuCo alloy and Cu metal increases and the size is smaller. Through exsolution process, the resulting oxygen vacancy and more doped ions exsolved expose a significant number of active sites that enhance the charge transfer and catalytic activity. Therefore, the charge resistance (Rct) smaller and can be better decomposed due to the generated small‐size Li2O2 with nano‐sheet morphology. Meanwhile, theoretical calculation shows that the exsolution of the catalyst enhances the adsorption of the intermediate LiO2 that makes the surface mechanism more advantageous. The reversibility of the battery is improved, and the cycle stability reaches 195 cycles. This work can serve as a guide for the development of exsolution that directs the design of high efficiency cathode catalyst.

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

AbstractLithium‐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.

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.

A lithiated zeolite-based protective layer to boost the cycle performance of lithium−oxygen batteries via redox mediator sieving

Lithium–oxygen (Li–O2) batteries with ultra-high theoretical specific energy (3500 Wh kg−1) have attracted significant attention, but the sluggish electrochemical processes of discharge product Li2O2 lead to poor cycling stability. Redox mediators (RMs) as soluble catalysts are widely used to assist with the electrochemical formation/decomposition of Li2O2. However, the shuttle effect of RMs causes severe deterioration of both RMs and Li metal anodes. Herein, for the first time we synthesize a lithiated zeolite-based protective layer on Li anodes to mitigate the shuttle effect of 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) in Li–O2 batteries. The protective layer successfully blocks the migration of TEMPO toward the Li anode owing to the angstrom-level aperture size of lithiated zeolite. Due to the excellent redox-mediator-sieving capability of the protective layer, the cycle life of the Li−O2 batteries is significantly prolonged more than ten times at a current density of 250 mA g−1 and a limited capacity of 500 mA h g−1. This work demonstrates that the lithiated zeolite-based protective layer capable of molecular sieving is a facile and scalable way to mitigate the shuttle effect of RMs in Li–O2 batteries.

Modulation Strategies and Activity Descriptors of Spinel Electrocatalysts for Lithium−Oxygen Batteries

AbstractThe exploitation of high energy density lithium−oxygen batteries (LOBs) holds significant importance for energy storage and applications. An efficient cathode catalyst can effectively prevent the accumulation of the insulating insoluble discharge product Li2O2, thereby enhancing the electrochemical performance. Spinel materials, widely available and cost‐effective, exhibit superior catalytic activity, making them ideal candidates for LOBs cathode catalysts. This review aims to offer a comprehensive and insightful overview of the recent progress in the design of spinel‐type electrocatalysts for LOBs. This review exhaustively summarizes various modification strategies applied to spinel materials and emphasizes the influential role of catalytic descriptors in designing highly active spinel‐type catalysts. This review provides guidance for the design and utilization of high‐performance spinel‐type catalysts, thereby contributing to the dynamic development of LOBs.

Characteristic analysis of lithium–oxygen batteries considering the discontinuous deposit and electrolyte degradation effects during discharge

The modeling research plays a crucial role in grasping the reaction mechanisms and forecasting the performance of lithium‑oxygen (LiO2) batteries. A transient LiO2 battery model including continuity, transportation, and reaction kinetics by simultaneously considering the discontinuous deposit of discharge product Li2O2 and the formation of by-product Li2CO3 due to electrolyte degradation, is developed to reveal the discharge phenomena. The effects of operating conditions and electrolyte and electrode properties on the discharge behaviors including voltage-capacity curve, energy density, profiles of O2 concentration (CO2) and porosity (ɛ) at the cathode are quantitatively studied. It is found that enhancing O2 solubility (SO2) and diffusivity (DO2) significantly improves discharge capacity and voltage plateau; the promotion of voltage plateau will be inconspicuous as electrolyte conductivity (κ) is enlarged over 1 S/m. With the rise of ɛ from 0.73 to 0.93, the specific capacity is boosted from 874 to 6122 mAh/g‑carbon, and the corresponding specific energy upgrades from 2260 to 15,610 mWh/g‑carbon. Shortening cathode thickness (Lca) facilitates the efficient utilization of carbon cathode material but this comes at the expense of lowering the mass loading of carbon, the practical energy drops 59.4 % as Lca reduces from 750 μm to 100 μm. After 20 consecutive charge-discharge cycles, the capacity retention obtained is 36.884 %, accompanied by a 13.8 % volume fraction of Li2CO3 formation inside the cathode. This work may guide in designing electrodes and electrolytes and provide performance regulation strategies for LiO2 batteries.

