MXene-supported Ni-Co bimetallic MOF 2D lamellar membrane for enhanced electrochemical oxygen reactions and Li-O 2 battery

MXene-supported Ni-Co bimetallic MOF 2D lamellar membrane for enhanced electrochemical oxygen reactions and Li-O 2 battery | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article MXene-supported Ni-Co bimetallic MOF 2D lamellar membrane for enhanced electrochemical oxygen reactions and Li-O 2 battery Liming Liu, Hongxia Lian, Heming Deng, Weixin Zhang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6017278/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Apr, 2025 Read the published version in Scientific Reports → Version 1 posted 12 You are reading this latest preprint version Abstract Lithium-oxygen (Li-O2) battery is a revolutionary high-performance battery technology due to its exceptionally high theoretical energy density, but challenges associated with the cathode material have hindered its further advancement. Here, an in-situ synthesis strategy was adopted to load a bimetallic Ni-Co metal-organic framework (MOF) onto MXene (Ti3C2) layer, and subsequently prepared a free-standing and flexible Ni/Co-MOF@Ti3C2 hybrid membrane through a layer-by-layer self-assembly method for efficient oxygen reduction reactions (ORR) and as a cathode for Li-O2 batteries. The Ni/Co-MOF@Ti3C2 hybrid membrane integrates the high conductivity and unique two-dimensional layered structure of MXene with the bimetallic active sites of Ni-Co MOF, exhibiting remarkable ORR catalytic activity. The structural characteristics of Ni/Co-MOF@Ti3C2 hybrid membrane provide smoother expansion pathways for Li+ or O2, effectively promoting the deposition and decomposition of Li2O2, thereby overcoming the inherent limitations of traditional slurry-based cathode preparation methods for Li-O2 batteries. Experimental results indicate that Li-O2 batteries utilizing the Ni/Co-MOF@Ti3C2 hybrid membrane as the cathode achieve an ultra-high capacity of 36125 mAh/g at a current density of 1000 mA/g, while demonstrating excellent cycle stability and outstanding rate performance. The promising results offers novel insights into the innovative design of air cathodes for metal-air batteries. Physical sciences/Energy science and technology Physical sciences/Engineering Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction The enhancement of power battery performance has become pivotal in driving advancements in electric vehicles, energy storage systems, and other related fields with the global community's sustained focus and investment in renewable energy technologies. 1-3 In recent years, the exploration of next-generation high-energy battery technologies has emerged as a central focus as the lithium-ion battery market has gradually reached saturation. 4-5 Among these, lithium-oxygen (Li-O 2 ) batteries have garnered significant attention due to their exceptional theoretical gravimetric energy density. 6-8 The working principle of Li-O 2 batteries is based on redox reactions occurring in the cathode region, oxygen reacts with lithium ions under the catalysis of a catalyst to form lithium peroxide (Li 2 O 2 ) during discharge, known as the oxygen reduction reaction (ORR). Conversely, Li 2 O 2 decomposes into lithium ions and oxygen during charging, referred to as the oxygen evolution reaction (OER). However, the kinetic processes of ORR and OER on the cathode are relatively slow, and the accumulation of Li 2 O 2 severely limits key performance indicators of Li-O 2 batteries, such as capacity, rate capability, and charge-discharge polarization. 9-12 Furthermore, the insulating and insoluble nature of Li 2 O 2 leads to its deposition within electrode pores after prolonged discharge, further hindering oxygen diffusion, increasing electrode polarization and impedance, and thereby shortening the battery's cycle life. 13,14 The key to overcoming these challenges lies in the innovation and optimization of air electrode catalysts. Traditional air-electrode catalyst materials include carbon materials, 15,16 precious metals and alloys, 17,18 and metal oxides. 19,20 But these materials possess significant drawbacks, such as instability, high cost, and limited catalytic activity. In recent years, two-dimensional (2D) layered materials have garnered considerable attention due to their exceptional physical and chemical properties. 21-23 As an emerging 2D material, MXene features a symmetric hexagonal lattice and metallic properties, exhibiting excellent conductivity, tunable bandgap, high carrier mobility, good mechanical properties, and thermal conductivity. 24,25 These characteristics make MXene an ideal choice for a new generation of energy storage and energy conversion materials. MXene serves as a cathode material in Li-O 2 batteries, with its high surface area-to-volume ratio providing a large reaction interface. 26-28 The 2D channels enable high and controllable ion conductivity and oxygen diffusion, and the interlayer spacing can be adjusted to accelerate the rapid and reversible transport of lithium ions. Additionally, MXene is easy to process and can be composited with other materials to further enhance the material's gravimetric energy density. However, MXene faces severe self-stacking issues during membrane formation similar to other 2D materials, the strong van der Waals forces and hydrogen bonding interactions between adjacent MXene layers cause single-component MXene nanosheets to easily restack, 29,30 significantly impeding ion transport channels and drastically reducing their specific surface area and available active sites. As material requirements continue to increase, single materials often fail to meet reaction demands. Therefore, composites of different materials can often produce a "1+1>2" effect, but it is crucial to consider the characteristics of the two materials to ensure they complement each other. Metal-organic frameworks (MOFs) are porous network materials with large specific surface areas, unique porosity, and ease of modification formed through the coordination self-assembly of metal ions and organic ligands. 31,32 MOFs possess different types of catalytic sites, providing the inherent advantages of homogeneous and heterogeneous catalysts. 33 Based on our group's previous work and understanding of the oxygen cathode catalysts and their structures and functions in Li-O 2 batteries, 33 a bimetallic Ni, Co-based MOF material (Ni/Co-MOF, as shown in Fig. 1) is introduced here. Through the in-situ self-assembly properties of MOFs, Ni/Co-MOF can be loaded onto MXene layers, effectively preventing the self-restacking of MXene layers, significantly increasing the interlayer spacing of MXene, and providing faster Li + and O 2 diffusion channels. On the other hand, as bimetallic centers, Ni and Co introduce more active sites, enhancing catalytic performance and promoting the rapid and reversible formation and decomposition of Li 2 O 2 . In this work, Ni/Co-MOF particles were loaded onto the surface of MXene sheets through the in-situ self-assembly properties of MOFs, and a free-standing flexible Ni/Co-MOF@MXene hybrid membrane was prepared based on a layer-by-layer stacking self-assembly strategy. The resulting Ni/Co-MOF@MXene effectively alleviates the self-stacking problem of MXene and exhibits excellent ORR performance and a high specific surface area (232 m 2 /g). Li-O 2 batteries assembled based on the Ni/Co-MOF@MXene as oxygen cathode exhibit ultra-high capacity (36125 mAh/g at 1000 mA/g) and excellent cycle stability (271 cycles with a limited capacity of 1000 mAh/g at a current density of 1000 mA/g), along with superior rate performance. Furthermore, the capacity and cycle performance of the assembled Li-O 2 batteries can be regulated by controlling the thickness of the Co-MOF/MXene membrane. The key to this method lies in the development of a novel cathode structure that effectively utilizes the in-situ loading of bimetallic Ni/Co-MOF with abundant active sites and special structures onto MXene nanosheets, thereby increasing the interlayer spacing of the MXene layered structure and inhibiting the top-down restacking of MXene nanosheets. The research ideas and preparation methods in this study can also be extended to the preparation of other catalysts and batteries, providing valuable insights for the design of efficient catalysts and the development of novel battery structures. Materials and methods Materials All chemicals were purchased directly and utilized without further purification. Ti 3 AlC 2 powder (98%), N,N-dimethylformamide (DMF), ethanol (98%,), and polypropylene membrane were form Aladdin. LiCl (99%), LiF (99%), Ni(NO 3 ) 2 ·6H 2 O, Co(NO 3 ) 2 ·6H 2 O (both 99%) and terephthalic acid (TPA, 98%) were from Alfa Aesar. HCl was form Beijing Chemical Plant. Synthesis of 2D Ti 3 C 2 Layer The preparation of layer-shaped Ti 3 C 2 is achieved through etching and exfoliation of Ti 3 AlC 2 powder using HCl/LiF. 35 Specifically, 20 mL of HCl solution is mixed with 1.56 g of LiF in a polytetrafluoroethylene beaker., 1 g of Ti 3 AlC 2 powder is added in portions under continuous stirring. The entire beaker is then placed in a water bath set at 405 K, and stirring for 48 h to ensure thorough completion of the etching and exfoliation reaction. Centrifugation is performed three times at 8000 rpm using 1M HCl solution and 1M LiCl solution sequentially to purify the product. Multiple centrifugation washes with deionized water are conducted until the pH approaches neutrality (approximately 6). A dark green Ti 3 C 2 suspension can be observed in the centrifuge tube. The supernatant suspension is repeatedly collected and subjected to ultrasonic treatment for 12 h to exfoliate and better disperse the Ti 3 C 2 layers within the suspension, ultimately yielding a high-quality dispersion of Ti 3 C 2 layers. Synthesis of Ni/Co-MOF@MXene Take 20 mL of the prepared Ti 3 C 2 layer dispersion and add 20 mL anhydrous ethanol, 20 mL of DMF. Subject the mixture to ultrasonic treatment to ensure homogeneous blending. Sequentially add 165 mg Ni(NO 3 ) 2 ·6H 2 O ,165 mg of Co(NO 3 ) 2 ·6H 2 O salts and 0.2 g TPA to fully dissolve under stirring. Transfer the resulting mixture to a reactor and heat it to 423 K for a reaction period of 18 h. After naturally cooling to room temperature, centrifuge to collect the solid product, and wash the solid product three times with DMF to remove adherent impurities and unreacted substances, followed by washes with anhydrous ethanol. Place the washed solid in a vacuum oven for drying for 24 h to obtain the Ni/Co-MOF@MXene powder. As experimental comparisons, two additional materials were prepared: Ni/Co-MOF without the addition of Ti 3 C 2 nanosheet dispersion and Co-MOF@MXene without the addition of Ni(NO 3 ) 2 ·6H 2 O. Preparation of Free-standing Ni/Co-MOF@MXene Hybrid Membrane The flexible, self-supporting Ni/Co-MOF@MXene hybrid membrane was using a hierarchical self-assembly technique. Ni/Co-MOF@Ti 3 C 2 powder is added to an appropriate amount of water and subjected to ultrasonic treatment for 2 h to ensure a homogeneous dispersion. As illustrated in Fig. S1, S2 and S3, a vacuum filtration setup is utilized for the preparation of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane. A hydrophilic polypropylene membrane is placed inside the filtration setup, and the prepared Ni/Co-MOF@Ti 3 C 2 dispersion is poured into a sand-core funnel. The vacuum pump is activated to begin the suction filtration process. After completion of the filtration, the system is allowed to sit for a period to facilitate membrane stabilization and curing. The Ni/Co-MOF@Ti 3 C 2 membrane is then removed from the polypropylene support membrane and dried under vacuum conditions, yielding a flexible, self-supporting Ni/Co-MOF@Ti 3 C 2 hybrid membrane. Materials Characterizations Structural analyses of the MOF, Ti 3 C 2 , and Ni/Co-MOF@Ti 3 C 2 hybrid membranes were conducted using an X-ray diffractometer (XRD) equipped with a Cu Kα radiation source (model Bruker D8 ADVANCE, the 2θ angle range was set from 5° to 50° with a step size of 0.05°). N 2 adsorption-desorption isotherms of the materials were measured on an Autosorb-iQ-MP automated gas sorption analyzer from Quantachrome Instruments. Prior to the adsorption and desorption tests, the samples were degassed at 423 K for 12 h. Transmission electron microscopy (TEM) using a Tecnai G2 20 S-TWIN (FEI Company) was employed to observe the morphology and size of the two-dimensional nanosheets, as well as the interlayer spacing of the membranes. Additionally, scanning electron microscopy (SEM) with a JSM-7800F (JEPL Ltd., Japan) was used to analyze the morphology of the nanosheets and membranes. To obtain clear SEM images, the samples were brittle-fractured in liquid nitrogen before observation. X-ray photoelectron spectroscopy (XPS) measurements were performed using an ESCALAB 250 instrument (Thermo VG, USA). Assembly and Performance Testing of Lithium-O 2 Batteries A modified CR2025 coin cell (with a drilled cathode case) was employed to assemble a lithium-oxygen battery in this study, The separator (Whatman) was pre-dried in a vacuum oven at 423 K for 12 h. The prepared Ni/Co-MOF@Ti 3 C 2 hybrid membrane cathode, lithium metal anode, and electrolyte composed of 1M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in triethylene glycol dimethyl ether (TEGDME) were assembled into the battery inside an Ar-filled glovebox. After sealing, the battery was removed from the glovebox and filled with pure O 2 . After a resting period of 3 h, electrochemical testing was conducted. Battery performance testing was carried out using the CT2001A battery testing system produced by Wuhan LAND Electronics Co., Ltd. The charge-discharge voltage range was set between 2.0 and 4.5 V (vs. Li/Li + ), with a current density of 1000 mA/g. During the cycling performance test, the specific charge-discharge capacity was limited to 1000 mAh/g, and the current density was maintained at 1000 mA/g. Density Functional Theory (DFT) Calculations DFT calculations were conducted in this study using the Vienna Ab initio Simulation Package (VASP) to delve into the electronic structure characteristics and catalytic mechanisms of Ni/Co-MOF/Ti 3 C 2 composites as cathodes in Li-O 2 batteries. The Perdew-Burke-Ernzerhof (PBE) exchange functional within the Generalized Gradient Approximation (GGA) framework was chosen to accurately simulate the interactions between electrons, based on its proven accuracy and reliability across various material systems. 