O2 Batteries Research Articles

Recycling, Regeneration, and Reutilization of Cathode Materials of Spent LiNixCoyMn(1-x-y)O2 Batteries

Recycling, Regeneration, and Reutilization of Cathode Materials of Spent LiNixCoyMn(1-x-y)O2 Batteries

Improvement of electrochemical performance by surface modification of LiNi0.65Co0.15Mn0.2O2 cathode materials with SnO2

LiNi0.65Co0.15Mn0.2O2 batteries have attracted more and more attention due to their high energy density. However, LiNi0.65Co0.15Mn0.2O2 possesses adverse factors such as severe Li-Ni mixing and side reactions between active substance and electrolyte, which limits its electrochemical performance. Hence, we employed the SnO2 surface coating method to enhance its performance. SnO2 coating inhibits the direct contact between LiNi0.65Co0.15Mn0.2O2 and the electrolyte, which reduces the lithium-nickel mixing, enlarges the lithium layer spacing, and contributes to the improvement of the specific capacity of discharge and the cycling performance. The electrochemical results indicate the optimal SnO2-coated LiNi0.65Co0.15Mn0.2O2 show excellent cycling performance (85.0 % capacity retention for 100 cycles at 0.1 C) and multiplicative performance (124.1 mA·h·g−1 discharge specific capacity at 2 C). The paper highlights the SnO2 cladding technology which provides an excellent research idea to improve lithium-ion batteries.

Influence of laminated porous cathode structure on the performance and mass transfer of Li[sbnd]O2 batteries

The porous cathode is a crucial component of LiO2 batteries, and its porous structure significantly impacts the battery's performance. In this study, a stacked porous cathode was fabricated via roller pressing. The influence of the cathode structure on the battery performance and mass transfer characteristics were examined using experimental and simulation methods. The structural characteristics, electrochemical properties, and overall battery performance of the stacked porous cathode were analyzed. Furthermore, the effects of the cathode structure on mass transfer within the cathode and battery performance were explored through numerical simulation. The results indicate that when the mass ratio of CNTs to ACET on the diaphragm side is 5:1, the cathode exhibits optimal structural parameters, with an average pore size of 24 nm and a maximum pore volume of 0.85564 cm3/g. Concurrently, the battery demonstrates an exceptionally high area specific capacity of 30.35 mAh/cm2. Integrating the simulation findings, it was observed that adjusting the structural parameters of the cathode enhances material transfer efficiency, thereby improving battery performance.

Magnetic field and photon co-enhanced S-scheme MXene/In2S3/CoFe2O4 heterojunction for high-performance lithium-oxygen batteries

Under the spotlight for their potential to reduce over-potential, photo-assisted Li–O2 batteries still face a key challenge: the rapid recombination of photo-generated electron-hole pairs, which limits their efficiency. In this study, we address this limitation by designing a Li–O2 battery that integrates both photo and magnetic field assistance, using an S-scheme MXene/In2S3/CoFe2O4 heterojunction photocathode. This unique combination enhances visible light absorption and generates a strong built-in electric field, facilitating effective charge separation and boosting photocatalytic activity. During discharge, photo-generated electrons participate in the oxygen reduction reaction, while photo-induced holes contribute to the decomposition of discharge products during charging. Furthermore, the introduction of a magnetic field, confirmed through vibrating sample magnetometer, Mössbauer spectroscopy, X-ray absorption near edge structure, and cyclic voltammetry analyses, enhances electron-hole separation via Lorentz forces and spin–orbit coupling, accelerating the formation and decomposition of Li2O2. With this synergistic approach, the battery achieves a high specific capacity of 26500 mAh g−1, ultra-low oxygen reduction/evolution reaction over-potentials of 0.08 V/0.17 V, and a long cycle life of 2000 cycles with energy efficiency of 98.11 %. This work demonstrates the promising potential of combining photo and magnetic field effects to improve the electrochemical performance of Li–O2 batteries, opening new avenues for high-performance energy storage systems.

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

AbstractLi−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.