Strain‐rich high‐entropy perovskite oxide of (La0.8Sr0.2)(Mn0.2Fe0.2Cr0.2Co0.2Ni0.2)O3 for durable and effective catalysis of oxygen redox reactions in lithium‐oxygen battery

AbstractDespite their great promise as high‐energy‐density alternatives to Li‐ion batteries, the extensive use of lithium‐oxygen (Li‐O2) batteries is constrained by the slow kinetics of both the oxygen evolution reaction and oxygen reduction reaction. To increase the overall performance of Li‐O2 batteries, it is essential to increase the efficiency of oxygen electrode reactions by constructing effective electrocatalysts. As a high‐efficiency catalyst for Li‐O2 batteries, high entropy perovskite oxide (La0.8Sr0.2)(Mn0.2Fe0.2Cr0.2Co0.2Ni0.2)O3 (referred to as LS(MFCCN)O3) is designed and investigated in this article. The introduction of dissimilar metals in LS(MFCCN)O3 has the potential to cause lattice deformation, thereby enhancing electron transfer between transition metal ions and facilitating the formation of numerous oxygen vacancies. This feature is advantageous for the reversible production and breakdown of discharge product Li2O2. Consequently, the Li‐O2 battery utilizing LS(MFCCN)O3 as a catalyst achieves an impressive discharge capacity of 17,078.2 mAh g−1 and exhibits an extended cycling life of 435 cycles. This study offers a useful method for adjusting the catalytic performance of perovskite oxides toward oxygen redox reactions in Li‐O2 batteries.

A Grafted Hybrid Nanosheet Array Architecture Enables Efficient Bifunctional Oxygen Catalytic Electrodes for Rechargeable Lithium−Oxygen Batteries

AbstractTo fully manifest the high energy densities of lithium−oxygen (Li−O2) batteries, bifunctional catalytic cathodes that efficiently facilitate both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are mandatorily required. However, catalysts with intrinsic bifunctional catalytic activities are limited in practice. In addition, the practical utilization rate of oxygen catalytic cathodes is usually lower due to the deposition of insoluble discharge product Li2O2. To address these issues, this work proposes a grafted hybrid nanosheet array architecture to enable efficient bifunctional oxygen catalytic cathodes for Li−O2 batteries. As a demonstration, Co3O4 nanosheet arrays (MnO2−Co3O4@CC) grafted with MnO2 nanosheets are prepared on carbon cloth by facile electrodeposition followed by calcination in air. The mutually perpendicular Co3O4 and MnO2 nanosheets in the grafted architecture enable both the ORR catalytically active site of MnO2 and the OER catalytically active site of Co3O4 easily accessible during repeated cycling. Thus, the synergistic bifunctional catalysis of hybrid MnO2−Co3O4@CC is effectively realized to deliver a high specific capacity of 8115 mA h g−1 and a low overall overpotential of 0.64 V. This work provides a universal and effective approach for fabricating various efficient catalytic electrodes via the facile integration of different nanomaterials on nanoarray architectures.

Air activation enhances the porosity and N,O synergistic effect towards an efficient metal free carbon cathode for Li-O2 battery

The achievement of Li-O2 batteries with high energy density and extended cycle life is often hindered by the disorderly growth of solid discharge product Li2O2 on the cathode and its sluggish decomposition reaction kinetics. Herein, under the guidance of DFT simulations, the N,O co-doped carbon was identified as a potential efficient metal free cathode catalyst to remit these problem in Li-O2 batteries. Then, a spherical shell-like N,O co-doped carbon was prepared through the direct pyrolysis of guanosine 5′-monophosphate disodium salt (5′-GMP, 2Na). After a further activation process in air, the carbon shells exhibit a finer porous surface with greatly enhanced specific surface area and surface N,O contents. As a result, the morphology of Li2O2 changed from large toroidal to film by using the activated carbon as a cathode catalyst due to its tailored surface structure with improved N and O synergistic effect. What's more, the film-like Li2O2 with Li vacancy can not only form an increased interfacial contact and interaction with the active sites on carbon, but also be conducive to the transfer of Li+/electrons during the decomposition of Li2O2, thus accelerating the electrochemical performances of the battery.

