A mechanical strategy of surface anchoring to enhance the electrochemical performance of ZnO/NiCo2O4@NF self-supporting anode for lithium-ion batteries

A mechanical strategy of surface anchoring to enhance the electrochemical performance of ZnO/NiCo2O4@NF self-supporting anode for lithium-ion batteries | 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 Research Article A mechanical strategy of surface anchoring to enhance the electrochemical performance of ZnO/NiCo 2 O 4 @NF self-supporting anode for lithium-ion batteries Yanbin Xu, Xingang Liu, Shuai Wang, Zhenyu Fu, Lixiang Sun, Wenfan Feng, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4970654/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 12 Nov, 2024 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted 10 You are reading this latest preprint version Abstract NiCo 2 O 4 has the advantages of high energy density, low cost, and environment-friendly as the anode materials of lithium-ion batteries. However, NiCo 2 O 4 is adversely affected by the slow transmission rate of lithium-ion and the collapse of its three-dimensional loose and porous nano-flake structure causes its poor cycling performance. In this study, to address this issue, the NiCo 2 O 4 @ nickel foam(NF) composite was formed by depositing ZIF-67 on nickel foam through room temperature standing and 350 ℃ treatment, and then short ZnO nanorods with an anchoring structure were grown on its surface through heat treatment and hydrothermal treatment to obtain ZnO/NiCo 2 O 4 @NF compound materials. The nano-rod structure of ZnO material increases the contact between the electrode material and electrolyte, reduces the charge transfer resistance, and its anchoring structure stabilizes the porous sheet architecture of NiCo 2 O 4 @NF. After 100 cycles (100 mA∙g − 1 ), the discharge capacity of the ZnO/NiCo 2 O 4 @NF composite electrode remained at 475.2 mAh∙g − 1 , which is significantly higher than 313.8 mAh∙g − 1 of NiCo 2 O 4 @NF electrode and 245.4 mAh∙g − 1 of ZnO@NF electrode. mechanical strategy ZnO/NiCo2O4@NF composite electrode materials surface anchoring Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction Lithium-ion batteries (LIB) are now widely used in a range of applications, from portable electronic devices such as smartphones and laptops to electric vehicles and energy storage systems for the grid[ 1 , 2 , 3 , 4 ]. The demand for high-energy-density batteries has stimulated the pursuit of advanced anode materials that can replace graphite anodes currently widely used commercially. To achieve this goal, many researchers have explored alternative materials, including silicon, titanium, and transition metal oxides, as high-capacity anode materials[ 5 , 6 , 7 , 8 , 9 , 10 ]. NiCo 2 O 4 has attracted much attention due to its high energy density, low cost, environment-friendly, and other advantages[ 11 ]. Moreover, it has a theoretical capacity of 890 mAh∙g − 1 . However, it suffers from poor cyclability due to the collapse of the three-dimensional loose and porous nano-flake structure during cycling[ 12 ]. To overcome this issue, research by Yuan et al.[ 13 ] utilized the electrostatic spray deposition (ESD) technique to deposit 3D porous NiO-NiCo 2 O 4 films directly onto the surface of 3D porous NF. The results showed that this porous NiO-NiCo 2 O 4 structure significantly improved the material's electrochemical performance. This structure exhibited high specific capacity and stable cycling behavior. Another research by Wang et al[ 14 ] synthesized carbonaceous microspheres (CMSs) using cobalt acetate tetrahydrate as a catalyst, resulting in the formation of six-shelled NiCo 2 O 4 hollow multi-shelled structures (6S-NiCo 2 O 4 -HoMSs). These low-dimensional nanostructures have a high specific surface area and excellent mass transport properties. Its multi-shelled structure effectively manages volume expansion, reduces stress and strain, promotes uniform lithium deposition, and improves battery cycle stability. Another way to mitigate the capacity decay phenomenon due to the volume effect is surface coating[ 15 ]. Surface coatings for lithium-ion battery anodes come in various structures, including monolayer, bilayer, core-shell, and hierarchical structures. And achieved by some techniques such as chemical vapor deposition (CVD)[ 16 ], atomic layer deposition (ALD)[ 17 ], and electrochemical deposition (ECD)[ 18 ]. Although these coatings offer simple and effective protection for the anode material, they may also have drawbacks such as decreased flexibility and increased cracking susceptibility[ 19 ]. Among many potential coating materials, ZnO nanorods have attracted much attention due to their high mechanical strength, more resistance to mechanical damage, and can be engineered to allow volume change[ 20 ]. In Fig. 1 , a mechanical strategy was assumed, the nanorod structure of ZnO was grown on the surface of NiCo 2 O 4 @NF composites by hydrothermal through an anchoring structure. The size of the nanorod-like ZnO is tailored to match the loose and porous nano-flake structure of NiCo 2 O 4 , enabling the ZnO/NiCo 2 O 4 @NF composite to remain stable during cycling without collapsing. The final experimental results of the anode material showed better electrical conductivity, kinetics, and cyclability. 2. Experimental methods 2.1 Experimental Preparation Procedure Firstly, 0.1455 g of Co(NO 3 ) 2 ·6H 2 O was added to 10 mL of deionized water with constant stirring to obtain solution A. Add 0.328 g of dimethylimidazole to 10 mL of deionized water and stir magnetically for 5 min to prepare Solution B. Then add Solution B quickly into Solution A and continue to stir magnetically for 5 min to obtain Solution C. Add the cleaned and pre-treated NF to Solution C, sonicate for 3 min to remove air bubbles, and let stand at room temperature for 6 h. After that, rinse the NF with anhydrous ethanol, and dry it in a vacuum oven overnight to obtain ZIF-67@ NF samples. ZIF-67@NF was then placed in a tube furnace. And the tube furnace was increased temperature to 350 ℃ with a heating rate of 2 ℃/min, then held at 350 ℃ for 2 h under an air atmosphere, and finally cooled to room temperature naturally to obtain the NiCo 2 O 4 @NF composites. A 0.05 M ethanolic solution of Zinc acetate was prepared, and the NiCo 2 O 4 @NF material was immersed in the above solution for 5 min, then dried at 80 ℃ and the above steps were repeated three times. Then, the NiCo 2 O 4 @NF material was held at 350 ℃ for 30 min under an air atmosphere with an increase rate of 2 ℃/min and then lowered to room temperature. Dissolve 0.015 M Zn(NO 3 ) 2 ∙6H 2 O, 0.015 M urotropine, and 0.6 mL ammonia in 20 mL of deionized water and keep stirring for 30 min, then pour the well-mixed solution into a 25 mL hydrothermal reactor, add annealed NF, react at 90 ℃ for 24 h. After it is lowered to room temperature, remove and wash with deionized water and anhydrous ethanol 3 times, and finally dried in an oven at 60 ℃ for 8 h. ZnO/NiCo 2 O 4 @NF target composites were obtained. In addition, the above steps were repeated directly on the pretreated clean NF. The ZnO@NF composite grown in situ on blank NF was generated and used as a comparison material for analysis together with the NiCo 2 O 4 @NF composite. The compositions and properties were analyzed together with NiCo 2 O 4 @NF composites as comparison materials. 2.2 Characterization The surface morphology was observed by scanning electron microscope (SEM, JEOL, JSM-7900F). The phase composition was determined by X-ray diffraction (XRD, Smart Lab III, Rigaku, Cu K radiation, λ = 0.1542 nm). The XRD data were collected from 2θ = 10°-80° at a scanning rate of 5°∙min − 1 . 2.3 Electrochemical performance measurements The electrode materials synthesized in the experiment were pressed together with a blank NF tablet press of the same size (pressure of 10 MPa). Then dry at 80°C for 6 hours. Put in an argon glove box and assemble it into a button battery for CR2025. The separator material was Celgard 2400 polypropylene. The electrolyte was a solution of LiPF 6 (1M) in ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) (1:1:1 in volume). Then the assembled button battery was placed in the groove of the sealing machine and applied 8 MPa pressure. After the battery is built, aging for one night, conducting a series of electrochemical performance tests. In this paper, the cycle performance and rate performance of the battery were tested by the LAND battery-testing system (CT2001A, China). Cyclic voltammetry (CV) was performed at the electrochemical workstation (CHI660E, Shanghai Chenhua, China). Tested at 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 mV s − 1 scan rate in the voltage range of 0.01-3 V. Electrochemical impedance spectrum (EIS) was carried out by electrochemical workstation (CHI660E, Shanghai Chenhua, China) in the frequency range of 100000-0.01 Hz. 3. Results and discussion To analyze the phase composition of the synthesized materials, XRD characterization was performed on the target and comparison materials. Figure 