Partial‐Oxidation Enabling Homologous Ru/RuO2 Heterostructures With Proper d‐Dand Center as Efficient and Durable Cathode Catalysts for Ultralong Cycle Life in Li–O2 Batteries

AbstractThe sluggish cycle kinetics is one of the major obstacles to the commercial application of Li–O2 batteries (LOBs), despite their large theoretical energy density. Efficient and long‐term durable cathode catalysts are urgently desired to strengthen their cycle stability and rate performance. Density functional theory calculations reveal that Ru/RuO2 Mott–Schottky heterostructures can manipulate the adsorption capacities of intermediates by modulating the d‐band center and redistribute interfacial charges, enabling efficient redox kinetics, reducing overpotentials, and optimizing the growth pathway of discharge products. Herein, a wet impregnation approach followed by partial oxidization of Ru nanodots to construct homologous Ru/RuO2 heterostructures as advanced cathode catalysts for boosting the electrochemical activities of LOBs is employed. They exhibit superior electrochemical performance, including high discharge specific capacity (17 120 mAh g−1 at 200 mA g−1), small overpotential (0.96 V), and ultralong cycle lifetime of 1209 cycles (>2400 h) at 500 mA g−1. Over 1260‐h stable cycle in air atmosphere at 500 mA g−1 demonstrates the potential application prospects of the Ru/RuO2 heterostructures in Li‐air batteries. Multiple ex/in situ measurements and theoretical calculation are conducted to investigate the optimizing mechanism of electrochemical performances.

Conformal Li2O2 Growth and Decomposition Within 3D Lithiophilic Nanocages of Metal–Organic Frameworks for High‐Performance Li─O2 Batteries

AbstractLi─O2 batteries (LOBs) have the largest theoretical capacity among current batteries, but the irreversible growth and decomposition of Li2O2 products in positive electrodes cause dramatic degradation of their capacities over charging–discharging cycles. Herein, a metal–organic framework is reported with bipyridinic N linkers attached to graphene (bpyN‐MOF/g) as a positive electrode material to overcome the challenge. The bpyN‐MOF/g promotes conformal Li2O2 growth during discharging, while allowing Li2O2 decomposition at a low overpotential (0.487 V vs Li+/Li at 200 mA gc−1) during charging process, outperforming the Pt/C‐based electrode (0.857 V). Moreover, 3D‐tomography and density functional theory calculations consistently support the Li2O2 growth and decomposition mechanism inside bpyN‐MOF/g. Furthermore, bpyN‐MOF/g//Li LOBs achieve an exceptional discharge capacity (17 275 mAh gc−1 at 100 mA gc−1) and steady cycling for 270 cycles at 1000 mAh gc−1 under 2000 mA gc−1. Additionally, high gravimetric capacity at low mass loadings (0.27–0.44 mg cm−2) and stable cycle operation at a high areal current density (0.5 mA cm−2) open new opportunities for various practical applications.

Fly-ash derived crystalline Si (cSi) Improves the capacity and energy density of LiNi0.8Co0.1Mn0.1O2 battery: Synthesis and performance

For decades, graphite has been the key ingredient in the anode of Li-ion batteries (LIBs). The search for high-capacity anode materials for Li-ion batteries (LIBs) has led to increasing interest in silicon (Si) as a potential replacement for graphite. This study presents an innovative approach to synthesizing crystalline Si (cSi) from type C fly ash, addressing both the need for improved LIB anodes and the challenge of industrial waste management. Our novel process involves a stepwise method of extraction, gelation using various mineral acids (HCl, H2SO4, and HNO3), magnesiothermic reduction, and purification. X-ray diffraction and energy-dispersive X-ray spectroscopy confirmed the production of high-purity SiO2 and cSi. Notably, a cSi-doped graphite anode (5 % Si) paired with LiNi0.8Mn0.1Co0.1O2 (NMC811) in a cylindrical cell achieved a minimum specific discharge capacity of 388 mAh/ganode after formation, surpassing the theoretical capacity of graphite (372 mAh/g). This demonstrates that even a small amount of cSi can significantly enhance anode performance. Our scalable, simple, and economical process offers a dual benefit: improving battery characteristics while providing an efficient method for fly ash waste utilization. This approach paves the way for sustainable production of high-performance LIB anodes while addressing critical waste management challenges.

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

HighlightsStrategic materials design of polyrotaxane-based electrolytes was suggested by aligning the ion conduction pathways and dispersing hydrophobic chains for solid-state Li–O2 batteries.Owing to intentional design, solid-state Li–O2 battery resulted in stable potential over 300 cycles at 25 °C.