Epitaxial Growth of Li2O2 Achieved by a Rational Designed Fe3O4@N‐doped Carbon Nanoflower Structure for Improving the Performance of Li−O2 Batteries

AbstractThe insulated and insoluble discharge product Li2O2 can cause excessive charge overpotential, eventually leading to the deactivation of the Li−O2 battery. Here, a nanoflower structure (Fe3O4@NC) fabricated by coating Fe3O4 with N‐doped carbon was used as an effective catalyst for Li−O2 cathode. The N‐doped defective carbon layer provides sufficient active sites for the formation of discharge intermediates and exhibits a coating effect on Fe3O4, thereby facilitating the maintenance of structural stability. The hierarchical structure of Fe3O4 can effectively mitigate the agglomeration of the carbon layer, thus promoting a homogeneous distribution and optimal utilization of active sites on the carbon layer. As a result, the synergistic effect of Fe3O4 combined with the N‐doped carbon layer enhances the Li+/e− transfer rate and effectively accelerates the kinetic of oxygen reduction/evolution reaction (ORR/OER). Furthermore, the unique functionality of Fe3O4@NC induces the epitaxial growth of Li2O2 into uniform nanosheets, thereby increasing the utilization of cathode space and ultimately promoting the energy release of Li−O2 batteries. The Li−O2 battery with Fe3O4@NC cathode exhibits remarkable full discharge capacity of 16495 mAh g−1 and significantly improved round‐trip performances for 120 cycles at a cutoff capacity of 1000 mAh g−1 with a current density of 200 mA g−1.

Tunable Oxygen Vacancies of Cobalt Oxides in Lithium-Oxygen Batteries: Morphology Control of Discharge Product.

The discharge product Li2O2 is difficult to decompose in lithium-oxygen batteries, resulting in poor reversibility and cycling stability of the battery, and the morphology of Li2O2 has a great influence on its decomposition during the charging process. Therefore, reasonable design of the catalyst structure to improve the density of catalyst active sites and make Li2O2 form a morphology which is easy to decompose in the charging process will help improve the performance of battery. Here, we demonstrate a series of hollow nanoboxes stacked by Co3O4 nanoparticles with different sizes. The results show that the surface of the nanoboxes composed of smaller size Co3O4 nanoparticles contains abundant pore structure and higher concentration of oxygen vacancies, which changes the adsorption energy of reactants and intermediates, providing more nucleation sites for Li2O2, thereby forming Li2O2 with high dispersion, which is easier to decompose during charging, and eventually improve the performance of the battery. This provides an important idea for the structural design of the cathode catalyst in lithium-oxygen batteries and the regulation of Li2O2 morphology.

The Role of Self-Catalysis Induced by Co Doping in Nonaqueous Li-O2 Batteries.

This work systematically studies the product self-catalysis of in situ electrochemical cobalt doping of Li2O2 and reveals its potential mechanism for improving the performance of lithium-oxygen (Li-O2) batteries. Theoretical calculations demonstrate that the discharge products contain substituted and interstitial Co impurities, which serve as active sites to promote the formation of Li3O4 crystallization, thus switching the nucleation mechanism from the main discharge product Li2O2 to Li3O4. This Co-doping behavior leads to the thermodynamically favorable and dynamically stable formation of Li3O4 crystals during the discharge process. Through systematic investigation of the structural, energetic, electronic, diffusive, and catalytic properties of the Co-doped Li2O2 and Li3O4 compounds, we found that Li3O4 has better charge/mass transport and a lower overpotential for the Li3O4 formation/decomposition reaction. Consequently, this work elucidates that Co doping provides a simple and effective approach for increasing the proportion of Li3O4, which can significantly improve the Li-O2 battery performance.

Operando Observation of the De-Evolution/Evolution Process of Hydrated LiOH in Moisture-Assisted Li-O2 Batteries.

All-solid-state Li-O2 batteries that use ceramic electrolytes have been suggested to overcome the limitations posed by the decomposition of organic electrolytes. However, these systems show a low discharge capacity and high overpotential because the discharge product Li2O2 has low electronic conductivity. In this study, all-solid-state planar-type Li-O2 cells were constructed using a lithium anode, a Li1·3Al0·3Ti1·7(PO4) (LATP) inorganic solid electrolyte, and an air electrode composed of a Pt grid pattern. The discharge/charge process was observed in real time in a humidified O2 environment for the first time, which clarified both the hydration process of the discharge products and the charging process of the hydrated discharge products. The discharge product (LiOH) could be easily hydrated in water, which would facilitate ion transport, thereby increasing the discharge capacity and discharge voltage (vs Li/Li+; from 2.96 to 3.4 V). Thus, Li-O2 cells with a high energy density and a capacity of 3600 mAh/gcathode were achieved using a planar Pt-patterned electrode in a humidified O2 environment. This study is the first to demonstrate the hydration of the discharge products of a Li-O2 cell in humidified O2. Based on a thorough understanding of the hydration phenomenon/mechanism, our findings suggest new strategies for developing high-energy-density all-solid-state Li-O2 batteries using a simple, easy-to-manufacture planar Pt-patterned cathode.