2 (a) shows the XRD spectra of the comparison material ZnO@NF, the diffraction peaks at 2θ = 32.1°, 34.5°, 36.5°, and 57.2° correspond to the (100), (002), (101), and (110) crystal planes of ZnO (JDPDS NO. 75-1526), respectively, demonstrating that ZnO on the surface of NF was successfully synthesized. The XRD spectra of the NiCo 2 O 4 @NF composites are shown in Fig. 2 (b). The diffraction peaks at 2θ = 44.7°, 52.0°, and 76.5° of the composites correspond to the (111), (200), and (220) crystal planes of Ni (JDPDS NO.87–0712), respectively. The diffraction peaks at diffraction angles 2θ = 18.9°, 31.2°, 38.4°, 59.1°, and 65.0° are attributed to the (111), (220), (222), (511), and (440) crystal planes of NiCo 2 O 4 (JDPDS NO. 73-1702). Figure 2 (c) shows the XRD spectral characterization of the target material ZnO/NiCo 2 O 4 @NF, which was successfully synthesized as a ZnO/NiCo 2 O 4 @NF composite grown in situ on NF by comparing with the PDF card. The intensity of the diffraction peaks of the synthesized material is relatively low due to the three strong diffraction peaks of the monolithic nickel, but still, obvious diffraction peaks can be seen in this figure, and the presence of the elements Ni, Co, and O can also be proved by the Mapping characterization of NiCo 2 O 4 @NF composite material shown in Fig. 2 (d), and the distribution of the three elements is very homogeneous on the NF, which once again confirms the synthesis of NiCo 2 O 4 @NF composites and shows that the NiCo 2 O 4 @NF material grows uniformly on the NF. To observe the morphological characteristics of the composites, the target materials and two comparison materials were subjected to scanning electron microscopy (SEM) characterization of the target material and the two comparison materials. Figure 3 (a, b) show the morphological features of the NiCo 2 O 4 @NF composite material at different magnifications. A unique loose and porous nano-flake structure is formed in situ on the foam nickel substrate, its pores diameter is 40–70 µm. The nano-flakes exhibit a thickness of only a few tens of nanometers and are irregularly distributed on the surface of the NF. Figure 3 (c, d) present the morphological features of the reference material ZnO at different magnifications. ZnO exhibits a disordered distribution of short rod structures on the microscale, randomly dispersed on the NF substrate. The appearance of a few conical clusters in the image may be attributed to the corrosion of the foam nickel substrate by the ZnO solution during the preparation process, resulting in the formation of a small amount of NiO morphology. Figure 3 (e, f) display the surface morphology of the ZnO/NiCo 2 O 4 @NF composite material. It is evident from the images that a layer of short rod-like ZnO structures has grown on the surface of the NiCo 2 O 4 @NF composite material. The diameter of these rods ranges from 40 to 60 nanometers, with lengths varying between 100 and 400 nanometers. Notably, a comparison between Fig. 3 (b) and Fig. 3 (e) reveals a significant increase in the synthesized ZnO when ZnO grows on the surface of the NiCo 2 O 4 @NF composite material. This increase can be attributed to the fact that the sheet-like porous structure of the NiCo 2 O 4 @NF composite material, with its diameter-matched pores of 400–700 nanometers, provides a favorable surface for the attachment and anchoring of ZnO nanorods. Consequently, the quantity of hydrothermally synthesized nano-rods is enhanced. The uniform coating of ZnO on the surface of the NiCo 2 O 4 @NF composite material is beneficial for improving the fragility associated with its loose and porous structure, thereby enhancing structural stability. The target material was utilized as a lithium-ion negative electrode material and assembled into a button cell to evaluate its electrochemical performance. Figure 4 (a) illustrates the cyclic voltammetry (CV) curves of the NiCo 2 O 4 @NF electrode, ZnO, and ZnO/NiCo 2 O 4 @NF electrode within the voltage range of 0.01-3.00 V at a scan rate of 0.1 mV s − 1 . The reduction peak of NiCo 2 O 4 @NF appears at 1.06 V during the negative scan, corresponding to the reduction process of Ni 2+ and Co 2+ to metallic Ni and Co, as indicated by the discharge plateau at 1.3 V in Fig. 4 (b) of the NiCo 2 O 4 @NF discharge curve. In Fig. 4 (a), the oxidation peaks observed at 0.3, 0.4, 0.55, 0.7, and 1.4 V during the positive scan for ZnO and ZnO/NiCo 2 O 4 @NF are associated with the oxidation of metallic Zn to Zn 2 [ 21 ]. The oxidation peak observed at 2.25 V for ZnO/NiCo 2 O 4 @NF corresponds to the oxidation of metallic Ni and Co to Ni 2+ and Co 2+ . The reduction peak at 1.1 V during the negative scan for ZnO/NiCo 2 O 4 @NF corresponds to the discharge plateau at 1.35 V in the galvanostatic charge-discharge curve. As shown in Fig. 4 (a), The peak potential gaps for NiCo 2 O 4 @NF, ZnO/NiCo 2 O 4 @NF, and ZnO are 1.217 V, 1.15 V, and 1.143 V, respectively. It is evident that after the anchoring of ZnO, NiCo 2 O 4 @NF composite material has a stronger anodic/cathodic peak intensity and a smaller potential gap between the reduction and oxidation peaks which indicates faster Li + diffusion kinetics and lower polarization[ 22 ]. Cycling and rate capability tests were conducted to investigate the electrochemical performance of the ZnO/NiCo 2 O 4 @NF electrodes in button battery. Figure 5 (a) presents the capacity and stability tests of the electrodes after 100 cycles at a current density of 100 mA∙g − 1 . The NiCo 2 O 4 @NF electrode, ZnO electrode, and ZnO/NiCo 2 O 4 @NF electrode exhibited initial discharge specific capacities of 1516.6/1116.9 mAh∙g − 1 , 1133.1/722.6 mAh∙g − 1 , and 1460.1/944.6 mAh∙g − 1 , respectively. The corresponding first-cycle coulombic efficiencies were 73.6%, 63.8%, and 64.7%. After 100 charge-discharge cycles, the discharge-specific capacities of the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF electrodes reached 313.8, 245.4, and 475.2 mAh∙g − 1 , respectively. The capacity retention rates after 100 cycles, relative to the second cycle, were 28.2%, 34.6%, and 51.5% for the three electrodes, respectively. The ZnO/NiCo 2 O 4 @NF electrode exhibited the highest capacity and capacity retention rate after 100 cycles. The addition of ZnO enhanced the stability of the material, resulting in slower capacity decay during cycling. Figure 5 (b) shows the rate capability test results of the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF electrodes. At current densities of 100, 200, 400, 800, and 1600 mA∙g − 1 , the discharge capacities of the NiCo 2 O 4 @NF electrode were 1409.8, 1261.8, 1021.1, 836.9, and 658.4 mAh∙g − 1 , respectively. The corresponding specific capacities of the ZnO@NF electrode were 541.2, 377.5, 296.8, 244.6, and 204.5 mAh∙g − 1 , while the ZnO/NiCo 2 O 4 @NF composite electrode exhibited specific capacities of 828.6, 657.2, 499.8, 432.4, and 357.3 mAh∙g − 1 . When the current density was restored from 1600 mA∙g − 1 to 100 mA∙g − 1 , the capacities of the NiCo 2 O 4 @NF electrodes were 917.0, 342.5, and 540.1 mAh∙g − 1 , respectively. The capacity loss rates, relative to the initial cycle at 100 mA g − 1 , were 35.0%, 36.7%, and 33.9% for the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF composite electrodes, indicating relatively good reversibility for the ZnO/NiCo 2 O 4 @NF composite electrode. The improved reversibility is likely attributed to the anchoring of the ZnO nanorod with high mechanical strength on the surface of the ZnO/NiCo 2 O 4 @NF composite electrode, which enhances its structural stability under high current conditions. To further analyze the factors influencing the electrochemical kinetics of the materials, cyclic voltammetry (CV) tests were conducted on the three electrodes at different scan rates. Figure 6 (a, c, e) displays the CV curves of the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF electrodes at scan rates of 0.2, 0.4, 0.6, 0.8, and 1.0 mV∙s − 1 . With different scan rates, the CV curves of the three electrodes exhibit similar shapes, with an increase in the magnitude of oxidation/reduction peaks and slight shifting, indicating minor polarization of the electrode materials. Figure 6 (b, d, f) presents the plots of log v versus log i for the cathodic and anodic scans. The relationship between the current density i and the scan rate ν follows the equation log i = b *log ν + log a , where the value of adjustable parameter b reflects the controlling process during electrode charge and discharge. The b values for the NiCo 2 O 4 @NF electrode are 0.44 and 0.6, while for the ZnO@NF electrode, the b values are 0.68 and 0.7. As for the ZnO/NiCo 2 O 4 @NF electrode, the b values are 0.5 and 0.64. Overall, the NiCo 2 O 4 @NF electrode is primarily controlled by the diffusion process, while the ZnO@NF electrode is controlled by a combination of capacitance and diffusion processes. The ZnO/NiCo 2 O 4 @NF electrode exhibits b values between those of the other two electrodes, indicating that the diffusion process remains the primary control mechanism. Finally, the