Aligned Ion Conduction Pathway of Polyrotaxane-Based Electrolyte with Dispersed Hydrophobic Chains for Solid-State Lithium-Oxygen Batteries.

A critical challenge hindering the practical application of lithium-oxygen batteries (LOBs) is the inevitable problems associated with liquid electrolytes, such as evaporation and safety problems. Our study addresses these problems by proposing a modified polyrotaxane (mPR)-based solid polymer electrolyte (SPE) design that simultaneously mitigates solvent-related problems and improves conductivity. mPR-SPE exhibits high ion conductivity (2.8 × 10-3 S cm-1 at 25 °C) through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion. Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles. In situ Raman spectroscopy reveals the presence of an LiO2 intermediate alongside Li2O2 during oxygen reactions. Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture, as demonstrated by the air permeability tests. The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.

A Supramolecular Deep Eutectic Electrolyte Enhancing Interfacial Stability and Solution Phase Discharge in Li-O2 Batteries.

Li-O2 batteries (LOBs) have gained widespread recognition for their exceptional energy densities. However, a major challenge faced by LOBs is the lack of appropriate electrolytes that can effectively balance reactant transport, interfacial compatibility, and non-volatility. To address this issue, a novel supramolecular deep eutectic electrolyte (DEE) has been developed, based on synergistic interaction between Li-bonds and H-bonds through a combination of lithium salt (LiTFSI), acetamide (Ace) and boric acid (BA). The incorporation of BA serves as an interface modification additive, acting as both Li-bonds acceptor and H-bonds donor/acceptor, thereby enhancing the redox stability of the electrolyte, facilitating a solution phase discharge process and improving compatibility with the Li anode. Our proposed DEE demonstrates a high oxidation voltage of 4.5 V, an ultrahigh discharge capacity of 15225 mAh g-1 and stable cycling performance of 196 cycles in LOBs. Additionally, the intrinsic non-flammability and successful operation of a Li-O2 pouch cell indicate promising practical applications of this electrolyte. This research broadens the design possibilities for LOBs electrolytes and provides theoretical insights for future studies.

Robust oxygen adsorbent mediated oxygen redox reactions for high performance lithium-oxygen battery.

Lithium-oxygen batteries (LOBs) have been widely studied because of their ultra-high energy density (∼3500 Wh kg-1). However, the reversibility and stability of LOBs are greatly limited by the sluggish kinetics of oxygen reduction/evolution reactions (ORR/OER) and severely parasitic reactions on oxygen electrodes. Electrolyte in LOBs plays an important role in the transport of reactive oxygen species and Li+, which greatly affects the kinetics and reversibility of the charging and discharging processes of batteries. In this work, perfluorooctane (PFO) is used as the additive in 1.0 M LiTFSI/TEGDEM electrolyte for LOBs to regulate the kinetics of oxygen electrode reactions. Due to the strong adsorption ability of PE toward oxygen, the oxygen concentration inside the electrolyte is greatly increased after the addition of PE. In addition, the PE-added electrolyte also exhibits superior electrochemical stability and is capable of triggering solution-mediated Li2O2 growth pathway during the discharge process of the LOBs. Therefore, with the increased oxygen concentration and the optimized electrode/electrolyte interface, the ORR/OER kinetics on the oxygen electrode is significantly promoted, which enables the LOBs with excellent energy efficiency and cycling life. This work provides a new idea for the design of oxygen-rich and high-performance electrolyte for lithium-oxygen batteries.

Synergistic effect of oxygen vacancies and in-situ formed bismuth metal centers on BiVO4 as an enhanced bifunctional Li-O2 batteries electrocatalyst.

Bismuth Vanadate (BiVO4) is a promising oxide-based photoanode for electrochemical applications, yet its practical use is constrained by poor charge transport properties, particularly under dark conditions. This study introduces a novel BiVO4 variant (Bi-BiVO4-10) that incorporates abundant oxygen vacancies and in-situ formed Bi metal, significantly enhancing its electrical conductivity and catalytic performance. Bi-BiVO4-10 demonstrates superior electrochemical performances compared to conventional BiVO4 (C-BiVO4), demonstrated by its most positive half-wave potential with the highest diffusion-limiting current in the oxygen reduction reaction (ORR) and earliest onset potential in the oxygen evolution reaction (OER). Notably, Bi-BiVO4-10 is explored for the first time as an electrocatalyst for lithium-oxygen (Li-O2) cells, showing reduced overcharge (610 mV) in the first cycle and extended cycle life (1050 h), outperforming carbon (320 h) and C-BiVO4 (450 h) references. The enhancement is attributed to the synergy of oxygen vacancies, Bi metal formation, increased surface area, and improved electrical conductivity, which collectively facilitate Li2O2 growth, enhance charge transport kinetics, and ensure stable cycling. Theoretical calculations reveal enhanced chemical interactions between intermediate molecules and the defect-rich surfaces of Bi-BiVO4-10, promoting efficient discharge and charge processes in Li-O2 batteries. This research highlights the potential of unconventional BiVO4-based materials as durable electrocatalysts and for broader electrochemical applications.