Engineering of MnTe/MnO Heterostructures with Interfacial Electric Field Modulation for Efficient and Durable Li–O2 Batteries

AbstractDesign and synthesis of highly active and robust bifunctional cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are of vital significance for practical applications of lithium–oxygen (Li–O2) batteries. Herein, a built‐in electric field (BIEF) strategy is reported to fabricate MnTe/MnO heterostructures with a large work function difference (ΔΦ) as a bifunctional cathode catalyst in Li–O2 batteries. The MnTe/MnO heterostructures with nanosheets and microporous structures result in an abundance of exposed active sites and facilitate mass transfer. More importantly, the heterogeneous MnTe/MnO nano‐interface region provides a BIEF that can trigger interfacial charge redistribution, fine‐tune the adsorption energy of oxygen intermediates, and alter the morphology of discharge products to accelerate ORR/OER kinetics. Impressively, the fabricated Li–O2 batteries with MnTe/MnO cathode showcases exhibit excellent electrochemical performances, including low charging overpotential, a high specific capacity of 11930 mA h g−1, and good cycle stability over 350 cycles even with a fixed specific capacity of 500 mA h g−1 at a current density of 500 mA g−1. This work provides an avenue for the rational design of high performance heterostructure electrocatalysts toward practical applications for rechargeable Li–O2 batteries.

Tri-anion solvation structure electrolyte improves the electrochemical performance of Li||LiNi0.8Co0.1Mn0.1O2 batteries.

Li||LiNi0.8Co0.1Mn0.1O2 batteries,which consist of lithiummetal anode (LMA) matchedwith NCM811 cathode, have an energy density more than twice that of lithium ion battery (LIB).However, the unstable electrode/electrolyte interface still hinders its practical application.Ether electrolytes show promise in improving the stability of LMA and NCM811 cathodes.However, a robust and stableelectrode/electrolyte interface in Li||NCM811 batteries cannot be easily and efficiently achieved with most of the ether electrolytes reported in present studies. Herein, we present a straightforwardand efficient tri-anion synergistic strategy to overcome this bottleneck. The addition of ClO4- and NO3- anions to LiFSI-based ether electrolytes forms a unique solvation structure with tri-anion (FSI-/ClO4-/NO3-) participation(LB511).This structure not only enhances the electrochemical window of the ether electrolytes but also achieves a stable Li||NCM811batteries interface.The interaction between electrode and electrolyte is suppressed andan inorganic-rich (LiF/Li3N/LiCl) SEI/CEI layer is formed. Meanwhile, the coordination structure in the LB511 electrolyte increases the overpotential for Li deposition, resulting in a uniform and dense layer of deposition.Therefore,the Li||Cu cells using the LB511 electrolytehave an average CE of 99.6%.TheLi||NCM811 batteries was cycled stably for 250 cycles with a capacity retention of 81% in the LB511 electrolyte (N/P = 2.5, 0.5 C).

Stable Lithium Oxygen Batteries Enabled by Solvent‐diluent Interaction in N,N‐dimethylacetamide‐based Electrolytes

AbstractIn the pursuit of next‐generation ultrahigh‐energy‐density Li−O2 batteries, it is imperative to develop an electrolyte with stability against the strong oxidation environments. N,N‐dimethylacetamide (DMA) is a recognized solvent known for its robust resistance to the highly reactive reduced oxygen species, yet its application in Li−O2 batteries has been constrained due to its poor compatibility with the Li metal anode. In this study, a rationally selected hydrofluoroether diluent, methyl nonafluorobutyl ether (M3), has been introduced into the DMA‐based electrolyte to construct a localized high concentration electrolyte. The stable −CH3 and C−F bonds within the M3 structure could not only augment the fundamental properties of the electrolyte but also fortify its resilience against attacks from O2− and 1O2. Additionally, the strong electron‐withdrawing groups (−F) presented in the M3 diluent could facilitate coordination with the electron‐donating groups (−CH3) in the DMA solvent. This intermolecular interaction promotes more alignments of Li+‐anions with a small amount of M3 addition, leading to the construction of an anion‐derived inorganic‐rich SEI that enhances the stability of the Li anode. As a result, the Li−O2 batteries with the DMA/M3 electrolyte exhibit superior cycling performance at both 30 °C (359th) and −10 °C (120th).