electrochemical impedance spectroscopy of the three electrodes was further discussed and analyzed. Figure 7 (a) shows the Nyquist plots of the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF electrodes before the charge-discharge cycling test. The plots for all three electrodes exhibit similar shapes, consisting of a semicircle and a sloping line. The semicircle in the high-frequency region represents the charge transfer impedance, while the sloping line in the low-frequency region indicates the Warburg diffusion impedance. From the graph, it can be observed that the charge transfer impedances of those electrodes are 908.5, 1162.9, and 245.8 Ω, respectively. The ZnO/NiCo 2 O 4 @NF electrode exhibits the smallest charge transfer impedance, which may be attributed to the formation of a dense layer of ZnO nanorods, increasing the contact area with the electrolyte. Figure 7 (b) shows the diffusion impedances of Li + within the materials for the three electrodes. It can be seen that the ZnO/NiCo 2 O 4 @NF electrode has the lowest diffusion impedance, indicating a relatively lower impedance within the material. Figure 7 (c) presents the impedance test curves of the NiCo 2 O 4 @NF, ZnO@NF, and ZnO/NiCo 2 O 4 @NF electrodes after 30 charge-discharge cycles. It is worth noting that the NiCo 2 O 4 @NF electrode exhibits a semicircle and a sloping line, while the ZnO@NF and ZnO/NiCo 2 O 4 @NF electrodes consist of two semicircles and a sloping line. The presence of two semicircles in the latter two electrodes indicates the existence of two interface electron transfer processes. The appearance of two semicircles in the ZnO@NF electrode is attributed to the interface between the rod-like ZnO and the accompanying clustered NiO with the electrolyte, while the two semicircles in the ZnO/NiCo 2 O 4 @NF electrode arise from the interfaces formed between the rod-like ZnO and the porous sheet-like NiCo 2 O 4 @NF material with the electrolyte. The smallest semicircle in the Nyquist plot of the ZnO/NiCo 2 O 4 @NF electrode indicates the lowest charge transfer impedance, while Fig. 7 (d) also shows the smallest diffusion impedance after 30 cycles among the three electrode materials, reflecting optimal interface charge transfer rate and bulk lithium-ion transport rate. 4. Conclusions In this work, NiCo 2 O 4 @NF composites were generated by calcination of the synthesized ZIF-67 with NF, followed by the growth of ZnO material on the surface to obtain ZnO/NiCo 2 O 4 @NF composites with optimized electrochemical properties compared to the comparison materials NiCo 2 O 4 @NF and ZnO@NF. The ZnO/NiCo 2 O 4 @NF morphology presents a short rod-like structure grown on the porous lamellar NiCo 2 O 4 @NF composite, which has a unique structure with significant stability in charge/discharge cycles and high specific capacity compared to the NiCo 2 O 4 @NF material with loose porous lamellar shape. The ZnO/NiCo 2 O 4 @NF composite electrode can reach a specific capacity of 475.2 mAh∙g − 1 after 100 cycles (100 mA∙g − 1 ), which is significantly higher than the 313.8 mAh∙g − 1 of NiCo 2 O 4 @NF electrode and 245.4 mAh∙g − 1 of ZnO@NF electrode under the same test conditions. The anchoring of ZnO nanorods on the surface of the composites effectively addressed the issue of the collapse of the NiCo 2 O 4 during cycling and resulted in improved electrical conductivity, kinetics, and cyclability. The results of this work suggest that the mechanical structure could be a promising strategy for improving the performance of high-capacity anode materials. Declarations Author contribution: Lixiang Sun, Zhenglong Yang and Zhe Wang designed this project and contributed to the main manuscript text. Yanbin Xu and Xingang Liu conducted experiments and contributed equally to this work. Shuai Wang, Zhenyu Fu, Wenfan Feng, Zhiqiang Lv, Yuming Cui, Xiao Li, Ping Yin, Ashely DeMerleand Ethan Burcar have contributed to conducting the experiments, preparing figures, and writing. All authors reviewed the manuscript. Funding: This work was supported by Yantai Science and Technology Innovation Development Planning(2022XDRH007, Campus Local Integration Project), and was partially supported by the National Natural Science Foundation of China (No. 52173075). ZW would like to acknowledge the support from Oakland University. Data availability: The authors declare that the data supporting the findings of this study are available within the paper. Should any raw data files be needed in another format, they are available from the corresponding author upon reasonable request. Competing Interests: The authors declare no competing interests. References Chen J, Wu J, Wang X, Yang Z (2021) Research progress and application prospect of solid-state electrolytes in commercial lithium-ion power batteries. Energy Storage Mater 35:70–87 Sethurajan M, Gaydardzhiev S (2021) Bioprocessing of spent lithium ion batteries for critical metals recovery–A review. Resources, Conservation and Recycling. ;165:105225 Zhu P, Gastol D, Marshall J, Sommerville R, Goodship V, Kendrick E (2021) A review of current collectors for lithium-ion batteries. J Power Sources 485:229321 Wang Y, Fu Z, Xu Y, Yin P, Yang L-X, Wang F, Guo X, Liu G, Yang Z-L (2022) Simple preparation of two-dimensional lamellar ammonium cobalt phosphate materials derived from ZIF-L and its application in supercapacitors. J Alloys Compd 927:167030 Qiao L, Wang X, Sun X, Li X, Zheng Y, He D (2013) Single electrospun porous NiO–ZnO hybrid nanofibers as anode materials for advanced lithium-ion batteries. Nanoscale 5:3037–3042 Xie J, Tang F, Li H, Jiang W, Yang Z, Zhao D, Xu Y, Meng Y, Sun W, Jiang Z (2023) FeMoO4/N-doped porous carbon composites as anode material for high-performance lithium-ion batteries. J Electroanal Chem. :117623 Zhou W, Cheng C, Liu J, Tay YY, Jiang J, Jia X, Zhang J, Gong H, Hng HH, Yu T (2011) Epitaxial growth of branched α-Fe2O3/SnO2 nano‐heterostructures with improved lithium‐ion battery performance. Adv Funct Mater 21:2439–2445 Xu Y, Burns R, Liu Z, Wang Z (2020) Nanostructure interface for lithium-ion batteries. Advanced Nanomaterials for Electrochemical-Based Energy Conversion and Storage. Elsevier, pp 35–67 Fu Z, Wang Y, Xu Y, Li H, Qiao Q, Yin P, Wang F, Guo X, Yang Z (2022) The surface coating strategy enhances the lithium storage performance of Ni3S2@ PPy self-supporting as anode materials for lithium-ion batteries. J Alloys Compd 926:166889 Wang D, Wang Y, Fu Z, Xu Y, Yang L-X, Wang F, Guo X, Sun W, Yang Z-L (2021) Cobalt–nickel phosphate composites for the all-phosphate asymmetric supercapacitor and oxygen evolution reaction. ACS Appl Mater Interfaces 13:34507–34517 Wang D, Xu Y, Guo X, Fu Z, Yang Z, Sun W (2021) Nickel foam as conductive substrate enhanced low-crystallinity two-dimensional iron hydrogen phosphate for oxygen evolution reaction. J Alloys Compd 870:159472 An C, Wang Y, Huang Y, Xu Y, Xu C, Jiao L, Yuan H (2014) Novel three-dimensional NiCo 2 O 4 hierarchitectures: solvothermal synthesis and electrochemical properties. CrystEngComm 16:385–392 Yuan J, Gao S, Lai W, Zheng S, Meng J, Zhang X, Zhu X, Yu H, Li X (2019) Facile fabrication of 3D porous NiO–NiCo 2 O 4 film for superior lithium storage. J Mater Sci: Mater Electron 30:16008–16014 Witherspoon E, Ling P, Winchester W, Zhao Q, Ibrahim A, Riley KE, Wang Z (2022) Highly Selective Electrochemical Synthesis of Urea Derivatives Initiated from Oxygen Reduction in Ionic Liquids. ACS omega 7:42828–42834 Huang X, Xia X, Yuan Y, Zhou F (2011) Porous ZnO nanosheets grown on copper substrates as anodes for lithium ion batteries. Electrochim Acta 56:4960–4965 Du ZZ, Guo CK, Wang LJ, Hu AJ, Jin S, Zhang TM, Jin HC, Qi ZK, Xin S, Kong XH, Guo YG, Ji HX, Wan LJ (2017) Atom-Thick Interlayer Made of CVD-Grown Graphene, Film on Separator for Advanced Lithium-Sulfur Batteries. ACS Appl Mater Interfaces 9:43696–43703 Aravindan V, Jinesh KB, Prabhakar RR, Kale VS, Madhavi S (2013) Atomic layer deposited (ALD) SnO2 anodes with exceptional cycleability for Li-ion batteries. Nano Energy 2:720–725 Li X, Shao CL, Wang XL, Wang JJ, Liu GX, Yu WS, Dong XT, Wang JX (2022) Preparation of Fe3O4/FexSy heterostructures via electrochemical deposition method and their enhanced electrochemical performance for lithium-sulfur batteries. Chem Eng J. ;446 Guan P, Zhou L, Yu Z, Sun Y, Liu Y, Wu F, Jiang Y, Chu D (2020) Recent progress of surface coating on cathode materials for high-performance lithium-ion batteries. J Energy Chem 43:220–235 Wang X, Ahmad M, Sun H (2017) Three-Dimensional ZnO Hierarchical Nanostructures: Solution Phase Synthesis and Applications. Materials 10:1304 Wu GL, Jia ZR, Cheng YH, Zhang HX, Zhou XF, Wu HJ (2019) Easy synthesis of multi-shelled ZnO hollow spheres and their conversion into hedgehog-like ZnO hollow spheres with superior rate performance for lithium ion batteries. Appl Surf Sci 464:472–478 Fan YC, He X, Li HJ, Huang YT, Sun CH, Liu HY, Huangzhang E, Sun F, Zhao XY, Nan JM (2022) Lithiophilic Ni3S2 layer decorated nickel foam (Ni3S2@Ni foam) with fast ion transfer kinetics for long-life lithium