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

Lithium-oxygen batteries (LOBs) with high energy density are a promising advanced energy storage technology. However, the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time, resulting in large polarization and battery failure in a short time. Therefore, a self-supporting interconnected nanosheet array network NiCo2O4/MnO2 with a Mott-Schottky heterostructure on titanium paper (TP-NCO/MO) is ingeniously designed as an efficient cathode catalyst material for LOBs. This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface, thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition, which is expected to solve the above problems. The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V. This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure, providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.

Binder-Free Three-Dimensional Porous Graphene Cathodes via Self-Assembly for High-Capacity Lithium-Oxygen Batteries.

The porous architectures of oxygen cathodes are highly desired for high-capacity lithium-oxygen batteries (LOBs) to support cathodic catalysts and provide accommodation for discharge products. However, controllable porosity is still a challenge for laminated cathodes with cathode materials and binders, since polymer binders usually shield the active sites of catalysts and block the pores of cathodes. In addition, polymer binders such as poly(vinylidene fluoride) (PVDF) are not stable under the nucleophilic attack of intermediate product superoxide radicals in the oxygen electrochemical environment. The parasitic reactions and blocking effect of binders deteriorate and then quickly shut down the operation of LOBs. Herein, the present work proposes a binder-free three-dimensional (3D) porous graphene (PG) cathode for LOBs, which is prepared by the self-assembly and the chemical reduction of GO with triblock copolymer soft templates (Pluronic F127). The interconnected mesoporous architecture of resultant 3D PG cathodes achieved an ultrahigh capacity of 10,300 mAh g-1 for LOBs. Further, the cathodic catalysts ruthenium (Ru) and manganese dioxide (MnO2) were, respectively, loaded onto the inner surface of PG cathodes to lower the polarization and enhance the cycling performance of LOBs. This work provides an effective way to fabricate free-standing 3D porous oxygen cathodes for high-performance 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.

Boosting the ORR/OER Activity of Cobalt-Based Nano-Catalysts by Co 3d Orbital Regulation.

The transition metal oxides/sulfides are considered promising catalysts due to their abundant resources, facile synthesis, and reasonable electrocatalytic activity. Herein, a significantly improved intrinsic catalytic activity is achieved for constructing a Co-based nanocrystal (Co-S@NC) with the coordination of Co─S, Co─S─C, and Co─Nx─C. The calculational and experimental results demonstrate that the diversified chemical environment of Co-cations induces the transition of 3d orbitals to a high spin-state that exhibits the coexistence of Co2+ with fully occupied dπ orbitals and Co3+ with unpaired electrons in dπ orbitals. The diverse dπ orbitals occupation contributes to an elevated d-band center of Co ions, which accelerates oxygen reduction reaction and oxygen evolution reaction electrocatalytic kinetics of the Co-S@NC nanocrystal. Therefore, the Li-O2 batteries with Co-S@NC as cathode catalyst exhibit 300 cycles at the current density of 500 mA g-1 with a cut-off capacity of 1000 mAh g-1. Moreover, the ultrahigh discharge specific capacity of 34 587 mAh g-1 is obtained at a current density of 1000 mA g-1, corresponding to the energy density 949 Wh kg-1 of a prototype Li-O2 battery. The study on 3d orbital regulation of nanocrystals provides an innovative strategy for bifunctional electrocatalysts toward the practical application of metal-air batteries.

New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li-O2 Batteries.

Aprotic Li-O2 battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O2 - ) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O2 - disproportionation and its kinetics in both the discharge and charge processes. RB captures O2 - dimer and promotes their intramolecular charge transfer, and it decreases the energy barrier of the disproportionation reaction from 7.70 to 0.70 kcal mol-1 . This facilitates the discharge and charge processes and simultaneously mitigates O2 - and singlet oxygen related side reactions. These endow the Li-O2 battery with reduced discharge/charge voltage gap of 0.72 V and prolonged lifespan for over 230 cycles when coupled with RuO2 catalyst. This work highlights the vital role of superoxide disproportionation for Li-O2 battery.