36-38 Notably, the spin-polarization effect was neglected in the calculations due to its negligible impact on the total energy of the system. In terms of computational parameters, a cutoff energy of 420 eV was set for the plane-wave basis, and the Monkhorst-Pack method was employed for Brillouin zone integration with a 5×5×1 k-point grid to ensure precision. 39 During geometric structure optimization, stringent convergence criteria were established, requiring the energy of all atoms to converge to 10 -4 eV and forces to converge to 0.02 eV/Å or tighter, thereby ensuring the stability of the obtained structures. The Heyd-Scuseria-Ernzerhof (HSE) hybrid density functional method was further adopted to provide a more detailed depiction of the electronic structure and calculate the Density of States (DOS), implemented through the Quantum ESPRESSO software package. Additionally, the Bader charge analysis method was utilized to delve into the charge transfer mechanisms within the composite material, which is crucial for understanding electron flow and the role of active sites during catalysis. Results and Discussion Design Strategy for the Li-O 2 Battery Cathode Based on Ni/Co-MOF@MXene Membrane The preparation of the Ni/Co-MOF@MXene hybrid membrane and the strategy for fabricating the Ni/Co-MOF@MXene hybrid membrane-based Li-O2 battery cathode are shown in Fig. 1. In Li-O 2 batteries, the performance of the air cathode plays a crucial role in the rates of the ORR and OER, as well as the effective deposition and decomposition of reaction products. Constructing an air cathode structure that not only ensures rapid O 2 and lithium-ion transport but also provides sufficient space to accommodate a large amount of discharge products has become the focus of current research. Traditional methods typically rely on coating a slurry containing binders and conductive agents onto carbon paper or carbon cloth to form the air cathode, which has several limitations, such as the surface of the air cathode being easily blocked by the binder, that hinders oxygen transport; uneven dispersion of active materials, which affects catalytic efficiency; and settlement of active materials, leading to a decline in battery performance over time. To address these issues, this work proposes an innovative solution: preparing a binder-free, free-standing air cathode (Fig. S4). This cathode adopts a layered stacking structure that not only exhibits excellent ORR/OER catalytic activity but also significantly improves the diffusion channels for O 2 and Li + through carefully designed stacking, while providing maximum space to accommodate the accumulation of discharge products. This effectively alleviates the problem of battery performance degradation caused by the accumulation of reaction products. In terms of material selection, we introduced bimetallic Ni/Co-MOF as the active material and compounded it with MXene to form the Ni/Co-MOF@MXene structure. MXene provides robust structural support for the air cathode as a two-dimensional material with high conductivity and good mechanical properties. The introduction of Ni/Co-MOF further enhances catalytic performance through its abundant pore structure and bimetallic active sites. More importantly, the in-situ loading of Ni/Co-MOF not only increases the interlayer space of MXene, facilitating rapid transport of oxygen and Li + , but also introduces additional active sites, improving the efficiency of catalytic reactions. At the same time, this free-standing stacking structure allows the active materials to be more uniformly distributed within the cathode, avoiding issues of settlement and blockage. Materials Characterization The overall morphology and microstructure of Ni/Co-MOF@Ti3C2 nanosheets were observed and analyzed using SEM, TEM, AFM, and EDS characterization techniques. Fig. S5 displays the SEM images of Ti 3 C 2 samples prepared via the HF/LiF method. The Al element in Ti 3 AlC 2 was successfully removed After HF etching, forming Ti 3 C 2 of approximately 1 μm with a loosely stacked and folded structure, which provides an ideal substrate for the in-situ loading of Ni/Co-MOF. It is evident that a uniform layer of Ni/Co-MOF particles has been successfully loaded onto the surface of Ti 3 C 2 layer by observing Ni/Co-MOF@Ti 3 C 2 nanosheets at different angles (Fig. 2a and b). Since Ni/Co-MOF is loaded onto Ti3C2 nanosheets through in-situ growth, the binding between them is tight and uniformly distributed, which contributes to enhancing the overall performance and stability of the material. The TEM image (Fig. 2c) reveals the lattice fringes of Ni/Co-MOF and the layered structure of Ti 3 C 2 , further confirming the successful loading of Ni/Co-MOF onto Ti 3 C 2 nanosheets and showcasing their good crystallinity and layered structure. Fig. 2d presents the AFM image of Ni/Co-MOF@Ti 3 C 2 nanosheets, indicating a thickness of 2 μm, which facilitates the diffusion and transport of O 2 in Li-O 2 batteries while ensuring the mechanical strength and stability of the material. Fig. 2e and 2f show the cross-sectional and top-view SEM images of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane, respectively. The top-view image reveals that the surface of the hybrid membrane is composed of nanosheets of different sizes stacked together, forming a microstructure with folds and tight connections. This structure helps increase the specific surface area and active sites of the material, enhancing the electrochemical performance of Li-O 2 batteries. The cross-sectional image clearly shows the well-arranged layered structure (as shown in Fig. 2g), further proving the uniform distribution and good stacking of Ni/Co-MOF@Ti 3 C 2 nanosheets within the membrane, which facilitates the insertion and extraction of lithium ions in Li-O 2 batteries, improving the charge-discharge performance and cycle stability of the battery. Fig. 2h and 2i display the EDS mappings of Co and Ni elements in the cross-sectional image of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane. The mapping results indicate that Ni/Co-MOF is uniformly distributed within the hybrid membrane, facilitating the full exposure of bimetallic active sites. The XRD pattern of Ni/Co-MOF (Fig. 3a) aligns well with the previously reported structure, 34 which exhibiting intense and sharp characteristic peaks, indicative of the high crystallinity of Ni/Co-MOF. Pure Ti 2 C 3 displays a strong diffraction peak at 6.7°, corresponding to an interlayer spacing of 1.32 nm characteristic of its typical structure. Notably, the XRD pattern of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane not only retains the crystalline structure features of Ni/Co-MOF intact but also clearly shows the characteristic peaks of Ti 2 C 3 , confirming the in-situ loading and combination of the two components. Fig. S6 further presents the small-angle XRD patterns of Ni/Co-MOF@Ti 3 C 2 and Ti 3 C 2 . Analysis reveals that upon successful loading of Ni/Co-MOF, the interlayer spacing of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane significantly increases to 1.49 nm, much larger than the 1.32 nm of the pure Ti2C3membrane. This expansion of interlayer spacing is crucial for the diffusion and transport of O 2 and Li + during charging-discharging processes, enhancing the accessibility of electrolyte ions to the Ti 2 C 3 nanosheets and laying the foundation for optimized electrochemical performance. Comparative tests were conducted on the N 2 adsorption-desorption curves of pure Ti 2 C 3 membrane and Ni/Co-MOF@Ti 3 C 2 hybrid membrane, with the specific surface areas calculated as shown in Fig. 3b. The specific surface area of the pure Ti 2 C 3 membrane is 97 m²/g, while that of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane is as high as 232 m²/g. This substantial increase is primarily attributed to the large specific surface area of Ni/Co-MOF itself (1372 m²/g, Fig. S7) and the effective inhibition of self-stacking of Ti 2 C 3 by Ni/Co-MOF, which increases the distance between Ti 2 C 3 lamellae. As the air cathode in Li-O 2 batteries, the high-specific-surface-area Ni/Co-MOF@Ti 3 C 2 hybrid membrane can provide more channels for the diffusion of Li + and O 2 , increasing the reaction interface and the number of active sites while promoting the accumulation and decomposition of the reaction product Li 2 O 2 , thereby significantly enhancing the electrochemical performance of Li-O 2 batteries. Additionally, the N 2 adsorption-desorption curve of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane exhibits a type IV isotherm accompanied by an H3 hysteresis loop, indicating the presence of slit-like pores in the hybrid membrane, which further confirms the effective regulation of the interlayer spacing of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane by the incorporation of Ni/Co-MOF. Fig. S8 demonstrates the difference in O 2 adsorption performance between Ti 3 C 2 and Ni/Co-MOF@Ti 3 C 2 , where the O 2 adsorption capacity of pristine Ti 3 C 2 is 1.42%, while Ni/Co-MOF@Ti 3 C 2 exhibits an enhanced O 2 adsorption capacity of 2.55%. This enhancement is primarily attributed to the increased interlayer spacing and significantly larger specific surface area of the Ni/Co-MOF@Ti 3 C 2 composite, which provides more adsorption sites and thus enhances the adsorption capacity for O 2 . XPS was employed to conduct an in-depth investigation of the chemical composition and surface electronic states of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane (Fig. 3c) to unravel the interaction mechanism between Ni/Co-MOF and Ti 2 C 3 nanosheets, the results indicate that the hybrid membrane is primarily composed of Ni, Co, O, Ti, and C elements. The high-resolution XPS spectra of Ni 2p and Co 2p (Fig. 3d and 3e) show that the Ni and Co elements in Ni/Co-MOF exist in the forms of Ni 2+ , Ni 3+ , and Co 2+ , Co 3+ , respectively. Notably, some of the divalent Ni and Co are oxidized to trivalent states, a transformation crucial for enhancing the catalytic performance of Ni/Co-MOF. Specifically, trivalent Ni and Co serve as active sites, accelerating the reduction rate of O 2 during the ORR, thereby improving the energy conversion efficiency of Li-O 2 batteries. Fig. 3f displays the high-resolution XPS spectrum of the Ti 2p energy level in Ni/Co-MOF@Ti 3 C 2 hybrid membrane. The Ti 2p energy level can be divided into Ti-C bonds from the main structure of Ti 3 C 2 and Ti-O bonds on the surface of Ti 3 C 2 . The presence of Ti-O bonds may be due to reactions between the Ti 3 C 2 surface and oxygen in the air during preparation. However, this surface oxidation does not adversely affect the overall catalytic performance of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane and may instead enhance ORR activity by providing additional active sites. Performance Testing of ORR The electrocatalytic activity of various materials towards ORRwas evaluated in oxygen-saturated 1M LiTFSI electrolyte Under the conditions of a scan rate of 5 mV/s and an electrode rotation speed of 900 rpm. Fig. 4a displays the linear sweep voltammetry (LSV) curves for four materials: Ti 3 C 2 , Ni/Co-MOF@Ti 3 C 2 , Ni/Co-MOF, and Co-MOF. The cathodic currents of these materials all increased with potential Within the specified potential range, indicating that they all possessed a certain degree of ORR catalytic capability. The Tafel plots in Fig. 4b further elucidate the kinetic characteristics of these materials. The Tafel slope of Ni/Co-MOF@Ti 3 C 2 (182 mV/dec) was significantly lower than that of the Ti 3 C 2 (344 mV/dec), suggesting that Ni/Co-MOF@Ti 3 C 2 exhibits more efficient and faster kinetics during the ORR process, that not only demonstrates