metal anodes. Chem Eng J. ;450 Additional Declarations No competing interests reported. Supplementary Files SupportingInformation.docx Graphicalabstract.png Graphical Abstract Cite Share Download PDF Status: Published Journal Publication published 12 Nov, 2024 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted Editorial decision: Revision requested 14 Oct, 2024 Reviews received at journal 14 Oct, 2024 Reviewers agreed at journal 05 Oct, 2024 Reviews received at journal 30 Sep, 2024 Reviewers agreed at journal 19 Sep, 2024 Reviewers agreed at journal 19 Sep, 2024 Reviewers invited by journal 14 Sep, 2024 Editor assigned by journal 14 Sep, 2024 Submission checks completed at journal 29 Aug, 2024 First submitted to journal 24 Aug, 2024 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-4970654","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":356399237,"identity":"0deb0f8b-715c-4721-b2ab-1b80d32b4f5b","order_by":0,"name":"Yanbin Xu","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Yanbin","middleName":"","lastName":"Xu","suffix":""},{"id":356399238,"identity":"b5ef941c-5b34-49d4-8e12-1adf4170dda1","order_by":1,"name":"Xingang Liu","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Xingang","middleName":"","lastName":"Liu","suffix":""},{"id":356399239,"identity":"7dc20825-1505-4544-8245-eb7c2aae018c","order_by":2,"name":"Shuai Wang","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Shuai","middleName":"","lastName":"Wang","suffix":""},{"id":356399240,"identity":"af4e497c-66cf-4691-8127-a4cf8aa8db3f","order_by":3,"name":"Zhenyu Fu","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Zhenyu","middleName":"","lastName":"Fu","suffix":""},{"id":356399241,"identity":"7ca7816b-2269-4159-a311-b18949bef1b4","order_by":4,"name":"Lixiang Sun","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Lixiang","middleName":"","lastName":"Sun","suffix":""},{"id":356399242,"identity":"185a962a-c74f-496a-9cb3-b9963e8cd616","order_by":5,"name":"Wenfan Feng","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Wenfan","middleName":"","lastName":"Feng","suffix":""},{"id":356399243,"identity":"bb788e43-89b7-40dd-892e-daf75792407e","order_by":6,"name":"Zhiqiang Lv","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Zhiqiang","middleName":"","lastName":"Lv","suffix":""},{"id":356399244,"identity":"0f8ecf83-ee43-4d55-b35b-1fb0a9602921","order_by":7,"name":"Yuming Cui","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Yuming","middleName":"","lastName":"Cui","suffix":""},{"id":356399245,"identity":"08e13eec-3394-4e8b-b07b-1844d59ac963","order_by":8,"name":"Xiao Li","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Xiao","middleName":"","lastName":"Li","suffix":""},{"id":356399246,"identity":"d610f46d-d3a2-4bec-bef6-63802f2c1e22","order_by":9,"name":"Ping Yin","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Ping","middleName":"","lastName":"Yin","suffix":""},{"id":356399247,"identity":"f33869e6-e24a-4339-a5ec-246d6efc1762","order_by":10,"name":"Ashely DeMerle","email":"","orcid":"","institution":"Oakland University","correspondingAuthor":false,"prefix":"","firstName":"Ashely","middleName":"","lastName":"DeMerle","suffix":""},{"id":356399248,"identity":"0a44c53a-968b-45db-91c6-706a075b056f","order_by":11,"name":"Ethan Burcar","email":"","orcid":"","institution":"Oakland University","correspondingAuthor":false,"prefix":"","firstName":"Ethan","middleName":"","lastName":"Burcar","suffix":""},{"id":356399249,"identity":"b99faa44-8a0a-4dd0-8f25-c03cdbb6439c","order_by":12,"name":"Zhe Wang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA5ElEQVRIiWNgGAWjYDACCQglx8DAxniAgYEZyE4gTosxUAsDaVoSG4jWIj+7+ZjEzx216f3sxxIO/NxhzcDPnmOAVwvjnGNpkr1njufO7Ek7cLD3TDqDZM8b/FqYJXLMbvC2HcvdcCC94QBv22EGgxsEbGGTyP9282/bsXSD888bDv4FarEnpIVHIoftNm9bTYLBjbQDh8G2SBDQIiGRZv5btu2A4cwZzxIOy7al80iceVaAV4v8jOTHhm/b6uT5+dMMH75ts5bjb0/egFcLFBxGuJQY5SBQR6zCUTAKRsEoGIkAAI2GS9xm4iXdAAAAAElFTkSuQmCC","orcid":"","institution":"Oakland University","correspondingAuthor":true,"prefix":"","firstName":"Zhe","middleName":"","lastName":"Wang","suffix":""},{"id":356399250,"identity":"29748946-ccd7-44b2-bf92-3a02beb717cd","order_by":13,"name":"Zhenglong Yang","email":"","orcid":"","institution":"Ludong University","correspondingAuthor":false,"prefix":"","firstName":"Zhenglong","middleName":"","lastName":"Yang","suffix":""}],"badges":[],"createdAt":"2024-08-24 21:53:20","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4970654/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4970654/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s42114-024-01058-3","type":"published","date":"2024-11-12T15:56:54+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":65568887,"identity":"94014d3c-8357-4cb3-8dd4-0cbc6bb0e8d4","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":321486,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic illustration of the preparation procedure for ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/321130fc48a3ea6bdee46e9c.png"},{"id":65568894,"identity":"7c070170-f9c2-4e6c-9b49-5e86642f93cb","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":248254,"visible":true,"origin":"","legend":"\u003cp\u003eXRD pattern (a) ZnO@NF; (b) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; (c) ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF. (d) Mapping characterization of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/116c95574a62e60a59fa0895.png"},{"id":65569566,"identity":"eecdd3c7-ab03-483a-85e6-778766ab7375","added_by":"auto","created_at":"2024-09-30 06:10:34","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":349021,"visible":true,"origin":"","legend":"\u003cp\u003eSEM of (a, b) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; (c, d) ZnO@NF; (e, f) ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/a09157d0ea0d531f27c120cd.png"},{"id":65568890,"identity":"7d321360-200d-4084-8314-6daf46c2ec70","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":139998,"visible":true,"origin":"","legend":"\u003cp\u003e(a) CV curves and (b) Charge and Discharge curves of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; ZnO@NF and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/5eb4fd5dbaab5d5c850e8735.png"},{"id":65568891,"identity":"81db0e20-625b-405f-bf6f-5164f23438c0","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":184814,"visible":true,"origin":"","legend":"\u003cp\u003eCycle properties of (a) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; Rate properties of (b) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/38e73740e8bac69d683b66a1.png"},{"id":65568892,"identity":"5eacadf5-89fd-4767-8b4a-fa8933245c70","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":240412,"visible":true,"origin":"","legend":"\u003cp\u003eCV curves of (a) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; (c) ZnO@NF and (e) ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF at scanning rates of 0.2-1.0 mV s\u003csup\u003e-1\u003c/sup\u003e . The log v versus log i plots of the three electrodes: (b) NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF; (d)\u003c/p\u003e\n\u003cp\u003eZnO@NF and (f) ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/e5433622004b742f4f6ebeb5.png"},{"id":65569567,"identity":"1570e10e-f9c0-4b91-9bdf-2ea354c2837c","added_by":"auto","created_at":"2024-09-30 06:10:34","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":113549,"visible":true,"origin":"","legend":"\u003cp\u003eNyquist plots for NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF (a) before the cycle and (c) after 30 cycles of charge and discharge. Relationship between the real part of impedance with low frequency of (b) before the cycle and (d) after 30 cycles of charge and discharge\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/1e2e4673d84d18e90627cf4b.png"},{"id":69274614,"identity":"4006c3b1-1eda-4c9a-8b9b-354e38aacf49","added_by":"auto","created_at":"2024-11-18 16:10:51","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2046590,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/b4accef3-43d6-48f0-8e48-fd61b1111851.pdf"},{"id":65568888,"identity":"425a9380-64f1-42ae-b059-f70f89126eef","added_by":"auto","created_at":"2024-09-30 06:02:34","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":72961,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/e70d30905ac0dba8ff176d6e.docx"},{"id":65569565,"identity":"d7758fd1-3b3d-44b7-8a8c-55782d5295f7","added_by":"auto","created_at":"2024-09-30 06:10:34","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":225650,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical Abstract\u003c/p\u003e","description":"","filename":"Graphicalabstract.png","url":"https://assets-eu.researchsquare.com/files/rs-4970654/v1/4b5c0f289fc072522a1664d2.