Enhanced Redox Electrocatalysis in High-Entropy Perovskite Fluorides by Tailoring d-p Hybridization.

High-entropy catalysts featuring exceptional properties are, in no doubt, playing an increasingly significant role in aprotic lithium-oxygen batteries. Despite extensive effort devoted to tracing the origin of their unparalleled performance, the relationships between multiple active sites and reaction intermediates are still obscure. Here, enlightened by theoretical screening, we tailor a high-entropy perovskite fluoride (KCoMnNiMgZnF3-HEC) with various active sites to overcome the limitations of conventional catalysts in redox process. The entropy effect modulates the d-band center and d orbital occupancy of active centers, which optimizes the d-p hybridization between catalytic sites and key intermediates, enabling a moderate adsorption of LiO2 and thus reinforcing the reaction kinetics. As a result, the Li-O2 battery with KCoMnNiMgZnF3-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, preceding majority of traditional catalysts reported. These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.

Orbital Coupling of PbO7 Node in Single-Crystal Metal-Organic Framework Enhances Li-O2 Battery Electrocatalysis.

Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O2) batteries. Herein, we report the synthesis of a class of PbO7 nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO6 node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO7 node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO2 to Li2O2 and the oxidation of LiO2 to O2 for reducing the activation energy of the overall reaction. Consequently, Li-O2 batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles.

A "Trinity" Design of Li-O2 Battery Engaging the Slow-Release Capsule of Redox Mediators.

Nonaqueous Li-O2 battery (LOB) represents one of the promising next-gen energy storage solutions owing to its ultrahigh energy density but suffers from problems such as high charging overpotential, slow redox kinetics, Li anode corrosion, etc., calling for a systemic optimization of the battery configuration and structural components. Herein, an ingenious "trinity" design of LOB is initiated by implementing a hollowed cobalt metal organic framework (MOF) impregnating iodized polypyrrole simultaneously as the cathode catalyst, anode protection layer, and slow-release capsule of redox mediators, so as to systemically address issues of impeded mass transport and redox kinetics on the cathode, dendrite growth, and surface corrosion on the anode, as well as limited intermediate solubility in the low donor-number (DN) solvent. As a result of the systemic effort, the LOB constructed demonstrates an ultralow discharge/charge polarization of 0.2 V, prolonged cycle life of 1244 h and total discharge capacity of 28.41 mAh cm-2 . Mechanistic investigations attribute the superb LOB performance to the redox-mediated solution growth mechanism of crystalline Li2 O2 with both enhanced reaction kinetics and reversibility. This study offers a paradigm in designing smart materials to raise the performance bar of Li-O2 battery toward realistic applications.

B-N Co-Doped Biphenylene as a Metal-Free Cathode Catalyst for Li-O2 Batteries: a Computational Study.

Lithium-oxygen batteries (LOBs) meet the growing demand for long-distance transportation over electric vehicles but face challenges because of the lack of high-performance cathode catalysts. Herein, using density functional theory calculations, we report a unique graphene allotrope, biphenylene, of which the doping structures exhibit great potential as metal-free catalysts for LOBs. Our modeling results demonstrate that the biphenylene nanosheets retain metallic properties after B doping, N doping, or B-N co-doping. Compared with the pristine biphenylene, the catalytic activity of the doped biphenylene is greatly improved due to charge redistributions. Notably, the overpotentials of the B-N co-doped biphenylene are as low as 0.19 and 0.18 V for the discharge and charge processes, respectively. Based on the electronic structure and bonding analysis, we identify two factors, i. e., Li-O bond strength and *Li2 O2 adsorption energy, that can influence the Li-O2 electrochemical reactions. This study not only proposes a promising cathode catalyst but also provides insights into optimizing cathode catalysts for LOBs.

Tailoring the Growth and Morphology of Lithium Peroxide: Nickel Sulfide/Nickel Phosphate Nanotubes with Optimized Electronic Structure for Lithium-Oxygen Batteries.