Study on performance of hybrid lithium-air batteries with different alkaline cation pairs in ambient environment

Hybrid lithium-air batteries (HLABs) effectively solve the bottleneck problem of discharge product Li2O2 blocking non-aqueous lithium-air batteries' electrode pores, attracting extensive attention. This paper analyzes the battery's cycle performance, deep discharge performance, and main failure reasons in an ambient environment using the LiOH and KOH aqueous solutions as cathode electrolytes. Meanwhile, the authors intensely study the internal mechanism of mass transfer by molecular dynamics simulation method based on these two cases of electrolytes. The KOH aqueous solution as cathode electrolytes of HLABs has superior deep discharge performance due to the better diffusion ability of K+, and the hydration of cations weakened. However, because the KOH is more alkaline than LiOH, the corrosion on LAGP plates will be severe, affecting the battery's cycle performance. So, the cycle discharge performance of the LiOH aqueous solution as cathode electrolytes of HLABs is significantly better than that of the KOH solution. Under the external electric field, the hydration of cations weakened, which is more favorable to the mass transfer of batteries. Therefore, the HLABs with KOH perform better in deep discharge, and the HLABs with LiOH perform better in long cycles. The research results provide a particular reference for subsequent research and application.

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 Li2 O2 , 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% H2 O 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 2.83V and a large discharge capacity of 12760.8 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.

Interfacial catalytic behaviors of atomic thin SnS2 layer in Li-O2 batteries

Li-O2 battery has been considered to be one of the promising energy storage devices due to its extreme large theoretical energy density. However, the severe electrochemical polarization and irreversible decomposition of the discharge product Li2O2 dramatically prevent its widely applications. In this article, a low-cost 2D atomic thin few-layer SnS2 catalysts synthesized via a modified hydrothermal method are employed as the catalyst cathode for the Li-O2 batteries. The catalytic properties of atomic thin SnS2 layer in the Li-O2 batteries are discussed through systematic experiments and theoretical calculations. It is found that the generation of Sn4+/Sn2+ redox couple in the SnS2 catalyst may act as the active catalytic sites on promoting formation/decomposition for the intermediate LiO2 and discharge product Li2O2 throughout the cycling processes. Moreover, it is calculated that the (001) plane for the SnS2 cathode can reduce the adsorption energy barrier and the catalytic reaction energy gaps for the interface electrochemical reaction in the Li-O2 batteries. Our work may not only reveal the catalystic mechanism of SnS2 for promoting ORR/OER processes in Li-O2 batteries, but also pave a way to explore new SnS2-based electrocatalysts for energy conversion and storage in the future.

Single-Atom-Mediated Spinel Octahedral Structures for Elevated Performances of Li-Oxygen Batteries.

Li-oxygen batteries have attracted much attention due to its ultra-high theoretical specific capacity, but the discharge product Li2 O2 is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high-efficiency cathode catalysts of Co3 O4 loaded with single-atomic metals (M=Ru, Pd, Pt, Au, Ir). The single-atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co3+ exposed, providing rich nucleation sites for Li2 O2 deposition. And the loaded M atoms could separate the active Co3+ centers, thereby regulating the dispersion of Li2 O2 to obtained a sheet-like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.

Single‐Atom‐Mediated Spinel Octahedral Structures for Elevated Performances of Li‐Oxygen Batteries

AbstractLi‐oxygen batteries have attracted much attention due to its ultra‐high theoretical specific capacity, but the discharge product Li2O2is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high‐efficiency cathode catalysts of Co3O4loaded with single‐atomic metals (M=Ru, Pd, Pt, Au, Ir). The single‐atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co3+exposed, providing rich nucleation sites for Li2O2deposition. And the loaded M atoms could separate the active Co3+centers, thereby regulating the dispersion of Li2O2to obtained a sheet‐like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.