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eA mechanical strategy of surface anchoring to enhance the electrochemical performance of ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF self-supporting anode for lithium-ion batteries\u003c/p\u003e","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eLithium-ion batteries (LIB) are now widely used in a range of applications, from portable electronic devices such as smartphones and laptops to electric vehicles and energy storage systems for the grid[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. The demand for high-energy-density batteries has stimulated the pursuit of advanced anode materials that can replace graphite anodes currently widely used commercially. To achieve this goal, many researchers have explored alternative materials, including silicon, titanium, and transition metal oxides, as high-capacity anode materials[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eNiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e has attracted much attention due to its high energy density, low cost, environment-friendly, and other advantages[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Moreover, it has a theoretical capacity of 890 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. However, it suffers from poor cyclability due to the collapse of the three-dimensional loose and porous nano-flake structure during cycling[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. To overcome this issue, research by Yuan et al.[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e] utilized the electrostatic spray deposition (ESD) technique to deposit 3D porous NiO-NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e films directly onto the surface of 3D porous NF. The results showed that this porous NiO-NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e structure significantly improved the material's electrochemical performance. This structure exhibited high specific capacity and stable cycling behavior. Another research by Wang et al[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e] synthesized carbonaceous microspheres (CMSs) using cobalt acetate tetrahydrate as a catalyst, resulting in the formation of six-shelled NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e hollow multi-shelled structures (6S-NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-HoMSs). These low-dimensional nanostructures have a high specific surface area and excellent mass transport properties. Its multi-shelled structure effectively manages volume expansion, reduces stress and strain, promotes uniform lithium deposition, and improves battery cycle stability.\u003c/p\u003e \u003cp\u003eAnother way to mitigate the capacity decay phenomenon due to the volume effect is surface coating[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Surface coatings for lithium-ion battery anodes come in various structures, including monolayer, bilayer, core-shell, and hierarchical structures. And achieved by some techniques such as chemical vapor deposition (CVD)[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], atomic layer deposition (ALD)[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], and electrochemical deposition (ECD)[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Although these coatings offer simple and effective protection for the anode material, they may also have drawbacks such as decreased flexibility and increased cracking susceptibility[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Among many potential coating materials, ZnO nanorods have attracted much attention due to their high mechanical strength, more resistance to mechanical damage, and can be engineered to allow volume change[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, a mechanical strategy was assumed, the nanorod structure of ZnO was grown on the surface of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites by hydrothermal through an anchoring structure. The size of the nanorod-like ZnO is tailored to match the loose and porous nano-flake structure of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, enabling the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite to remain stable during cycling without collapsing. The final experimental results of the anode material showed better electrical conductivity, kinetics, and cyclability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e2.1 Experimental Preparation Procedure\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eFirstly, 0.1455 g of Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO was added to 10 mL of deionized water with constant stirring to obtain solution A. Add 0.328 g of dimethylimidazole to 10 mL of deionized water and stir magnetically for 5 min to prepare Solution B. Then add Solution B quickly into Solution A and continue to stir magnetically for 5 min to obtain Solution C. Add the cleaned and pre-treated NF to Solution C, sonicate for 3 min to remove air bubbles, and let stand at room temperature for 6 h. After that, rinse the NF with anhydrous ethanol, and dry it in a vacuum oven overnight to obtain ZIF-67@ NF samples.\u003c/p\u003e \u003cp\u003eZIF-67@NF was then placed in a tube furnace. And the tube furnace was increased temperature to 350 ℃ with a heating rate of 2 ℃/min, then held at 350 ℃ for 2 h under an air atmosphere, and finally cooled to room temperature naturally to obtain the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites.\u003c/p\u003e \u003cp\u003eA 0.05 M ethanolic solution of Zinc acetate was prepared, and the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF material was immersed in the above solution for 5 min, then dried at 80 ℃ and the above steps were repeated three times. Then, the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF material was held at 350 ℃ for 30 min under an air atmosphere with an increase rate of 2 ℃/min and then lowered to room temperature. Dissolve 0.015 M Zn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e∙6H\u003csub\u003e2\u003c/sub\u003eO, 0.015 M urotropine, and 0.6 mL ammonia in 20 mL of deionized water and keep stirring for 30 min, then pour the well-mixed solution into a 25 mL hydrothermal reactor, add annealed NF, react at 90 ℃ for 24 h. After it is lowered to room temperature, remove and wash with deionized water and anhydrous ethanol 3 times, and finally dried in an oven at 60 ℃ for 8 h. ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF target composites were obtained. In addition, the above steps were repeated directly on the pretreated clean NF. The ZnO@NF composite grown in situ on blank NF was generated and used as a comparison material for analysis together with the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite. The compositions and properties were analyzed together with NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites as comparison materials.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Characterization\u003c/h2\u003e \u003cp\u003eThe surface morphology was observed by scanning electron microscope (SEM, JEOL, JSM-7900F). The phase composition was determined by X-ray diffraction (XRD, Smart Lab III, Rigaku, Cu K radiation, λ\u0026thinsp;=\u0026thinsp;0.1542 nm). The XRD data were collected from 2θ\u0026thinsp;=\u0026thinsp;10\u0026deg;-80\u0026deg; at a scanning rate of 5\u0026deg;∙min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Electrochemical performance measurements\u003c/h2\u003e \u003cp\u003eThe electrode materials synthesized in the experiment were pressed together with a blank NF tablet press of the same size (pressure of 10 MPa). Then dry at 80\u0026deg;C for 6 hours. Put in an argon glove box and assemble it into a button battery for CR2025. The separator material was Celgard 2400 polypropylene. The electrolyte was a solution of LiPF\u003csub\u003e6\u003c/sub\u003e(1M) in ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) (1:1:1 in volume). Then the assembled button battery was placed in the groove of the sealing machine and applied 8 MPa pressure. After the battery is built, aging for one night, conducting a series of electrochemical performance tests. In this paper, the cycle performance and rate performance of the battery were tested by the LAND battery-testing system (CT2001A, China). Cyclic voltammetry (CV) was performed at the electrochemical workstation (CHI660E, Shanghai Chenhua, China). Tested at 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e scan rate in the voltage range of 0.01-3 V. Electrochemical impedance spectrum (EIS) was carried out by electrochemical workstation (CHI660E, Shanghai Chenhua, China) in the frequency range of 100000-0.01 Hz.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eTo analyze the phase composition of the synthesized materials, XRD characterization was performed on the target and comparison materials. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a) shows the XRD spectra of the comparison material ZnO@NF, the diffraction peaks at 2θ\u0026thinsp;=\u0026thinsp;32.1\u0026deg;, 34.5\u0026deg;, 36.5\u0026deg;, and 57.2\u0026deg; correspond to the (100), (002), (101), and (110) crystal planes of ZnO (JDPDS NO. 75-1526), respectively, demonstrating that ZnO on the surface of NF was successfully synthesized. The XRD spectra of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b). The diffraction peaks at 2θ\u0026thinsp;=\u0026thinsp;44.7\u0026deg;, 52.0\u0026deg;, and 76.5\u0026deg; of the composites correspond to the (111), (200), and (220) crystal planes of Ni (JDPDS NO.87\u0026ndash;0712), respectively. The diffraction peaks at diffraction angles 2θ\u0026thinsp;=\u0026thinsp;18.9\u0026deg;, 31.2\u0026deg;, 38.4\u0026deg;, 59.1\u0026deg;, and 65.0\u0026deg; are attributed to the (111), (220), (222), (511), and (440) crystal planes of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (JDPDS NO. 73-1702). Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(c) shows the XRD spectral characterization of the target material ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, which was successfully synthesized as a ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite grown in situ on NF by comparing with the PDF card. The intensity of the diffraction peaks of the synthesized material is relatively low due to the three strong diffraction peaks of the monolithic nickel, but still, obvious diffraction peaks can be seen in this figure, and the presence of the elements Ni, Co, and O can also be proved by the Mapping characterization of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(d), and the distribution of the three elements is very homogeneous on the NF, which once again confirms the synthesis of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites and shows that the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF material grows uniformly on the NF.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo observe the morphological characteristics of the composites, the target materials and two comparison materials were subjected to scanning electron microscopy (SEM) characterization of the target material and the two comparison materials. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (a, b) show the morphological features of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material at different magnifications. A unique loose and porous nano-flake structure is formed in situ on the foam nickel substrate, its pores diameter is 40\u0026ndash;70 \u0026micro;m. The nano-flakes exhibit a thickness of only a few tens of nanometers and are irregularly distributed on the surface of the NF. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (c, d) present the morphological features of the reference material ZnO at different magnifications. ZnO exhibits a disordered distribution of short rod structures on the microscale, randomly dispersed on the NF substrate. The appearance of a few conical clusters in the image may be attributed to the corrosion of the foam nickel substrate by the ZnO solution during the preparation process, resulting in the formation of a small amount of NiO morphology.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (e, f) display the surface morphology of the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material. It is evident from the images that a layer of short rod-like ZnO structures has grown on the surface of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material. The diameter of these rods ranges from 40 to 60 nanometers, with lengths varying between 100 and 400 nanometers. Notably, a comparison between Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (b) and Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (e) reveals a significant increase in the synthesized ZnO when ZnO grows on the surface of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material. This increase can be attributed to the fact that the sheet-like porous structure of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material, with its diameter-matched pores of 400\u0026ndash;700 nanometers, provides a favorable surface for the attachment and anchoring of ZnO nanorods. Consequently, the quantity of hydrothermally synthesized nano-rods is enhanced. The uniform coating of ZnO on the surface of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material is beneficial for improving the fragility associated with its loose and porous structure, thereby enhancing structural stability.\u003c/p\u003e \u003cp\u003eThe target material was utilized as a lithium-ion negative electrode material and assembled into a button cell to evaluate its electrochemical performance. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(a) illustrates the cyclic voltammetry (CV) curves of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode, ZnO, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode within the voltage range of 0.01-3.00 V at a scan rate of 0.1 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The reduction peak of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF appears at 1.06 V during the negative scan, corresponding to the reduction process of Ni\u003csup\u003e2+\u003c/sup\u003e and Co\u003csup\u003e2+\u003c/sup\u003e to metallic Ni and Co, as indicated by the discharge plateau at 1.3 V in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(b) of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF discharge curve. In Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(a), the oxidation peaks observed at 0.3, 0.4, 0.55, 0.7, and 1.4 V during the positive scan for ZnO and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF are associated with the oxidation of metallic Zn to Zn\u003csup\u003e2\u003c/sup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. The oxidation peak observed at 2.25 V for ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF corresponds to the oxidation of metallic Ni and Co to Ni\u003csup\u003e2+\u003c/sup\u003e and Co\u003csup\u003e2+\u003c/sup\u003e. The reduction peak at 1.1 V during the negative scan for ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF corresponds to the discharge plateau at 1.35 V in the galvanostatic charge-discharge curve. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(a), The peak potential gaps for NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, and ZnO are 1.217 V, 1.15 V, and 1.143 V, respectively. It is evident that after the anchoring of ZnO, NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite material has a stronger anodic/cathodic peak intensity and a smaller potential gap between the reduction and oxidation peaks which indicates faster Li\u003csup\u003e+\u003c/sup\u003e diffusion kinetics and lower polarization[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eCycling and rate capability tests were conducted to investigate the electrochemical performance of the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes in button battery. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a) presents the capacity and stability tests of the electrodes after 100 cycles at a current density of 100 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode, ZnO electrode, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode exhibited initial discharge specific capacities of 1516.6/1116.9 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1133.1/722.6 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 1460.1/944.6 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The corresponding first-cycle coulombic efficiencies were 73.6%, 63.8%, and 64.7%. After 100 charge-discharge cycles, the discharge-specific capacities of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes reached 313.8, 245.4, and 475.2 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The capacity retention rates after 100 cycles, relative to the second cycle, were 28.2%, 34.6%, and 51.5% for the three electrodes, respectively. The ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode exhibited the highest capacity and capacity retention rate after 100 cycles. The addition of ZnO enhanced the stability of the material, resulting in slower capacity decay during cycling.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(b) shows the rate capability test results of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes. At current densities of 100, 200, 400, 800, and 1600 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the discharge capacities of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode were 1409.8, 1261.8, 1021.1, 836.9, and 658.4 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The corresponding specific capacities of the ZnO@NF electrode were 541.2, 377.5, 296.8, 244.6, and 204.5 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, while the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrode exhibited specific capacities of 828.6, 657.2, 499.8, 432.4, and 357.3 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. When the current density was restored from 1600 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 100 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the capacities of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes were 917.0, 342.5, and 540.1 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The capacity loss rates, relative to the initial cycle at 100 mA g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, were 35.0%, 36.7%, and 33.9% for the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrodes, indicating relatively good reversibility for the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrode. The improved reversibility is likely attributed to the anchoring of the ZnO nanorod with high mechanical strength on the surface of the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrode, which enhances its structural stability under high current conditions.