Heterogeneous crystalline-amorphous structures, with tunable electronic structures and morphology, hold immense promise as catalysts for lithium-oxygen batteries (LOBs). Herein, a nanotube network constructed by crystalline nickel sulfide/amorphous nickel phosphate (NiS/NiPO) heterostructure is prepared on Ni foam through the sulfurization of the precursor generated hydrothermally. Used as cathodes, the NiS/NiPO nanotubes with optimized electronic structure can induce the deposition of the highly porous and interconnected structure of Li2 O2 with rich Li2 O2 -electrolyte interfaces. Abundant active sites can be created on NiS/NiPO through the charge redistribution for the uniform nucleation and growth of Li2 O2 . Moreover, nanotube networks endow cathodes with efficient transport channels and sufficient space for the accommodation of Li2 O2 . A high discharge capacity of 27 003.6 mAh g-1 and a low charge overpotential of 0.58 V at 1000 mAh g-1 can be achieved at 200 mA g-1 . This work provides valuable insight into the unique role of the electronic structure and morphology of catalysts in the formation mechanisms of Li2 O2 and the performances of LOBs.

Cascaded orbital-oriented hybridization of intermetallic Pd3Pb boosts electrocatalysis of Li-O2 battery.

Catalysts with a refined electronic structure are highly desirable for promoting the oxygen evolution reaction (OER) kinetics and reduce the charge overpotentials for lithium-oxygen (Li-O2) batteries. However, bridging the orbital interactions inside the catalyst with external orbital coupling between catalysts and intermediates for reinforcing OER catalytic activities remains a grand challenge. Herein, we report a cascaded orbital-oriented hybridization, namely alloying hybridization in intermetallic Pd3Pb followed by intermolecular orbital hybridization between low-energy Pd atom and reaction intermediates, for greatly enhancing the OER electrocatalytic activity in Li-O2 battery. The oriented orbital hybridization in two axes between Pb and Pd first lowers the d band energy level of Pd atoms in the intermetallic Pd3Pb; during the charging process, the low-lying 4dxz/yz and 4dz2 orbital of the Pd further hybridizes with 2π* and 5σ orbitals of lithium superoxide (LiO2) (key reaction intermediate), eventually leading to lower energy levels of antibonding and, thus, weakened orbital interaction toward LiO2. As a consequence, the cascaded orbital-oriented hybridization in intermetallic Pd3Pb considerably decreases the activation energy and accelerates the OER kinetics. The Pd3Pb-based Li-O2 batteries exhibit a low OER overpotential of 0.45 V and superior cycle stability of 175 cycles at a fixed capacity of 1,000 mAh g-1, which is among the best in the reported catalysts. The present work opens up a way for designing sophisticated Li-O2 batteries at the orbital level.

Solvation Structure with Enhanced Anionic Coordination for Stable Anodes in Lithium-Oxygen Batteries.

Li-O2 batteries have garnered much attention due to their high theoretical energy density. However, the irreversible lithium plating/stripping on the anode limits their performance, which has been paid little attention. Herein, a solvation-regulated strategy for stable lithium anodes in tetraethylene glycol dimethyl ether (G4) based electrolyte is attempted in Li-O2 batteries. Trifluoroacetate anions (TFA- ) with strong Li+ affinity are incorporated into the lithium bis(fluorosulfonyl)imide (LiTFSI)/G4 electrolyte to attenuate the Li+ -G4 interaction and form anion-dominant solvates. The bisalt electrolyte with 0.5 M LiTFA and 0.5 M LiTFSI mitigates G4 decomposition and induces an inorganic-rich solid electrolyte interphase (SEI). This contributes to decreased desolvation energy barrier from 58.20 to 46.31 kJ mol-1 , compared with 1.0 M LiTFSI/G4, for facile interfacial Li+ diffusion and high efficiency. It yields extended lifespan of 120 cycles in Li-O2 battery with a limited Li anode (7 mAh cm-2 ). This work gains comprehensive insights into rational electrolyte design for Li-O2 batteries.

Identifying the Role of Lewis-base Sites for the Chemistry in Lithium-Oxygen Batteries.