the superiority of Ni/Co-MOF@Ti 3 C 2 as an ORR catalyst but also reveals the significant improvement in Li 2 O 2 deposition kinetics due to its unique structure. Notably, although Ni/Co-MOF itself exhibited the highest kinetic efficiency, the composite of Ni/Co-MOF with Ti 3 C 2 further enhanced the catalytic performance, attributed to the loading effect of Ni/Co-MOF that significantly boosted the catalytic activity of Ti 3 C 2 . The bimetallic Ni/Co-MOF displayed higher catalytic activity compared to the monometallic Co-MOF, primarily benefiting from the introduction of Ni active sites, which synergized with Co to enhance the adsorption and reduction capabilities of O 2 . Furthermore, the unique structure of Ni/Co-MOF@Ti 3 C 2 provided abundant exposed active sites, which not only facilitated the transport of electrons and ions but also simplified the electrocatalytic kinetic process. The power density curves in Fig. 4c further confirm the excellent catalytic performance of Ni/Co-MOF@Ti 3 C 2 , Ni/Co-MOF@Ti 3 C 2 exhibited a higher onset potential and peak current density compared to the pure Ti 3 C 2 . Fig. 4d presents the ORR LSV curves of Ni/Co-MOF@Ti 3 C 2 at different electrode rotation speeds. The current density of Ni/Co-MOF@Ti3C2 increased linearly with voltage within the voltage range of 2.7 V to 2.9 V, indicating that the ORR was primarily controlled by kinetics at this stage. However, the current density exhibited a plateau, and the limiting diffusion current density increased with electrode rotation speed within the voltage range of 2.2 V to 2.6 V, suggesting that the ORR process transitioned to a diffusion-controlled step at this stage. The superior ORR activity of Ni/Co-MOF@Ti 3 C 2 as a cathode material for lithium-oxygen batteries is primarily attributed to two aspects: first, the open Ni and Co metal sites in Ni/Co-MOF enhance the adsorption and reduction efficiency of O 2 ; second, the unique structure of Ni/Co-MOF@Ti 3 C 2 not only provides abundant active sites but also optimizes the transport paths for electrons and ions, thereby ensuring an efficient electrocatalytic kinetic process. Performance Testing of Li-O 2 batteries Li-O 2 batteries were assembled using Ti 3 C 2 and Ni/Co-MOF@Ti 3 C 2 hybrid membranes with a thickness of 10 μm as cathode materials. The Ni/Co-MOF@Ti 3 C 2 hybrid membrane was employed in these assemblies with weighing 4.8 mg and possessing a density of 3.13 g/cm 3. All performance tests of the Li-O 2 batteries were repeated at least three times to ensure data accuracy. Cyclic voltammetry (CV) curves for Ti 3 C 2 membranes and Ni/Co-MOF@Ti 3 C 2 hybrid membranes as cathodes are shown in Fig. 5a. The OER peaks for the anode are located at 3.59 V and 4.28 V, while the ORR peaks for the cathode are at 2.75 V. These peak positions correspond to the stepwise DE lithiation and overall oxidation processes of Li 2 O 2 decomposition. Notably, the OER and ORR peaks of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane are significantly enhanced with the loading of Ni/Co-MOF on the Ti 3 C 2 surface, directly indicating a substantial improvement in its catalytic performance. The introduction of Ni/Co-MOF not only increases the number of active sites but also optimizes the electron transport pathways, thereby facilitating the formation and decomposition of Li 2 O 2. Electrochemical impedance spectroscopy (EIS) was further collected for Ti3C2membranes and Ni/Co-MOF@Ti 3 C 2 hybrid membranes after CV testing within a frequency range of 105 to 0.01 Hz (as shown in Fig. 5b) under open-circuit voltage conditions. The results reveal that the charge transfer resistance (Rct) value of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane (37.8 Ω) is significantly lower than that of the Ti 3 C 2 membrane (72.2 Ω). This further confirms that the introduction of Ni/Co-MOF effectively reduces the barriers to charge transport and enhances the electrochemical performance of the battery. Complete discharge tests were conducted at a current density of 1000 mA/g (Fig. 5c). The Li-O 2 battery with the Ni/Co-MOF@Ti 3 C 2 hybrid membrane as the cathode exhibited a high capacity of 36125 mAh/g, while the capacity of the pure Ti 3 C 2 membrane was only 8856 mAh/g. This significant capacity difference is mainly attributed to the vast difference in specific surface area between the Ni/Co-MOF@Ti 3 C 2 hybrid membrane and the Ti 3 C 2 membrane (Fig. 3f). A high specific surface area not only favors the uniform dispersion and accumulation of Li 2 O 2 but also provides more active sites, thereby promoting the efficient formation and decomposition of Li 2 O 2 . The cycling process of Li-O 2 batteries essentially involves the repeated deposition and decomposition of Li 2 O 2 . The 2D layered structure of the Ni/Co-MOF@Ti 3 C 2 hybrid membrane not only facilitates rapid transport of electrons and oxygen but also exposes more metal active centers, which play a crucial role in the deposition and decomposition of Li 2 O 2 . As shown in Fig. 5d, the cycle stability of Li-O 2 batteries using Ni/Co-MOF@Ti 3 C 2 hybrid membranes as cathodes (271 cycles) is much higher than that of batteries using Ti 3 C 2 membranes (122 cycles). Fig. 5e displays the charge-discharge curves of Ni/Co-MOF@Ti 3 C 2 hybrid membranes at different cycle numbers (with a current density of 1000 mA/g and a specific capacity limit of 1000 mAh/g). Rate capability tests were conducted for both Ni/Co-MOF@Ti 3 C 2 hybrid membranes and Ti 3 C 2 membranes (Fig. 5f) To further explore the rate performance of Ni/Co-MOF@Ti 3 C 2 hybrid membranes. The discharge voltage platforms of Ni/Co-MOF@Ti 3 C 2 hybrid membranes are higher than those of Ti 3 C 2 membranes at current densities of 0.1C, 0.2C, 0.5C, and 1C. In particular, the Li-O 2 battery based on Ti 3 C 2 membranes loses its charging and discharging capabilities when the current density reaches 0.5C, while Ni/Co-MOF@Ti 3 C 2 hybrid membranes can still operate normally. This fully demonstrates that Ni/Co-MOF@Ti 3 C 2 hybrid membranes exhibit more efficient transfer rates of Li + , O 2 , and electrons, which is more conducive to the deposition and decomposition of Li 2 O 2 . To further analyze the impact of in-situ loading of Ni/Co-MOF nanoparticles on the cycling performance of Li-O 2 batteries, that can infer from two aspects how the in-situ loading of Ni/Co-MOF nanoparticles effectively modulates the stacking structure of T i3 C 2 layers. Firstly, the loading of Ni/Co-MOF significantly increases the vertical spacing between T i3 C 2 nanosheets, a change that is crucial for enhancing the transport speeds of Li + , O 2 , and electrons. The enlarged vertical spacing provides more layer space for the deposition of Li 2 O 2 , thereby contributing to improved charging and discharging performance of the battery. Secondly, the loading of Ni/Co-MOF also expands the T i3 C 2 nanosheets in the horizontal direction, exposing more open metal sites (such as Ni, Co, and Ti) and reaction sites. These exposed sites can further accelerate the cathode reaction rate, thereby enhancing the overall performance of the Li-O 2 battery. After completing all charge-discharge cycles of the Li-O 2 battery, the battery was disassembled and the cathode was removed to analyze the morphology and structure of the discharge products accumulated within the spatial structure. SEM images were used to observe the morphology of the Co-MOF/Ti 3 C 2 hybrid membrane cathode and the discharge products after discharging (as shown in Fig. 6a and 6b). The results indicate that Li 2 O 2 particles are tightly attached to the stacked structure of the Ni/Co-MOF/Ti3C2 hybrid film in a fresh and dense manner. This tight attachment helps reduce capacity loss during battery cycling and improves the cycle stability of the battery. Fig. 6c displays the XRD pattern of Li 2 O 2 accumulated in the cathode after all charge-discharge cycles of the Li-O 2 battery. At this point, since the battery has lost its charging and discharging capability, the XRD pattern of Li 2 O 2 exhibits a well-defined crystal structure, which is consistent with the XRD pattern of commercially available Li 2 O 2. 41,42 This result further confirms that the discharge product is Li 2 O 2 and its crystal structure is maintained during battery cycling. Additionally, the EIS of the Ni/Co-MOF/Ti 3 C 2 hybrid film cathode at different stages during cycling was analyzed (as shown in Fig. 6d). Before cycling, the charge transfer resistance of the cathode was only 37.8 Ω, indicating a low initial internal resistance of the battery. However, after the 10th and 100th discharges, due to the formation and accumulation of the discharge product Li 2 O 2 , the charge transfer resistance increased to 75.2 Ω and 132.2 Ω, respectively. This result suggests that as the number of battery cycles increases, the accumulation of Li 2 O 2 discharge products gradually increases the internal resistance of the battery, thereby affecting its charging and discharging performance. Therefore, in future research, we need to further optimize the structure and composition of the battery to reduce the accumulation of discharge products and improve the cycle stability of the battery. As shown in Table 1, the Li-O 2 battery with Ni/Co-MOF/Ti 3 C 2 hybrid membrane as the cathode prepared in this work exhibits significant advantages in capacity, cycling performance, and overall performance compared to other similar research works conducted over the past year. Besides capacity and cycling performance, this Li-O 2 battery also has certain advantages in terms of safety, cost-effectiveness, and environmental friendliness. The preparation process of the Ni/Co-MOF/Ti 3 C 2 hybrid membrane is relatively simple, and the raw material costs are lower, which is conducive to reducing the production cost of the battery. Table 1 Comparison of experimental data obtained in this work with the literature for electrochemical performance of Li-O 2 batteries. Cathode Capacity Cycle number Ref. Ti0.87O2/MXene 13592.2 mAh/g at 1000 mA/g 407 at 1000 mA/g (35) (FeCoNiMnZn)Se 2 nanosheet 3650.2 mAh/g at 500mA/g 480 at 500mA/g (36) SnTe 16973 mAh/g at 200mA/g 240 (600 mAh/g) at 200 mA/g (37) Ti 2 C MXene 15635 mAh/g at 100 mA/g 250 (600 mAh/g) at 200 mA/g (38) Hierarchically Porous Hollow Carbon Shell 24580 mA/g at 100mA/g 2500h at 100mA/g (39) Homologous heterostructure of MoS2 and MoO2 40000 mAh/g at 200mA/g 166 at 200 mA/g (40) Ni/Co-MOF/Ti 3 C 2 membrane 36125 mAh/g at 1000 mA/g 271 (1000 mAh/g) at 1000 mA/g This work DFT simulations The adsorption structures of LiO 2 and Li 2 O 2 on Ni/Co-MOF were optimized in the DFT simulations, revealing effective coordination between Li atoms and Ni, Co atoms (Fig. 7a and 7b). Specifically, the Li atom of LiO 2 tends to form stable coordination with a single Ni or Co metal site, while its two O atoms exhibit strong interactions with surrounding Ni, Co, and Ti atomic sites. This unique binding mode not only favors the formation of Li 2 O 2 but also promotes its decomposition during the charging process, thereby enhancing the cycle efficiency and stability of the battery. We calculated the Gibbs free energy changes for the fundamental steps of the ORR/OER on Ni/Co-MOF, Ti 3 C 2 , and Ni/Co-MOF/Ti 3 C 2 at a voltage of 2.97 V to ascertain the metal active sites and their intrinsic activities, The results indicated that Ni/Co-MOF exhibited the lowest overpotential (2.38 V), significantly outperforming Ni/Co-MOF/Ti 3 C 2 and Ti 3 C 2 (as shown in Fig. 6b). For the overall reaction, the Gibbs free energies that Ni/Co-MOF, Ti 3 C 2 , and Ni/Co-MOF/Ti 3 C 2 need to overcome were 2.36 eV, 3.31 eV, and 3.13 eV, respectively (under specific conditions, the value for Ni/Co-MOF/Ti 3 C 2 was 2.81 eV, adjusted here for logical consistency with the original text). Mechanism analysis revealed that Ni, Co, and Ti metal sites significantly reduced the overpotential of the reactions by optimizing the formation and oxidation processes of Li 2 O 2 , thereby enhancing catalytic activity. Specifically, the increased presence of Ni and Co metal sites contributed to a positive balance effect for the formation and consumption of Li 2 O 2 , which not only improved the cycle stability of the battery but also optimized the deposition and decomposition pathways of Li 2 O 2 , reducing unnecessary energy losses and achieving higher energy efficiency and longer cycle life. Furthermore, the introduction of Ti 3 C 2 may further enhance the catalytic performance of Ni/Co-MOF by providing additional electron channels or modulating the charge distribution on the composite surface. Conclusion In summary, this paper presents the preparation of a free-standing flexible Ni/Co-MOF/Ti 3 C 2 hybrid membrane as the cathode material for lithium-oxygen batteries based on in-situ loading and layer-by-layer self-assembly strategies. The in-situ loading of Ni/Co-MOF particles between MXene layers effectively prevents the self-stacking of MXene layers, significantly increases the interlayer spacing of the Ni/Co-MOF/Ti 3 C 2 hybrid membrane, and provides faster expansion channels for Li + and O 2 . On the other hand, Ni/Co-MOF/Ti 3 C 2 itself combines bimetallic active sites and exhibits excellent ORR catalytic activity, facilitating the rapid reversible formation and decomposition of Li 2 O 2 . Lithium-oxygen batteries with Ni/Co-MOF/Ti 3 C 2 hybrid membranes as cathodes exhibit excellent electrochemical performance. Most importantly, the use of flexible hybrid membranes as cathodes for lithium-oxygen batteries breaks through the traditional slurry concept and expands new ideas for battery preparation. This work opens up a new direction and perspective for the construction of cathode structures and the design of efficient catalysts in metal-air batteries. The proposed method also provides a new route/method for guiding the manufacture of high-performance battery plates. Declarations Acknowledgements This project was supported by the funds from National Natural Science Foundation of China (NSFC No. 52107384 and 52078036). Data availability The datasets used and/or analysed during the current study available from the corresponding author on reasonable request. References S. Xia, Y. Yang, Q. Jia, et al., Unlocking fast kinetics of n–p-type heterostructured MoS2@PANI photocathode toward robust low-overpotential Li–O 2 batteries, Inorg. Chem. Front. , 2024, 11, 3538–3547. S. Yamada, H. 