\u003c/p\u003e \u003cp\u003eTo further analyze the factors influencing the electrochemical kinetics of the materials, cyclic voltammetry (CV) tests were conducted on the three electrodes at different scan rates. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e (a, c, e) displays the CV curves of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes at scan rates of 0.2, 0.4, 0.6, 0.8, and 1.0 mV∙s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. With different scan rates, the CV curves of the three electrodes exhibit similar shapes, with an increase in the magnitude of oxidation/reduction peaks and slight shifting, indicating minor polarization of the electrode materials. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e (b, d, f) presents the plots of log\u003cem\u003ev\u003c/em\u003e versus log\u003cem\u003ei\u003c/em\u003e for the cathodic and anodic scans. The relationship between the current density \u003cem\u003ei\u003c/em\u003e and the scan rate ν follows the equation log\u003cem\u003ei\u003c/em\u003e\u0026thinsp;=\u0026thinsp;\u003cem\u003eb\u003c/em\u003e*log\u003cem\u003eν\u003c/em\u003e\u0026thinsp;+\u0026thinsp;log\u003cem\u003ea\u003c/em\u003e, where the value of adjustable parameter \u003cem\u003eb\u003c/em\u003e reflects the controlling process during electrode charge and discharge. The \u003cem\u003eb\u003c/em\u003e values for the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode are 0.44 and 0.6, while for the ZnO@NF electrode, the \u003cem\u003eb\u003c/em\u003e values are 0.68 and 0.7. As for the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode, the \u003cem\u003eb\u003c/em\u003e values are 0.5 and 0.64. Overall, the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode is primarily controlled by the diffusion process, while the ZnO@NF electrode is controlled by a combination of capacitance and diffusion processes. The ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode exhibits \u003cem\u003eb\u003c/em\u003e values between those of the other two electrodes, indicating that the diffusion process remains the primary control mechanism.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFinally, the electrochemical impedance spectroscopy of the three electrodes was further discussed and analyzed. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(a) shows the Nyquist plots of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes before the charge-discharge cycling test. The plots for all three electrodes exhibit similar shapes, consisting of a semicircle and a sloping line. The semicircle in the high-frequency region represents the charge transfer impedance, while the sloping line in the low-frequency region indicates the Warburg diffusion impedance. From the graph, it can be observed that the charge transfer impedances of those electrodes are 908.5, 1162.9, and 245.8 Ω, respectively. The ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode exhibits the smallest charge transfer impedance, which may be attributed to the formation of a dense layer of ZnO nanorods, increasing the contact area with the electrolyte.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(b) shows the diffusion impedances of Li\u003csup\u003e+\u003c/sup\u003e within the materials for the three electrodes. It can be seen that the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode has the lowest diffusion impedance, indicating a relatively lower impedance within the material. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(c) presents the impedance test curves of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF, ZnO@NF, and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes after 30 charge-discharge cycles. It is worth noting that the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode exhibits a semicircle and a sloping line, while the ZnO@NF and ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrodes consist of two semicircles and a sloping line. The presence of two semicircles in the latter two electrodes indicates the existence of two interface electron transfer processes. The appearance of two semicircles in the ZnO@NF electrode is attributed to the interface between the rod-like ZnO and the accompanying clustered NiO with the electrolyte, while the two semicircles in the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode arise from the interfaces formed between the rod-like ZnO and the porous sheet-like NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF material with the electrolyte. The smallest semicircle in the Nyquist plot of the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode indicates the lowest charge transfer impedance, while Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(d) also shows the smallest diffusion impedance after 30 cycles among the three electrode materials, reflecting optimal interface charge transfer rate and bulk lithium-ion transport rate.\u003c/p\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this work, NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites were generated by calcination of the synthesized ZIF-67 with NF, followed by the growth of ZnO material on the surface to obtain ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composites with optimized electrochemical properties compared to the comparison materials NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF and ZnO@NF.\u003c/p\u003e \u003cp\u003eThe ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF morphology presents a short rod-like structure grown on the porous lamellar NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite, which has a unique structure with significant stability in charge/discharge cycles and high specific capacity compared to the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF material with loose porous lamellar shape. The ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrode can reach a specific capacity of 475.2 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 100 cycles (100 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), which is significantly higher than the 313.8 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode and 245.4 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of ZnO@NF electrode under the same test conditions. The anchoring of ZnO nanorods on the surface of the composites effectively addressed the issue of the collapse of the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e during cycling and resulted in improved electrical conductivity, kinetics, and cyclability. The results of this work suggest that the mechanical structure could be a promising strategy for improving the performance of high-capacity anode materials.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor contribution:\u003c/strong\u003e Lixiang Sun, Zhenglong Yang and Zhe Wang designed this project and contributed to the main manuscript text. Yanbin Xu and Xingang Liu conducted experiments and contributed equally to this work. Shuai Wang, Zhenyu Fu, Wenfan Feng, Zhiqiang Lv, Yuming Cui, Xiao Li, Ping Yin, Ashely DeMerleand Ethan Burcar have contributed to conducting the experiments, preparing figures, and writing. All authors reviewed the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e This work was supported by Yantai Science and Technology Innovation Development Planning(2022XDRH007, Campus Local Integration Project), and was partially supported by the National Natural Science Foundation of China (No. 52173075). ZW would like to acknowledge the support from Oakland University.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability:\u0026nbsp;\u003c/strong\u003eThe authors declare that the data supporting the findings of this study are available within the paper. Should any raw data files be needed in another format, they are available from the corresponding author upon reasonable request.