Rationalizing the catalytic surface area of oxygen vacancy‐enriched layered perovskite LaSrCrO4 nanowires on oxygen electrocatalyst for enhanced performance of Li–O2 batteries

AbstractEfficient electrocatalysis at the cathode is crucial to addressing the limited stability and low rate capability of Li−O2 batteries. This study examines the kinetic behavior of Li−O2 batteries utilizing layered perovskite LaSrCrO4 nanowires (NWs) composed of lower oxidation states. Layered perovskite LaSrCrO4 NWs exhibited improved rate capability over a wide range of current densities and longer cycle life in Li−O2 batteries than V‐based layered perovskite (LaSrVO4) and simple perovskite (La0.8Sr0.2CrO3) NWs. X‐ray photoelectron spectroscopy and electrochemical surface area analyses showed that the observed performance variations primarily stemmed from active sites such as oxygen vacancies. In situ Raman analysis showed that these active sites significantly modulate the kinetics of oxygen reduction and evolution, which are related to LiO2 intermediate adsorption. Electrochemical impedance spectroscopy showed that the active sites in layered perovskite LaSrCrO4 NWs contributed to their high charge transfer capability and reduced polarization. This study presents an appealing method for the precise fabrication and analysis of Cr‐based layered perovskites, aimed at achieving highly efficient and stable bifunctional oxygen electrocatalysis.

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

AbstractThe 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.

A novel hybrid sodium ion capacitor based on Na [Ni0.60Mn0.35Co0.05] O2 battery type cathode and presodiated D-Ti3C2Tx pseudocapacitive anode

The combination of the high-power density of supercapacitors and the high energy density of batteries makes hybrid sodium-ion capacitors (HSICs) a promising device. HSICs can provide better performance characteristics by harnessing both ion adsorption/desorption in the capacitor-type electrode and sodium-ion intercalation in the battery-type electrode. Here, the synthesis of MXene (Ti3C2Tx), a two-dimensional (2D) carbide and nitride is reported. Delaminated MXene (D-Ti3C2Tx) is a promising candidate for anode material in HSIC due to its large surface area (∼ 42 m2/g) and good electronic conductivity. Electrochemical study indicates that D-Ti3C2Tx anode exhibits a high discharge capacity of ∼213 mAh/g at a current rate of 20 mA/g. Further the presodiated D-Ti3C2Tx anode is paired with Na [Ni0.60Mn0.35Co0.05] O2 (P2-NMC) cathode to obtain the configuration of HSIC. The HSIC exhibits good specific capacitance of ∼187 F/g and specific discharge capacity of ∼110 mAh/g at a current density of 10 mA/g, according to the electrochemical analysis. A notable improvement in specific energy density (∼ 256 Wh/kg) and specific power density (∼579 W/kg) is also demonstrated by the HSIC. With P2-NMC being used as the cathode material rather than traditional activated carbon, there has been a rise in specific energy density.

Atomic Ni-catalyzed cathode and stabilized Li metal anode for high-performance Li–O2 batteries

The Li–O2 battery (LOB) has attracted growing interest, including for its great potential in next-generation energy storage systems due to its extremely high theoretical specific capacity. However, a series of challenges have seriously hindered LOB development, such as sluggish kinetics during the oxygen reduction and oxygen evolution reactions (ORR/OER) at the cathode, the formation of lithium dendrites, and undesirable corrosion at the lithium metal anode. Herein, we propose a strategy based on the ultra-low loading of atomic Ni catalysts to simultaneously boost the ORR/OER at the cathode while stabilizing the Li metal anode. The resultant LOB delivers a superior discharge capacity (>16000 mA h g−1), excellent long-term cycling stability (>200 cycles), and enhanced high rate capability (>300 cycles @ 500 mA g−1). The working mechanisms of these atomic Ni catalysts are revealed through carefully designed in situ experiments and theoretical calculations. This work provides a novel research paradigm for designing high-performance LOBs that are usable in practical applications.