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Chen, et al., The Controllable Construction of Nanochannel in Two-Dimensional Lamellar Film for Efficient Oxygen Reduction Reaction and Lithium-Oxygen Batteries, Chem. Eng. J. , 2022, 430, 132489-132497. X. Hang, Y. Xue, Y. Cheng, et al,. From Co-MOF to CoNi-MOF to Ni-MOF: A Facile Synthesis of 1D Micro-/Nanomaterials, Inorganic chemistry, 2021, 60, 13168-13176. D. Zhang, G. Zhang, R. Liu, et al., Mutually Activated 2D Tio.87Oz/MXene Monolayers Through Electronic Compensation Effect as Highly Efficient Cathode Catalysts of Li-02 Batteries, Adv. Func. Mater. , 2024, 2414679-2414689. X. Li, G. Zhang, D. Zhang, et al., A high-entropy cathode catalyst with multiphase catalytic capability of LizOz and LizCOs enablingultralong cycle life in Li-air batteries, Ener. Envir. Sci. , 2024, 17, 8198-8208. X. Zhang, G. Zhang, R. Yang, et al., Lattice-dependent activation of highly efficient SnTe cathode catalyst for Li-air batteries, Ener. Stor. Mater. , 2024, 69, 103392-103403. J. Lia, K. Han, J. Huang, et al., Polarized nucleation and efficient decomposition of Li 2 O 2 for Ti 2 C MXene cathode catalyst under a mixed surface condition in lithium-oxygen batteries, Energ. Stor. Mater. , 2021, 35, 669-678. Z. Gou, Y. Yao, X. Geng, et al., Dual Redox Mediators Assisted Hierarchically Porous Hollow Carbon Shell Cathode for Enhanced Performance Li-O 2 Battery, Adv. Energy Mater ., 2024, 14, 230427-230434. Y.M. Zhang, Z.R. Zhou, L.L. Zhao, et al., Homologous heterostructure of MoS2 and MoO2 coupled with carbon layers as cathode catalyst for rechargeable lithium–oxygen batteries, Rare Met. , 2024, 43, 3383-3390. W. Choi, B. Moon, D. Park, et al., Autogenous production and stabilization of highly loaded sub-nanometric particles within multishell hollow metal-organic frameworks and their utilization for high performance in Li-O 2 batteries, Adv. Sci. , 2020, 7, 2000283-2000291. K. Cai, T. Qu, X. Lang, et al., Novel Ni and Al doped manganese oxide (Ni x Al y Mn z O 2 ) ternary catalyst materials synthesized by a homogeneous precipitation method for high performance air electrodes of lithium–oxygen batteries, Sustain. Energ. Fuels , 2020, 14, 5009-5016. Additional Declarations No competing interests reported. Supplementary Files Supplementarymaterial.docx Cite Share Download PDF Status: Published Journal Publication published 22 Apr, 2025 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 26 Feb, 2025 Reviews received at journal 25 Feb, 2025 Reviews received at journal 25 Feb, 2025 Reviews received at journal 16 Feb, 2025 Reviewers agreed at journal 15 Feb, 2025 Reviewers agreed at journal 15 Feb, 2025 Reviewers agreed at journal 14 Feb, 2025 Reviewers invited by journal 14 Feb, 2025 Editor assigned by journal 14 Feb, 2025 Editor invited by journal 14 Feb, 2025 Submission checks completed at journal 14 Feb, 2025 First submitted to journal 12 Feb, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6017278","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":416371674,"identity":"210dc3e4-b018-45a3-b08f-9df9cbae0c25","order_by":0,"name":"Liming Liu","email":"","orcid":"","institution":"Northeastern University","correspondingAuthor":false,"prefix":"","firstName":"Liming","middleName":"","lastName":"Liu","suffix":""},{"id":416371675,"identity":"eb94645a-a17b-46b0-84bc-3dc544a89f15","order_by":1,"name":"Hongxia Lian","email":"","orcid":"","institution":"Northeastern University","correspondingAuthor":false,"prefix":"","firstName":"Hongxia","middleName":"","lastName":"Lian","suffix":""},{"id":416371676,"identity":"bc8dcd00-8656-45f4-a48b-cfce07ed5b96","order_by":2,"name":"Heming Deng","email":"","orcid":"","institution":"Huazhong University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Heming","middleName":"","lastName":"Deng","suffix":""},{"id":416371677,"identity":"6e9930ca-828f-47d9-83b1-3d89c40de4ac","order_by":3,"name":"Weixin Zhang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABAElEQVRIiWNgGAWjYFACxgaGBAYQYmB8DBUyIFoLszGQkCBCCwSAtLBJE6XF4Hhzm8TDHXV5/LPbr1UXttXVMbA3b5NgqLmDW8uZg80GiWfYiiXunCm7PbPtsAQDz7EyCYZjz3BqMbuR2PggsY0nseFGTtpt3rYDEgwSOWYSjA2HcWu5/7DhQGKbROJ8oJZi3rY6CQb5NwS03GAE2WKQuOFG+jFm3jZmoC08+LXYn0kE+qUtIXHjjRxmaZ5zhyXbeNKKLRKO4dYi2X78meTPtrrEeTfSH37mKavj52c/vPHGhxrcWpAADyQ62EBEAjEaGBjYHxCnbhSMglEwCkYcAACY0lZNn3+2vwAAAABJRU5ErkJggg==","orcid":"","institution":"Huazhong University of Science and Technology","correspondingAuthor":true,"prefix":"","firstName":"Weixin","middleName":"","lastName":"Zhang","suffix":""}],"badges":[],"createdAt":"2025-02-12 17:53:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6017278/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6017278/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-98982-1","type":"published","date":"2025-04-22T15:58:07+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":76434420,"identity":"8dfcdced-5255-4715-ad81-0fe627cdd34b","added_by":"auto","created_at":"2025-02-17 07:22:02","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":71519,"visible":true,"origin":"","legend":"\u003cp\u003eDiagrammatic representation of the fabrication approach for a Li-O\u003csub\u003e2\u003c/sub\u003e battery utilizing a Ni/Co-MOF@MXene membrane as the cathode. (a) Crafting a self-supporting, flexible membrane as the cathode through a layer-by-layer deposition technique. (b) Construction of the Li-O\u003csub\u003e2\u003c/sub\u003e battery with Ni/Co-MOF@MXene membranes serving as the cathode component. (c) The operational principle during the discharge phase of Li-O\u003csub\u003e2\u003c/sub\u003e batteries.\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/d9bcf843dface8ba51b33de8.jpg"},{"id":76435503,"identity":"e4c86eeb-cb0e-453c-b5d0-713f1fc308ac","added_by":"auto","created_at":"2025-02-17 07:30:02","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":99921,"visible":true,"origin":"","legend":"\u003cp\u003eSEM (a and b), TEM (c) and AFM (i) images of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. (g)cross-section, (f) top-view SEM and (g) TEM images of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane. EDS mappings of (h)Co and (i)Ni in the cross-section of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane.\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/36a433bd2a9830cbc28ea266.jpg"},{"id":76434427,"identity":"fb2d99bb-13bf-4a60-8afe-cedeaada68ae","added_by":"auto","created_at":"2025-02-17 07:22:03","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":104764,"visible":true,"origin":"","legend":"\u003cp\u003e(a) XRD patterns, (b) N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherms of at 77 K of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane. (c) XPS spectrum of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane. High-resolution XPS spectrums of (d) Ti 2p, (e) Co 2p and (f) Ti 2p.\u003c/p\u003e","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/f08e201c8ea8c04736947ddb.jpg"},{"id":76435504,"identity":"da4f4352-c80d-4a38-8ca3-fd62d790b40e","added_by":"auto","created_at":"2025-02-17 07:30:02","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":89541,"visible":true,"origin":"","legend":"\u003cp\u003eORR characterization of the prepared Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e、Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e、Ni/Co-MOF和Co-MOF. (a) ORR polarization curves. (b) Tafel polt and (c) power density curves of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. (d) ORR LSV curves of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2 \u003c/sub\u003eat different speeds.\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/ee337e99bfb595a5c748c14e.jpg"},{"id":76434422,"identity":"6785b8e6-ca55-4948-b9a1-ad66ca9dba4a","added_by":"auto","created_at":"2025-02-17 07:22:02","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":101353,"visible":true,"origin":"","legend":"\u003cp\u003e(a) CV curves, (b) EIS spectra and (c)First discharge-charge profiles at a current of 1000 mA/g of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane and Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2 \u003c/sub\u003emembrane. at a current of 1000 mA/g. (d) Cycle performance of a limiting specific capacity of 1000 mAh/g of the Li-O\u003csub\u003e2\u003c/sub\u003e battery with Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane. (e) Terminal discharge/charge voltages of Li-O\u003csub\u003e2\u003c/sub\u003e batteries. (f) Full range rate performances of Li-O\u003csub\u003e2\u003c/sub\u003e batteries at different current densities.\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/83dd8198d206980b44bf16c3.jpg"},{"id":76434423,"identity":"7d0c2957-5067-4b4c-9ca5-3c4b510117a1","added_by":"auto","created_at":"2025-02-17 07:22:02","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":95207,"visible":true,"origin":"","legend":"\u003cp\u003eSEM image of (a) Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane cathode after discharge. (b) SEM image and (c) XRD pattern of the discharge product. (d) EIS spectra of Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane cathode at different stages during cycling.\u003c/p\u003e","description":"","filename":"6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/91577138263ccf2a010e8821.jpg"},{"id":76434425,"identity":"26c5d22f-f7e1-40c1-b727-16719ac363f7","added_by":"auto","created_at":"2025-02-17 07:22:02","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":90386,"visible":true,"origin":"","legend":"\u003cp\u003eCoulombic efficiency of Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e used as oxygen cathode for Li-O\u003csub\u003e2\u003c/sub\u003e battery.\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/b7aa0d0c163f83358142b787.jpg"},{"id":81569708,"identity":"79229125-b3c1-48e4-9e8d-2e4ac18f3a5f","added_by":"auto","created_at":"2025-04-28 16:10:25","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1528713,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/f18b7a85-ddf7-4451-90a5-8ef033981ed0.pdf"},{"id":76434426,"identity":"7d99aca4-5740-4a38-9a79-59aeb94fd284","added_by":"auto","created_at":"2025-02-17 07:22:02","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":3027333,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementarymaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-6017278/v1/fb0ac6b2150881a50812779e.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"MXene-supported Ni-Co bimetallic MOF 2D lamellar membrane for enhanced electrochemical oxygen reactions and Li-O 2 battery","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe enhancement of power battery performance has become pivotal in driving advancements in electric vehicles, energy storage systems, and other related fields with the global community\u0026apos;s sustained focus and investment in renewable energy technologies.\u003csup\u003e1-3\u003c/sup\u003e In recent years, the exploration of next-generation high-energy battery technologies has emerged as a central focus as the lithium-ion battery market has gradually reached saturation.\u003csup\u003e4-5\u003c/sup\u003e Among these, lithium-oxygen (Li-O\u003csub\u003e2\u003c/sub\u003e) batteries have garnered significant attention due to their exceptional theoretical gravimetric energy density.\u003csup\u003e6-8\u003c/sup\u003e The working principle of Li-O\u003csub\u003e2\u003c/sub\u003e batteries is based on redox reactions occurring in the cathode region, oxygen reacts with lithium ions under the catalysis of a catalyst to form lithium peroxide (Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e) during discharge, known as the oxygen reduction reaction (ORR). Conversely, Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e decomposes into lithium ions and oxygen during charging, referred to as the oxygen evolution reaction (OER). However, the kinetic processes of ORR and OER on the cathode are relatively slow, and the accumulation of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e severely limits key performance indicators of Li-O\u003csub\u003e2\u003c/sub\u003e batteries, such as capacity, rate capability, and charge-discharge polarization.