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interests:\u0026nbsp;\u003c/strong\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eChen J, Wu J, Wang X, Yang Z (2021) Research progress and application prospect of solid-state electrolytes in commercial lithium-ion power batteries. Energy Storage Mater 35:70\u0026ndash;87\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSethurajan M, Gaydardzhiev S (2021) Bioprocessing of spent lithium ion batteries for critical metals recovery\u0026ndash;A review. Resources, Conservation and Recycling. ;165:105225\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhu P, Gastol D, Marshall J, Sommerville R, Goodship V, Kendrick E (2021) A review of current collectors for lithium-ion batteries. J Power Sources 485:229321\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang Y, Fu Z, Xu Y, Yin P, Yang L-X, Wang F, Guo X, Liu G, Yang Z-L (2022) Simple preparation of two-dimensional lamellar ammonium cobalt phosphate materials derived from ZIF-L and its application in supercapacitors. J Alloys Compd 927:167030\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQiao L, Wang X, Sun X, Li X, Zheng Y, He D (2013) Single electrospun porous NiO\u0026ndash;ZnO hybrid nanofibers as anode materials for advanced lithium-ion batteries. Nanoscale 5:3037\u0026ndash;3042\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXie J, Tang F, Li H, Jiang W, Yang Z, Zhao D, Xu Y, Meng Y, Sun W, Jiang Z (2023) FeMoO4/N-doped porous carbon composites as anode material for high-performance lithium-ion batteries. J Electroanal Chem. :117623\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhou W, Cheng C, Liu J, Tay YY, Jiang J, Jia X, Zhang J, Gong H, Hng HH, Yu T (2011) Epitaxial growth of branched α-Fe2O3/SnO2 nano‐heterostructures with improved lithium‐ion battery performance. Adv Funct Mater 21:2439\u0026ndash;2445\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu Y, Burns R, Liu Z, Wang Z (2020) Nanostructure interface for lithium-ion batteries. Advanced Nanomaterials for Electrochemical-Based Energy Conversion and Storage. Elsevier, pp 35\u0026ndash;67\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFu Z, Wang Y, Xu Y, Li H, Qiao Q, Yin P, Wang F, Guo X, Yang Z (2022) The surface coating strategy enhances the lithium storage performance of Ni3S2@ PPy self-supporting as anode materials for lithium-ion batteries. J Alloys Compd 926:166889\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang D, Wang Y, Fu Z, Xu Y, Yang L-X, Wang F, Guo X, Sun W, Yang Z-L (2021) Cobalt\u0026ndash;nickel phosphate composites for the all-phosphate asymmetric supercapacitor and oxygen evolution reaction. ACS Appl Mater Interfaces 13:34507\u0026ndash;34517\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang D, Xu Y, Guo X, Fu Z, Yang Z, Sun W (2021) Nickel foam as conductive substrate enhanced low-crystallinity two-dimensional iron hydrogen phosphate for oxygen evolution reaction. J Alloys Compd 870:159472\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAn C, Wang Y, Huang Y, Xu Y, Xu C, Jiao L, Yuan H (2014) Novel three-dimensional NiCo 2 O 4 hierarchitectures: solvothermal synthesis and electrochemical properties. CrystEngComm 16:385\u0026ndash;392\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYuan J, Gao S, Lai W, Zheng S, Meng J, Zhang X, Zhu X, Yu H, Li X (2019) Facile fabrication of 3D porous NiO\u0026ndash;NiCo 2 O 4 film for superior lithium storage. J Mater Sci: Mater Electron 30:16008\u0026ndash;16014\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWitherspoon E, Ling P, Winchester W, Zhao Q, Ibrahim A, Riley KE, Wang Z (2022) Highly Selective Electrochemical Synthesis of Urea Derivatives Initiated from Oxygen Reduction in Ionic Liquids. ACS omega 7:42828\u0026ndash;42834\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHuang X, Xia X, Yuan Y, Zhou F (2011) Porous ZnO nanosheets grown on copper substrates as anodes for lithium ion batteries. Electrochim Acta 56:4960\u0026ndash;4965\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDu ZZ, Guo CK, Wang LJ, Hu AJ, Jin S, Zhang TM, Jin HC, Qi ZK, Xin S, Kong XH, Guo YG, Ji HX, Wan LJ (2017) Atom-Thick Interlayer Made of CVD-Grown Graphene, Film on Separator for Advanced Lithium-Sulfur Batteries. ACS Appl Mater Interfaces 9:43696\u0026ndash;43703\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAravindan V, Jinesh KB, Prabhakar RR, Kale VS, Madhavi S (2013) Atomic layer deposited (ALD) SnO2 anodes with exceptional cycleability for Li-ion batteries. Nano Energy 2:720\u0026ndash;725\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi X, Shao CL, Wang XL, Wang JJ, Liu GX, Yu WS, Dong XT, Wang JX (2022) Preparation of Fe3O4/FexSy heterostructures via electrochemical deposition method and their enhanced electrochemical performance for lithium-sulfur batteries. Chem Eng J. ;446\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGuan P, Zhou L, Yu Z, Sun Y, Liu Y, Wu F, Jiang Y, Chu D (2020) Recent progress of surface coating on cathode materials for high-performance lithium-ion batteries. J Energy Chem 43:220\u0026ndash;235\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang X, Ahmad M, Sun H (2017) Three-Dimensional ZnO Hierarchical Nanostructures: Solution Phase Synthesis and Applications. Materials 10:1304\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWu GL, Jia ZR, Cheng YH, Zhang HX, Zhou XF, Wu HJ (2019) Easy synthesis of multi-shelled ZnO hollow spheres and their conversion into hedgehog-like ZnO hollow spheres with superior rate performance for lithium ion batteries. Appl Surf Sci 464:472\u0026ndash;478\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFan YC, He X, Li HJ, Huang YT, Sun CH, Liu HY, Huangzhang E, Sun F, Zhao XY, Nan JM (2022) Lithiophilic Ni3S2 layer decorated nickel foam (Ni3S2@Ni foam) with fast ion transfer kinetics for long-life lithium metal anodes. Chem Eng J. ;450\u003c/span\u003e\u003c/li\u003e\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":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"mechanical strategy, ZnO/NiCo2O4@NF composite, electrode materials, surface anchoring","lastPublishedDoi":"10.21203/rs.3.rs-4970654/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4970654/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eNiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e has the advantages of high energy density, low cost, and environment-friendly as the anode materials of lithium-ion batteries. However, NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e is adversely affected by the slow transmission rate of lithium-ion and the collapse of its three-dimensional loose and porous nano-flake structure causes its poor cycling performance. In this study, to address this issue, the NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e @ nickel foam(NF) composite was formed by depositing ZIF-67 on nickel foam through room temperature standing and 350 ℃ treatment, and then short ZnO nanorods with an anchoring structure were grown on its surface through heat treatment and hydrothermal treatment to obtain ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF compound materials. The nano-rod structure of ZnO material increases the contact between the electrode material and electrolyte, reduces the charge transfer resistance, and its anchoring structure stabilizes the porous sheet architecture of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF. After 100 cycles (100 mA∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), the discharge capacity of the ZnO/NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF composite electrode remained at 475.2 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which is significantly higher than 313.8 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of NiCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@NF electrode and 245.4 mAh∙g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of ZnO@NF electrode.\u003c/p\u003e","manuscriptTitle":"A mechanical strategy of surface anchoring to enhance the electrochemical performance of ZnO/NiCo2O4@NF self-supporting anode for lithium-ion batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-09-30 06:02:29","doi":"10.21203/rs.3.rs-4970654/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-10-14T10:57:37+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-10-14T10:39:23+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"65816331542749717727736102164255725970","date":"2024-10-05T14:33:17+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-09-30T14:50:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"215441751498777446134638779091604788031","date":"2024-09-19T15:32:16+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"92585585979615325662880571603834191846","date":"2024-09-19T14:00:32+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-09-14T13:57:27+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-09-14T13:56:19+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-08-30T02:18:31+00:00","index":"","fulltext":""},{"type":"submitted","content":"Advanced Composites and Hybrid Materials","date":"2024-08-24T21:49:00+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"75ec74c5-f38d-4927-ac34-aed980a9103a","owner":[],"postedDate":"September 30th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-11-18T15:58:47+00:00","versionOfRecord":{"articleIdentity":"rs-4970654","link":"https://doi.org/10.1007/s42114-024-01058-3","journal":{"identity":"advanced-composites-and-hybrid-materials","isVorOnly":false,"title":"Advanced Composites and Hybrid Materials"},"publishedOn":"2024-11-12 15:56:54","publishedOnDateReadable":"November 12th, 2024"},"versionCreatedAt":"2024-09-30 06:02:29","video":"","vorDoi":"10.1007/s42114-024-01058-3","vorDoiUrl":"https://doi.org/10.1007/s42114-024-01058-3","workflowStages":[]},"version":"v1","identity":"rs-4970654","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4970654","identity":"rs-4970654","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}