A novel multifunctional electrolyte system for high performance Li-ion batteries

Lithium-ion batteries have advantages such as environmental protection and sustainable use, but the widespread application of lithium-ion battery-powered vehicles is limited by the inability to quickly charge and extreme ambient temperatures, and reasonable design of electrolyte components can effectively solve these problems. Here, a novel fluoroethylene carbonate (FEC)/ethyl acetate (EA) based electrolyte containing lithium difluorophosphate (LiPO2F2, 2 wt%) and lithium bis(fluorosulfonyl)imide salt (LiFSI, 1.0 M) is first reported. The electrolyte containing these components has the characteristics of low freezing point, low viscosity and high ionic conductivity. Especially, due to the preferential decomposition of FEC, LiFSI and LiPO2F2, uniform multiphase inorganic LiF and Li3N species are formed on the electrode surface with enhanced robustness and ion transfer kinetics. So, the graphite||LiNi0.5Co0.2Mn0.3O2&LiMn2O4 (Gr||LMO&NCM523) batteries in the designed electrolyte maintain high capacity and coulombic efficiency (100 %) after 200 times at 1C charge and discharge current density at 25 °C and 45 °C. At −20 °C, the batteries have a coulombic efficiency of 50 % and capacity of 38.0 mA h g−1 after 200 charging and discharging cycles, showing excellent low-temperature fast dynamics. Our work supplies an efficient way to accelerate the engineering application of Li-ion batteries.

Pulse Charge Suppressing Dendrite Growth at Low Temperature by Rapidly Replenishing Lithium Ion on Anode Surface.

Dendrite growth of lithium (Li) metal anodes is considered as one of the most tough issues for Li metal batteries with a theoretically high energy density. This is attributed to the rapid exhaustion of Li ions at the electrode/electrolyte interface, which is even worse at low temperatures with poor diffusion kinetics of Li ions. Here, pulse charge with intermittent rest time during battery charging is proposed to handle the dendrite growth issue of Li metal anodes at low temperatures. The depleted Li ions near the interfaces can be rapidly replenished during the rest time, thus effectively suppressing the dendrites growth. Further investigation found that the large dendrites can be suppressed at the Li ion nucleation stage. The equivalent lifespan considering the rest time is proposed. At -10 °C, the lifespan of Li||Li batteries cycled under 3 mA cm-2 and 1 mAh cm-2 is increased from 24 h to equivalent 64 h. Li||LiNi0.5Co0.2Mn0.3O2 batteries with 80% capacity retention can be stably operated from 39 cycles to 56 cycles. This design presents an efficient and convenient strategy to regulate the deposition behaviors of Li metal anodes with a dendrite-free morphology.

A multi-step discharge/charge model of Li[sbnd]O2 batteries coupled with electrolyte decomposition and carbon electrode corrosion reactions

Electrolyte decomposition and electrode corrosion stand as two primary side reactions in lithium‑oxygen (LiO2) batteries during their discharge/charge cycles. In this work, a comprehensive LiO2 battery model combining multi-step lithium peroxide (Li2O2) formation, electrolyte decomposition, and electrode corrosion is proposed. Based on this model, the deposition behaviors and cycling performance of the LiO2 battery under deep discharge/charge cycles are investigated. The stop of discharge is mainly ascribed to the loss of active surface area for the battery using tetraethylene glycol dimethyl ether (TEGDME) electrolyte, while both O2 transport limitation and active surface area loss lead to the discharge termination for battery using dimethyl sulfoxide (DMSO) electrolyte. The incomplete decomposition of Li2O2 and lithium carbonate (Li2CO3) clogs electrode pores, leading to a continuous decline in the discharge capacity of the LiO2 battery. For the TEGDME-based battery, the undecomposed Li2CO3 gradually dominates the deposition with cycles, wherein electrode corrosion becomes the primary source of the undecomposed Li2CO3 after 3 cycles. For the DMSO-based battery, undecomposed Li2O2 is always a dominant trigger for battery discharge capacity degradation, although electrode corrosion remains a key contributor to Li2CO3 generation. Despite the DMSO-based battery exhibiting lower rates of electrolyte decomposition and electrode corrosion, it demonstrates poorer cyclic performance than the TEGDME-based battery due to the generation of more toroidal Li2O2. Moreover, when the charging cut-off voltage is reduced to 4.2 V, discharge capacity diminishes more rapidly due to the increased accumulation of undecomposed Li2O2, despite suppressed Li2CO3 deposition. Finally, the results confirm that thick electrodes lead to deteriorating cycling performance, stemming from increased discharge/charge overpotential and extended discharge/charge times, thus intensifying the side reactions.

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.