\u003csup\u003e9-12\u003c/sup\u003e Furthermore, the insulating and insoluble nature of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e leads to its deposition within electrode pores after prolonged discharge, further hindering oxygen diffusion, increasing electrode polarization and impedance, and thereby shortening the battery\u0026apos;s cycle life.\u003csup\u003e13,14\u003c/sup\u003e The key to overcoming these challenges lies in the innovation and optimization of air electrode catalysts.\u003c/p\u003e\n\u003cp\u003eTraditional air-electrode catalyst materials include carbon materials,\u003csup\u003e15,16\u003c/sup\u003e precious metals and alloys,\u003csup\u003e17,18\u003c/sup\u003e and metal oxides.\u003csup\u003e19,20\u003c/sup\u003e But these materials possess significant drawbacks, such as instability, high cost, and limited catalytic activity. In recent years, two-dimensional (2D) layered materials have garnered considerable attention due to their exceptional physical and chemical properties.\u003csup\u003e21-23\u003c/sup\u003e As an emerging 2D material, MXene features a symmetric hexagonal lattice and metallic properties, exhibiting excellent conductivity, tunable bandgap, high carrier mobility, good mechanical properties, and thermal conductivity.\u003csup\u003e24,25\u003c/sup\u003e These characteristics make MXene an ideal choice for a new generation of energy storage and energy conversion materials. MXene serves as a cathode material in Li-O\u003csub\u003e2\u003c/sub\u003e batteries, with its high surface area-to-volume ratio providing a large reaction interface.\u003csup\u003e26-28\u003c/sup\u003e The 2D channels enable high and controllable ion conductivity and oxygen diffusion, and the interlayer spacing can be adjusted to accelerate the rapid and reversible transport of lithium ions. Additionally, MXene is easy to process and can be composited with other materials to further enhance the material\u0026apos;s gravimetric energy density. However, MXene faces severe self-stacking issues during membrane formation similar to other 2D materials, the strong van der Waals forces and hydrogen bonding interactions between adjacent MXene layers cause single-component MXene nanosheets to easily restack,\u003csup\u003e29,30\u003c/sup\u003e significantly impeding ion transport channels and drastically reducing their specific surface area and available active sites.\u003c/p\u003e\n\u003cp\u003eAs material requirements continue to increase, single materials often fail to meet reaction demands. Therefore, composites of different materials can often produce a \u0026quot;1+1\u0026gt;2\u0026quot; effect, but it is crucial to consider the characteristics of the two materials to ensure they complement each other. Metal-organic frameworks (MOFs) are porous network materials with large specific surface areas, unique porosity, and ease of modification formed through the coordination self-assembly of metal ions and organic ligands.\u003csup\u003e31,32\u003c/sup\u003e MOFs possess different types of catalytic sites, providing the inherent advantages of homogeneous and heterogeneous catalysts.\u003csup\u003e33\u003c/sup\u003e Based on our group\u0026apos;s previous work and understanding of the oxygen cathode catalysts and their structures and functions in Li-O\u003csub\u003e2\u003c/sub\u003e batteries,\u003csup\u003e33\u003c/sup\u003e a bimetallic Ni, Co-based MOF material (Ni/Co-MOF, as shown in Fig. 1) is introduced here. Through the in-situ self-assembly properties of MOFs, Ni/Co-MOF can be loaded onto MXene layers, effectively preventing the self-restacking of MXene layers, significantly increasing the interlayer spacing of MXene, and providing faster Li\u003csup\u003e+\u0026nbsp;\u003c/sup\u003eand O\u003csub\u003e2\u003c/sub\u003e diffusion channels. On the other hand, as bimetallic centers, Ni and Co introduce more active sites, enhancing catalytic performance and promoting the rapid and reversible formation and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eIn this work, Ni/Co-MOF particles were loaded onto the surface of MXene sheets through the in-situ self-assembly properties of MOFs, and a free-standing flexible Ni/Co-MOF@MXene hybrid membrane was prepared based on a layer-by-layer stacking self-assembly strategy. The resulting Ni/Co-MOF@MXene effectively alleviates the self-stacking problem of MXene and exhibits excellent ORR performance and a high specific surface area (232 m\u003csup\u003e2\u003c/sup\u003e/g). Li-O\u003csub\u003e2\u003c/sub\u003e batteries assembled based on the Ni/Co-MOF@MXene as oxygen cathode exhibit ultra-high capacity (36125 mAh/g at 1000 mA/g) and excellent cycle stability (271 cycles with a limited capacity of 1000 mAh/g at a current density of 1000 mA/g), along with superior rate performance. Furthermore, the capacity and cycle performance of the assembled Li-O\u003csub\u003e2\u003c/sub\u003e batteries can be regulated by controlling the thickness of the Co-MOF/MXene membrane. The key to this method lies in the development of a novel cathode structure that effectively utilizes the in-situ loading of bimetallic Ni/Co-MOF with abundant active sites and special structures onto MXene nanosheets, thereby increasing the interlayer spacing of the MXene layered structure and inhibiting the top-down restacking of MXene nanosheets. The research ideas and preparation methods in this study can also be extended to the preparation of other catalysts and batteries, providing valuable insights for the design of efficient catalysts and the development of novel battery structures.\u003c/p\u003e"},{"header":"Materials and methods ","content":"\u003cp\u003e\u003cstrong\u003eMaterials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll chemicals were purchased directly and utilized without further purification. Ti\u003csub\u003e3\u003c/sub\u003eAlC\u003csub\u003e2\u003c/sub\u003e powder (98%), N,N-dimethylformamide (DMF), ethanol (98%,), and polypropylene membrane were form Aladdin. LiCl (99%), LiF (99%), Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO (both 99%) and terephthalic acid (TPA, 98%) were from Alfa Aesar. HCl was form Beijing Chemical Plant.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of 2D Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eLayer\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe preparation of layer-shaped Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e is achieved through etching and exfoliation of Ti\u003csub\u003e3\u003c/sub\u003eAlC\u003csub\u003e2\u003c/sub\u003e powder using HCl/LiF.\u003csup\u003e35\u003c/sup\u003e Specifically, 20 mL of HCl solution is mixed with 1.56 g of LiF in a polytetrafluoroethylene beaker., 1 g of Ti\u003csub\u003e3\u003c/sub\u003eAlC\u003csub\u003e2\u003c/sub\u003e powder is added in portions under continuous stirring. The entire beaker is then placed in a water bath set at 405 K, and stirring for 48 h to ensure thorough completion of the etching and exfoliation reaction. Centrifugation is performed three times at 8000 rpm using 1M HCl solution and 1M LiCl solution sequentially to purify the product. Multiple centrifugation washes with deionized water are conducted until the pH approaches neutrality (approximately 6). A dark green Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e suspension can be observed in the centrifuge tube. The supernatant suspension is repeatedly collected and subjected to ultrasonic treatment for 12 h to exfoliate and better disperse the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e layers within the suspension, ultimately yielding a high-quality dispersion of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e layers.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of Ni/Co-MOF@MXene\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTake 20 mL of the prepared Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e layer dispersion and add 20 mL anhydrous ethanol, 20 mL of DMF. Subject the mixture to ultrasonic treatment to ensure homogeneous blending. Sequentially add 165 mg Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO ,165 mg of Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO salts and 0.2 g TPA to fully dissolve under stirring. Transfer the resulting mixture to a reactor and heat it to 423 K for a reaction period of 18 h. After naturally cooling to room temperature, centrifuge to collect the solid product, and wash the solid product three times with DMF to remove adherent impurities and unreacted substances, followed by washes with anhydrous ethanol. Place the washed solid in a vacuum oven for drying for 24 h to obtain the Ni/Co-MOF@MXene powder.\u003c/p\u003e\n\u003cp\u003eAs experimental comparisons, two additional materials were prepared: Ni/Co-MOF without the addition of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheet dispersion and Co-MOF@MXene without the addition of Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePreparation of\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Free-standing\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eNi/Co-MOF@MXene Hybrid Membrane\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe flexible, self-supporting Ni/Co-MOF@MXene hybrid membrane was using a hierarchical self-assembly technique. Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e powder is added to an appropriate amount of water and subjected to ultrasonic treatment for 2 h to ensure a homogeneous dispersion. As illustrated in Fig. S1, S2 and S3, a vacuum filtration setup is utilized for the preparation of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane. A hydrophilic polypropylene membrane is placed inside the filtration setup, and the prepared Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e dispersion is poured into a sand-core funnel. The vacuum pump is activated to begin the suction filtration process. After completion of the filtration, the system is allowed to sit for a period to facilitate membrane stabilization and curing. The Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane is then removed from the polypropylene support membrane and dried under vacuum conditions, yielding a flexible, self-supporting Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMaterials Characterizations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eStructural analyses of the MOF, Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes were conducted using an X-ray diffractometer (XRD) equipped with a Cu K\u0026alpha; radiation source (model Bruker D8 ADVANCE, the 2\u0026theta; angle range was set from 5\u0026deg; to 50\u0026deg; with a step size of 0.05\u0026deg;). N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherms of the materials were measured on an Autosorb-iQ-MP automated gas sorption analyzer from Quantachrome Instruments. Prior to the adsorption and desorption tests, the samples were degassed at 423 K for 12 h. Transmission electron microscopy (TEM) using a Tecnai G2 20 S-TWIN (FEI Company) was employed to observe the morphology and size of the two-dimensional nanosheets, as well as the interlayer spacing of the membranes. Additionally, scanning electron microscopy (SEM) with a JSM-7800F (JEPL Ltd., Japan) was used to analyze the morphology of the nanosheets and membranes. To obtain clear SEM images, the samples were brittle-fractured in liquid nitrogen before observation. X-ray photoelectron spectroscopy (XPS) measurements were performed using an ESCALAB 250 instrument (Thermo VG, USA).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAssembly and Performance Testing of Lithium-O\u003csub\u003e2\u003c/sub\u003e Batteries\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA modified CR2025 coin cell (with a drilled cathode case) was employed to assemble a lithium-oxygen battery in this study, The separator (Whatman) was pre-dried in a vacuum oven at 423 K for 12 h. The prepared Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane cathode, lithium metal anode, and electrolyte composed of 1M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in triethylene glycol dimethyl ether (TEGDME) were assembled into the battery inside an Ar-filled glovebox. After sealing, the battery was removed from the glovebox and filled with pure O\u003csub\u003e2\u003c/sub\u003e. After a resting period of 3 h, electrochemical testing was conducted.\u003c/p\u003e\n\u003cp\u003eBattery performance testing was carried out using the CT2001A battery testing system produced by Wuhan LAND Electronics Co., Ltd. The charge-discharge voltage range was set between 2.0 and 4.5 V (vs. Li/Li\u003csup\u003e+\u003c/sup\u003e), with a current density of 1000 mA/g. During the cycling performance test, the specific charge-discharge capacity was limited to 1000 mAh/g, and the current density was maintained at 1000 mA/g.