Lewis-base sites have been widely applied to regulate the properties of Lewis-acid sites in electrocatalysts for achieving a drastic technological leap of lithium-oxygen batteries (LOBs). Whereas, the direct role and underlying mechanism of Lewis-base in the chemistry for LOBs are still rarely elucidated. Herein, we comprehensively shed light on the pivotal mechanism of Lewis-base sites in promoting the electrocatalytic reaction processes of LOBs by constructing the metal-organic framework containing Lewis-base sites (named as UIO-66-NH2 ). The density functional theory (DFT) calculations demonstrate the Lewis-base sites can act as electron donors that boost the activation of O2 /Li2 O2 during the discharged-charged process, resulting in the accelerated reaction kinetics of LOBs. More importantly, the in situ Fourier transform infrared spectra and DFT calculations firstly demonstrate the Lewis-base sites can convert Li2 O2 growth mechanism from surface-adsorption growth to solvation-mediated growth due to the capture of Li+ by Lewis-base sites upon discharged process, which weakens the adsorption energy of UIO-66-NH2 towards LiO2 . As a proof of concept, LOB based on UIO-66-NH2 can achieve a high discharge specific capacity (12 661 mAh g-1 ), low discharged-charged overpotential (0.87 V) and long cycling life (169 cycles). This work reveals the direct role of Lewis-base sites, which can guide the design of electrocatalysts featuring Lewis-acid/base dual centers for LOBs.

Edge-Site-Free and Topological-Defect-Rich Carbon Cathode for High-Performance Lithium-Oxygen Batteries.

The rational design of a stable and catalytic carbon cathode is crucial for the development of rechargeable lithium-oxygen (LiO2 ) batteries. An edge-site-free and topological-defect-rich graphene-based material is proposed as a pure carbon cathode that drastically improves LiO2 battery performance, even in the absence of extra catalysts and mediators. The proposed graphene-based material is synthesized using the advanced template technique coupled with high-temperature annealing at 1800 °C. The material possesses an edge-site-free framework and mesoporosity, which is crucial to achieve excellent electrochemical stability and an ultra-large capacity (>6700 mAh g-1 ). Moreover, both experimental and theoretical structural characterization demonstrates the presence of a significant number of topological defects, which are non-hexagonal carbon rings in the graphene framework. In situ isotopic electrochemical mass spectrometry and theoretical calculations reveal the unique catalysis of topological defects in the formation of amorphous Li2 O2 , which may be decomposed at low potential (∼ 3.6 V versus Li/Li+ ) and leads to improved cycle performance. Furthermore, a flexible electrode sheet that excludes organic binders exhibits an extremely long lifetime of up to 307 cycles (>1535 h), in the absence of solid or soluble catalysts. These findings may be used to design robust carbon cathodes for LiO2 batteries.

Tailoring the p-Band Center of NS Pair for Accelerating High-Performance Lithium-Oxygen Battery.

The local coordination environment of catalytical moieties directly determines the performance of electrochemical energy storage and conversion devices, such as Li-O2 batteries (LOBs) cathode. However, understanding how the coordinative structure affects the performance, especially for non-metal system, is still insufficient. Herein, a strategy that introduces S-anion to tailor the electronic structure of nitrogen-carbon catalyst (SNC) is proposed to improve the LOBs performance. This study unveils that the introduced S-anion effectively manipulates the p-band center of pyridinic-N moiety, substantially reducing the battery overpotential by accelerating the generation and decomposition of intermediate products Li1-3 O4 . The lower adsorption energy of discharging product Li2 O2 on NS pair accounts for the long-term cyclic stability by exposing the high active area under operation condition. This work demonstrates an encouraging strategy to enhance LOBs performance by modulating the p-band center on non-metal active sites.

Unlock Restricted Capacity via OCe Hybridization for LiOxygen Batteries.

The aprotic Li-O2 battery (LOB) has the highest theoretical energy density of any rechargeable batteries. However, such system is largely restricted by the electrochemically formed lithium peroxide (Li2 O2 ) on the cathode surface, leading ultimately to low actual capacities and early cell death. In contrast to the surface-mediated growth of thin film with a thickness <50 nm, a non-crystalline Li2 O2 film with a thickness of >400 nm can be formed via an optimal OCe hybridized electronic structure. Specially, oxygen can react with dissolved cerium cations in the electrolyte via a cerium-oxygen reaction to form a high-energy faceted cerium oxide catalyst, which not only generates a great number of non-saturable active sites, but also erects electron transport bridges between the lattice O and adjacent Ce atoms. Such CeO orbital hybridization also forms a direct charge transfer channel from Ce-4f of CeO2 to O 2 2 - ${\rm{O}}_2^{2 - }$ -π* of Li2 O2 , eventually leading to submicron-thick Li2 O2 shells via a subsequent lithium-oxygen reaction. Relying on the above merits, this work unlocks the rechargeable capacities of LOB from restricted 1000 to unprecedented 10 000 mAh g-1 with good cyclabilities and reduced charge-discharge overpotentials.