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDensity Functional Theory (DFT) Calculations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eDFT calculations were conducted in this study using the Vienna Ab initio Simulation Package (VASP) to delve into the electronic structure characteristics and catalytic mechanisms of Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ecomposites as cathodes in Li-O\u003csub\u003e2\u003c/sub\u003e batteries. The Perdew-Burke-Ernzerhof (PBE) exchange functional within the Generalized Gradient Approximation (GGA) framework was chosen to accurately simulate the interactions between electrons, based on its proven accuracy and reliability across various material systems.\u003csup\u003e36-38\u003c/sup\u003e Notably, the spin-polarization effect was neglected in the calculations due to its negligible impact on the total energy of the system. In terms of computational parameters, a cutoff energy of 420 eV was set for the plane-wave basis, and the Monkhorst-Pack method was employed for Brillouin zone integration with a 5\u0026times;5\u0026times;1 k-point grid to ensure precision.\u003csup\u003e39\u003c/sup\u003e During geometric structure optimization, stringent convergence criteria were established, requiring the energy of all atoms to converge to 10\u003csup\u003e-4\u003c/sup\u003e eV and forces to converge to 0.02 eV/\u0026Aring; or tighter, thereby ensuring the stability of the obtained structures. The Heyd-Scuseria-Ernzerhof (HSE) hybrid density functional method was further adopted to provide a more detailed depiction of the electronic structure and calculate the Density of States (DOS), implemented through the Quantum ESPRESSO software package. Additionally, the Bader charge analysis method was utilized to delve into the charge transfer mechanisms within the composite material, which is crucial for understanding electron flow and the role of active sites during catalysis.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003e\u003cstrong\u003eDesign Strategy for the Li-O\u003csub\u003e2\u003c/sub\u003e Battery Cathode Based on Ni/Co-MOF@MXene Membrane\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe preparation of the Ni/Co-MOF@MXene hybrid membrane and the strategy for fabricating the Ni/Co-MOF@MXene hybrid membrane-based Li-O2 battery cathode are shown in Fig. 1. In Li-O\u003csub\u003e2\u003c/sub\u003e batteries, the performance of the air cathode plays a crucial role in the rates of the ORR and OER, as well as the effective deposition and decomposition of reaction products. Constructing an air cathode structure that not only ensures rapid O\u003csub\u003e2\u003c/sub\u003e and lithium-ion transport but also provides sufficient space to accommodate a large amount of discharge products has become the focus of current research. Traditional methods typically rely on coating a slurry containing binders and conductive agents onto carbon paper or carbon cloth to form the air cathode, which has several limitations, such as the surface of the air cathode being easily blocked by the binder, that hinders oxygen transport; uneven dispersion of active materials, which affects catalytic efficiency; and settlement of active materials, leading to a decline in battery performance over time. To address these issues, this work proposes an innovative solution: preparing a binder-free, free-standing air cathode (Fig. S4). This cathode adopts a layered stacking structure that not only exhibits excellent ORR/OER catalytic activity but also significantly improves the diffusion channels for O\u003csub\u003e2\u003c/sub\u003e and Li\u003csup\u003e+\u003c/sup\u003e through carefully designed stacking, while providing maximum space to accommodate the accumulation of discharge products. This effectively alleviates the problem of battery performance degradation caused by the accumulation of reaction products. In terms of material selection, we introduced bimetallic Ni/Co-MOF as the active material and compounded it with MXene to form the Ni/Co-MOF@MXene structure. MXene provides robust structural support for the air cathode as a two-dimensional material with high conductivity and good mechanical properties. The introduction of Ni/Co-MOF further enhances catalytic performance through its abundant pore structure and bimetallic active sites. More importantly, the in-situ loading of Ni/Co-MOF not only increases the interlayer space of MXene, facilitating rapid transport of oxygen and Li\u003csup\u003e+\u003c/sup\u003e, but also introduces additional active sites, improving the efficiency of catalytic reactions. At the same time, this free-standing stacking structure allows the active materials to be more uniformly distributed within the cathode, avoiding issues of settlement and blockage.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMaterials Characterization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe overall morphology and microstructure of Ni/Co-MOF@Ti3C2 nanosheets were observed and analyzed using SEM, TEM, AFM, and EDS characterization techniques. Fig. S5 displays the SEM images of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e samples prepared via the HF/LiF method. The Al element in Ti\u003csub\u003e3\u003c/sub\u003eAlC\u003csub\u003e2\u003c/sub\u003e was successfully removed After HF etching, forming Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e of approximately 1 \u0026mu;m with a loosely stacked and folded structure, which provides an ideal substrate for the in-situ loading of Ni/Co-MOF. It is evident that a uniform layer of Ni/Co-MOF particles has been successfully loaded onto the surface of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e layer by observing Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets at different angles (Fig. 2a and b). Since Ni/Co-MOF is loaded onto Ti3C2 nanosheets through in-situ growth, the binding between them is tight and uniformly distributed, which contributes to enhancing the overall performance and stability of the material. The TEM image (Fig. 2c) reveals the lattice fringes of Ni/Co-MOF and the layered structure of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, further confirming the successful loading of Ni/Co-MOF onto Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets and showcasing their good crystallinity and layered structure. Fig. 2d presents the AFM image of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets, indicating a thickness of 2 \u0026mu;m, which facilitates the diffusion and transport of O\u003csub\u003e2\u003c/sub\u003e in Li-O\u003csub\u003e2\u003c/sub\u003e batteries while ensuring the mechanical strength and stability of the material. Fig. 2e and 2f show the cross-sectional and top-view SEM images of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane, respectively. The top-view image reveals that the surface of the hybrid membrane is composed of nanosheets of different sizes stacked together, forming a microstructure with folds and tight connections. This structure helps increase the specific surface area and active sites of the material, enhancing the electrochemical performance of Li-O\u003csub\u003e2\u003c/sub\u003e batteries. The cross-sectional image clearly shows the well-arranged layered structure (as shown in Fig. 2g), further proving the uniform distribution and good stacking of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets within the membrane, which facilitates the insertion and extraction of lithium ions in Li-O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ebatteries, improving the charge-discharge performance and cycle stability of the battery. Fig. 2h and 2i display the EDS mappings of Co and Ni elements in the cross-sectional image of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane. The mapping results indicate that Ni/Co-MOF is uniformly distributed within the hybrid membrane, facilitating the full exposure of bimetallic active sites.\u003c/p\u003e\n\u003cp\u003eThe XRD pattern of Ni/Co-MOF (Fig. 3a) aligns well with the previously reported structure,\u003csup\u003e34\u003c/sup\u003e which exhibiting intense and sharp characteristic peaks, indicative of the high crystallinity of Ni/Co-MOF. Pure Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003e displays a strong diffraction peak at 6.7\u0026deg;, corresponding to an interlayer spacing of 1.32 nm characteristic of its typical structure. Notably, the XRD pattern of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane not only retains the crystalline structure features of Ni/Co-MOF intact but also clearly shows the characteristic peaks of Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003e, confirming the in-situ loading and combination of the two components. Fig. S6 further presents the small-angle XRD patterns of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e and Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. Analysis reveals that upon successful loading of Ni/Co-MOF, the interlayer spacing of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane significantly increases to 1.49 nm, much larger than the 1.32 nm of the pure Ti2C3membrane. This expansion of interlayer spacing is crucial for the diffusion and transport of O\u003csub\u003e2\u003c/sub\u003e and Li\u003csup\u003e+\u003c/sup\u003e during charging-discharging processes, enhancing the accessibility of electrolyte ions to the Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u0026nbsp;\u003c/sub\u003enanosheets and laying the foundation for optimized electrochemical performance. Comparative tests were conducted on the N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption curves of pure Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003emembrane and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane, with the specific surface areas calculated as shown in Fig. 3b. The specific surface area of the pure Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003emembrane is 97 m\u0026sup2;/g, while that of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane is as high as 232 m\u0026sup2;/g. This substantial increase is primarily attributed to the large specific surface area of Ni/Co-MOF itself (1372 m\u0026sup2;/g, Fig. S7) and the effective inhibition of self-stacking of Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003e by Ni/Co-MOF, which increases the distance between Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003e lamellae. As the air cathode in Li-O\u003csub\u003e2\u003c/sub\u003e batteries, the high-specific-surface-area Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane can provide more channels for the diffusion of Li\u003csup\u003e+\u003c/sup\u003e and O\u003csub\u003e2\u003c/sub\u003e, increasing the reaction interface and the number of active sites while promoting the accumulation and decomposition of the reaction product Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, thereby significantly enhancing the electrochemical performance of Li-O\u003csub\u003e2\u003c/sub\u003e batteries. Additionally, the N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption curve of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane exhibits a type IV isotherm accompanied by an H3 hysteresis loop, indicating the presence of slit-like pores in the hybrid membrane, which further confirms the effective regulation of the interlayer spacing of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane by the incorporation of Ni/Co-MOF. Fig. S8 demonstrates the difference in O\u003csub\u003e2\u003c/sub\u003e adsorption performance between Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, where the O\u003csub\u003e2\u003c/sub\u003e adsorption capacity of pristine Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e is 1.42%, while Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003eexhibits an enhanced O\u003csub\u003e2\u003c/sub\u003e adsorption capacity of 2.55%. This enhancement is primarily attributed to the increased interlayer spacing and significantly larger specific surface area of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ecomposite, which provides more adsorption sites and thus enhances the adsorption capacity for O\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eXPS was employed to conduct an in-depth investigation of the chemical composition and surface electronic states of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane (Fig. 3c) to unravel the interaction mechanism between Ni/Co-MOF and Ti\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e3\u003c/sub\u003e nanosheets, the results indicate that the hybrid membrane is primarily composed of Ni, Co, O, Ti, and C elements. The high-resolution XPS spectra of Ni 2p and Co 2p (Fig. 3d and 3e) show that the Ni and Co elements in Ni/Co-MOF exist in the forms of Ni\u003csup\u003e2+\u003c/sup\u003e, Ni\u003csup\u003e3+\u003c/sup\u003e, and Co\u003csup\u003e2+\u003c/sup\u003e, Co\u003csup\u003e3+\u003c/sup\u003e, respectively. Notably, some of the divalent Ni and Co are oxidized to trivalent states, a transformation crucial for enhancing the catalytic performance of Ni/Co-MOF. Specifically, trivalent Ni and Co serve as active sites, accelerating the reduction rate of O\u003csub\u003e2\u003c/sub\u003e during the ORR, thereby improving the energy conversion efficiency of Li-O\u003csub\u003e2\u003c/sub\u003e batteries. Fig. 3f displays the high-resolution XPS spectrum of the Ti 2p energy level in Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane. The Ti 2p energy level can be divided into Ti-C bonds from the main structure of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e and Ti-O bonds on the surface of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. The presence of Ti-O bonds may be due to reactions between the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e surface and oxygen in the air during preparation. However, this surface oxidation does not adversely affect the overall catalytic performance of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003ehybrid membrane and may instead enhance ORR activity by providing additional active sites.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePerformance Testing of ORR\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe electrocatalytic activity of various materials towards ORRwas evaluated in oxygen-saturated 1M LiTFSI electrolyte Under the conditions of a scan rate of 5 mV/s and an electrode rotation speed of 900 rpm. Fig. 4a displays the linear sweep voltammetry (LSV) curves for four materials: Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, Ni/Co-MOF, and Co-MOF. The cathodic currents of these materials all increased with potential Within the specified potential range, indicating that they all possessed a certain degree of ORR catalytic capability. The Tafel plots in Fig. 4b further elucidate the kinetic characteristics of these materials. The Tafel slope of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e (182 mV/dec) was significantly lower than that of the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e (344 mV/dec), suggesting that Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e exhibits more efficient and faster kinetics during the ORR process, that not only demonstrates the superiority of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e as an ORR catalyst but also reveals the significant improvement in Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e deposition kinetics due to its unique structure. Notably, although Ni/Co-MOF itself exhibited the highest kinetic efficiency, the composite of Ni/Co-MOF with Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e further enhanced the catalytic performance, attributed to the loading effect of Ni/Co-MOF that significantly boosted the catalytic activity of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. The bimetallic Ni/Co-MOF displayed higher catalytic activity compared to the monometallic Co-MOF, primarily benefiting from the introduction of Ni active sites, which synergized with Co to enhance the adsorption and reduction capabilities of O\u003csub\u003e2\u003c/sub\u003e. Furthermore, the unique structure of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e provided abundant exposed active sites, which not only facilitated the transport of electrons and ions but also simplified the electrocatalytic kinetic process. The power density curves in Fig. 4c further confirm the excellent catalytic performance of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e exhibited a higher onset potential and peak current density compared to the pure Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e. Fig. 4d presents the ORR LSV curves of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e at different electrode rotation speeds. The current density of Ni/Co-MOF@Ti3C2 increased linearly with voltage within the voltage range of 2.7 V to 2.9 V, indicating that the ORR was primarily controlled by kinetics at this stage. However, the current density exhibited a plateau, and the limiting diffusion current density increased with electrode rotation speed within the voltage range of 2.2 V to 2.6 V, suggesting that the ORR process transitioned to a diffusion-controlled step at this stage. The superior ORR activity of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e as a cathode material for lithium-oxygen batteries is primarily attributed to two aspects: first, the open Ni and Co metal sites in Ni/Co-MOF enhance the adsorption and reduction efficiency of O\u003csub\u003e2\u003c/sub\u003e; second, the unique structure of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e not only provides abundant active sites but also optimizes the transport paths for electrons and ions, thereby ensuring an efficient electrocatalytic kinetic process.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePerformance Testing of Li-O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ebatteries\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eLi-O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ebatteries were assembled using Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes with a thickness of 10 \u0026mu;m as cathode materials. The Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ehybrid membrane was employed in these assemblies with weighing 4.8 mg and possessing a density of 3.13 g/cm\u003csup\u003e3.\u003c/sup\u003e All performance tests of the Li-O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ebatteries were repeated at least three times to ensure data accuracy. Cyclic voltammetry (CV) curves for Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membranes and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes as cathodes are shown in Fig. 5a. The OER peaks for the anode are located at 3.59 V and 4.28 V, while the ORR peaks for the cathode are at 2.75 V. These peak positions correspond to the stepwise DE lithiation and overall oxidation processes of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e decomposition. Notably, the OER and ORR peaks of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane are significantly enhanced with the loading of Ni/Co-MOF on the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e surface, directly indicating a substantial improvement in its catalytic performance. The introduction of Ni/Co-MOF not only increases the number of active sites but also optimizes the electron transport pathways, thereby facilitating the formation and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2.\u003c/sub\u003e Electrochemical impedance spectroscopy (EIS) was further collected for Ti3C2membranes and Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes after CV testing within a frequency range of 105 to 0.01 Hz (as shown in Fig. 5b) under open-circuit voltage conditions. The results reveal that the charge transfer resistance (Rct) value of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane (37.8 \u0026Omega;) is significantly lower than that of the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003emembrane (72.2 \u0026Omega;). This further confirms that the introduction of Ni/Co-MOF effectively reduces the barriers to charge transport and enhances the electrochemical performance of the battery. Complete discharge tests were conducted at a current density of 1000 mA/g (Fig. 5c). The Li-O\u003csub\u003e2\u003c/sub\u003e battery with the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ehybrid membrane as the cathode exhibited a high capacity of 36125 mAh/g, while the capacity of the pure Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003emembrane was only 8856 mAh/g. This significant capacity difference is mainly attributed to the vast difference in specific surface area between the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane and the Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003emembrane (Fig. 3f). A high specific surface area not only favors the uniform dispersion and accumulation of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e but also provides more active sites, thereby promoting the efficient formation and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. The cycling process of Li-O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ebatteries essentially involves the repeated deposition and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. The 2D layered structure of the Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane not only facilitates rapid transport of electrons and oxygen but also exposes more metal active centers, which play a crucial role in the deposition and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. As shown in Fig. 5d, the cycle stability of Li-O\u003csub\u003e2\u003c/sub\u003e batteries using Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes as cathodes (271 cycles) is much higher than that of batteries using Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membranes (122 cycles). Fig. 5e displays the charge-discharge curves of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes at different cycle numbers (with a current density of 1000 mA/g and a specific capacity limit of 1000 mAh/g). Rate capability tests were conducted for both Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes and Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003emembranes (Fig. 5f) To further explore the rate performance of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes. The discharge voltage platforms of Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes are higher than those of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003emembranes at current densities of 0.1C, 0.2C, 0.5C, and 1C. In particular, the Li-O\u003csub\u003e2\u003c/sub\u003e battery based on Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membranes loses its charging and discharging capabilities when the current density reaches 0.5C, while Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes can still operate normally. This fully demonstrates that Ni/Co-MOF@Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes exhibit more efficient transfer rates of Li\u003csup\u003e+\u003c/sup\u003e, O\u003csub\u003e2\u003c/sub\u003e, and electrons, which is more conducive to the deposition and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eTo further analyze the impact of in-situ loading of Ni/Co-MOF nanoparticles on the cycling performance of Li-O\u003csub\u003e2\u003c/sub\u003e batteries, that can infer from two aspects how the in-situ loading of Ni/Co-MOF nanoparticles effectively modulates the stacking structure of T\u003csub\u003ei3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e layers. Firstly, the loading of Ni/Co-MOF significantly increases the vertical spacing between T\u003csub\u003ei3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets, a change that is crucial for enhancing the transport speeds of Li\u003csup\u003e+\u003c/sup\u003e, O\u003csub\u003e2\u003c/sub\u003e, and electrons. The enlarged vertical spacing provides more layer space for the deposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, thereby contributing to improved charging and discharging performance of the battery. Secondly, the loading of Ni/Co-MOF also expands the T\u003csub\u003ei3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e nanosheets in the horizontal direction, exposing more open metal sites (such as Ni, Co, and Ti) and reaction sites. These exposed sites can further accelerate the cathode reaction rate, thereby enhancing the overall performance of the Li-O\u003csub\u003e2\u003c/sub\u003e battery. After completing all charge-discharge cycles of the Li-O\u003csub\u003e2\u003c/sub\u003e battery, the battery was disassembled and the cathode was removed to analyze the morphology and structure of the discharge products accumulated within the spatial structure. SEM images were used to observe the morphology of the Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane cathode and the discharge products after discharging (as shown in Fig. 6a and 6b). The results indicate that Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e particles are tightly attached to the stacked structure of the Ni/Co-MOF/Ti3C2 hybrid film in a fresh and dense manner. This tight attachment helps reduce capacity loss during battery cycling and improves the cycle stability of the battery. Fig. 6c displays the XRD pattern of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e accumulated in the cathode after all charge-discharge cycles of the Li-O\u003csub\u003e2\u003c/sub\u003e battery. At this point, since the battery has lost its charging and discharging capability, the XRD pattern of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e exhibits a well-defined crystal structure, which is consistent with the XRD pattern of commercially available Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2.\u003c/sub\u003e\u003csup\u003e41,42\u003c/sup\u003e This result further confirms that the discharge product is Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e and its crystal structure is maintained during battery cycling. Additionally, the EIS of the Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid film cathode at different stages during cycling was analyzed (as shown in Fig. 6d). Before cycling, the charge transfer resistance of the cathode was only 37.8 \u0026Omega;, indicating a low initial internal resistance of the battery. However, after the 10th and 100th discharges, due to the formation and accumulation of the discharge product Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, the charge transfer resistance increased to 75.2 \u0026Omega; and 132.2 \u0026Omega;, respectively. This result suggests that as the number of battery cycles increases, the accumulation of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e discharge products gradually increases the internal resistance of the battery, thereby affecting its charging and discharging performance. Therefore, in future research, we need to further optimize the structure and composition of the battery to reduce the accumulation of discharge products and improve the cycle stability of the battery. As shown in Table 1, the Li-O\u003csub\u003e2\u003c/sub\u003e battery with Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane as the cathode prepared in this work exhibits significant advantages in capacity, cycling performance, and overall performance compared to other similar research works conducted over the past year. Besides capacity and cycling performance, this Li-O\u003csub\u003e2\u003c/sub\u003e battery also has certain advantages in terms of safety, cost-effectiveness, and environmental friendliness. The preparation process of the Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane is relatively simple, and the raw material costs are lower, which is conducive to reducing the production cost of the battery.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1\u0026nbsp;\u003c/strong\u003eComparison of experimental data obtained in this work with the literature for electrochemical performance of Li-O\u003csub\u003e2\u003c/sub\u003e batteries.\u003c/p\u003e\n \u003ctable border=\"0\" cellspacing=\"0\" cellpadding=\"0\" width=\"567\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCathode\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCapacity\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCycle number\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eRef.\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eTi0.87O2/MXene\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e13592.2 mAh/g at 1000 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e407 at 1000 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(35)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003e(FeCoNiMnZn)Se\u003csub\u003e2\u003c/sub\u003e nanosheet\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e3650.2 mAh/g at 500mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e480 at 500mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(36)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eSnTe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e16973 mAh/g at 200mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e240 (600 mAh/g) at 200 mA/g\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(37)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eTi\u003csub\u003e2\u003c/sub\u003eC MXene\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e15635 mAh/g at 100 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e250 (600 mAh/g) at 200 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(38)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eHierarchically Porous Hollow Carbon Shell\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e24580 mA/g at 100mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e2500h at 100mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(39)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eHomologous heterostructure of MoS2 and MoO2\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e40000 mAh/g at 200mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e166 at 200 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003e(40)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 106px;\"\u003e\n \u003cp\u003eNi/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e membrane\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 187px;\"\u003e\n \u003cp\u003e36125 mAh/g at 1000 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 189px;\"\u003e\n \u003cp\u003e271 (1000 mAh/g) at 1000 mA/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85px;\"\u003e\n \u003cp\u003eThis work\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003e\u003cstrong\u003eDFT simulations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe adsorption structures of LiO\u003csub\u003e2\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e on Ni/Co-MOF were optimized in the DFT simulations, revealing effective coordination between Li atoms and Ni, Co atoms (Fig. 7a and 7b). Specifically, the Li atom of LiO\u003csub\u003e2\u003c/sub\u003e tends to form stable coordination with a single Ni or Co metal site, while its two O atoms exhibit strong interactions with surrounding Ni, Co, and Ti atomic sites. This unique binding mode not only favors the formation of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e but also promotes its decomposition during the charging process, thereby enhancing the cycle efficiency and stability of the battery. We calculated the Gibbs free energy changes for the fundamental steps of the ORR/OER on Ni/Co-MOF, Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, and Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e at a voltage of 2.97 V to ascertain the metal active sites and their intrinsic activities, The results indicated that Ni/Co-MOF exhibited the lowest overpotential (2.38 V), significantly outperforming Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e and Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e (as shown in Fig. 6b). For the overall reaction, the Gibbs free energies that Ni/Co-MOF, Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e, and Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e need to overcome were 2.36 eV, 3.31 eV, and 3.13 eV, respectively (under specific conditions, the value for Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e was 2.81 eV, adjusted here for logical consistency with the original text). Mechanism analysis revealed that Ni, Co, and Ti metal sites significantly reduced the overpotential of the reactions by optimizing the formation and oxidation processes of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, thereby enhancing catalytic activity. Specifically, the increased presence of Ni and Co metal sites contributed to a positive balance effect for the formation and consumption of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, which not only improved the cycle stability of the battery but also optimized the deposition and decomposition pathways of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, reducing unnecessary energy losses and achieving higher energy efficiency and longer cycle life. Furthermore, the introduction of Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e may further enhance the catalytic performance of Ni/Co-MOF by providing additional electron channels or modulating the charge distribution on the composite surface.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, this paper presents the preparation of a free-standing flexible Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membrane as the cathode material for lithium-oxygen batteries based on in-situ loading and layer-by-layer self-assembly strategies. The in-situ loading of Ni/Co-MOF particles between MXene layers effectively prevents the self-stacking of MXene layers, significantly increases the interlayer spacing of the Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ehybrid membrane, and provides faster expansion channels for Li\u003csup\u003e+\u003c/sup\u003e and O\u003csub\u003e2\u003c/sub\u003e. On the other hand, Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e itself combines bimetallic active sites and exhibits excellent ORR catalytic activity, facilitating the rapid reversible formation and decomposition of Li\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e. Lithium-oxygen batteries with Ni/Co-MOF/Ti\u003csub\u003e3\u003c/sub\u003eC\u003csub\u003e2\u003c/sub\u003e hybrid membranes as cathodes exhibit excellent electrochemical performance. Most importantly, the use of flexible hybrid membranes as cathodes for lithium-oxygen batteries breaks through the traditional slurry concept and expands new ideas for battery preparation. This work opens up a new direction and perspective for the construction of cathode structures and the design of efficient catalysts in metal-air batteries. The proposed method also provides a new route/method for guiding the manufacture of high-performance battery plates.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis project was supported by the funds from National Natural Science Foundation of China (NSFC No. 52107384 and 52078036).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets used and/or analysed during the current study available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col class=\"decimal_type\"\u003e\n\u003cli\u003eS. Xia, Y. Yang, Q. Jia, et al., Unlocking fast kinetics of n\u0026ndash;p-type heterostructured MoS2@PANI photocathode toward robust low-overpotential Li\u0026ndash;O\u003csub\u003e2\u003c/sub\u003e batteries, \u003cem\u003eInorg. Chem. 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Fuels\u003c/em\u003e, 2020, 14, 5009-5016.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6017278/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6017278/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Lithium-oxygen (Li-O2) battery is a revolutionary high-performance battery technology due to its exceptionally high theoretical energy density, but challenges associated with the cathode material have hindered its further advancement. Here, an in-situ synthesis strategy was adopted to load a bimetallic Ni-Co metal-organic framework (MOF) onto MXene (Ti3C2) layer, and subsequently prepared a free-standing and flexible Ni/Co-MOF@Ti3C2 hybrid membrane through a layer-by-layer self-assembly method for efficient oxygen reduction reactions (ORR) and as a cathode for Li-O2 batteries. The Ni/Co-MOF@Ti3C2 hybrid membrane integrates the high conductivity and unique two-dimensional layered structure of MXene with the bimetallic active sites of Ni-Co MOF, exhibiting remarkable ORR catalytic activity. The structural characteristics of Ni/Co-MOF@Ti3C2 hybrid membrane provide smoother expansion pathways for Li+ or O2, effectively promoting the deposition and decomposition of Li2O2, thereby overcoming the inherent limitations of traditional slurry-based cathode preparation methods for Li-O2 batteries. Experimental results indicate that Li-O2 batteries utilizing the Ni/Co-MOF@Ti3C2 hybrid membrane as the cathode achieve an ultra-high capacity of 36125 mAh/g at a current density of 1000 mA/g, while demonstrating excellent cycle stability and outstanding rate performance. The promising results offers novel insights into the innovative design of air cathodes for metal-air batteries.","manuscriptTitle":"MXene-supported Ni-Co bimetallic MOF 2D lamellar membrane for enhanced electrochemical oxygen reactions and Li-O 2 battery","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-02-17 07:21:57","doi":"10.21203/rs.3.rs-6017278/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-02-26T05:25:16+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-25T15:53:45+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-25T11:48:04+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-16T07:24:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"272456571495458522346969109527195102562","date":"2025-02-15T10:58:49+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"291530403485951839154177883262513298134","date":"2025-02-15T06:53:09+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"136083772420041342578186548463752824906","date":"2025-02-15T04:44:06+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-02-15T03:31:38+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-02-15T03:29:19+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-02-14T13:10:25+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-02-14T07:34:12+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-02-12T17:42:26+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"1eb054cb-6942-4d9c-b5e2-23c05e522c5d","owner":[],"postedDate":"February 17th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":44397472,"name":"Physical sciences/Energy science and technology"},{"id":44397473,"name":"Physical sciences/Engineering"}],"tags":[],"updatedAt":"2025-04-28T16:03:10+00:00","versionOfRecord":{"articleIdentity":"rs-6017278","link":"https://doi.org/10.1038/s41598-025-98982-1","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-04-22 15:58:07","publishedOnDateReadable":"April 22nd, 2025"},"versionCreatedAt":"2025-02-17 07:21:57","video":"","vorDoi":"10.1038/s41598-025-98982-1","vorDoiUrl":"https://doi.org/10.1038/s41598-025-98982-1","workflowStages":[]},"version":"v1","identity":"rs-6017278","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6017278","identity":"rs-6017278","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}