Cyclooctatetrathiophene Based MOF-Derived Porous Materials as High- Performance Anode for Lithium-Ion Batteries

doi:10.21203/rs.3.rs-4948175/v1

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Cyclooctatetrathiophene Based MOF-Derived Porous Materials as High- Performance Anode for Lithium-Ion Batteries

https://doi.org/10.21203/rs.3.rs-4948175/v1

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Extensive research on anodes with higher capacity than carbon materials is driven by the demand for lithium-ion batteries with higher energy density. But cycling stability of high-capacity anodes is hindered by the structural collapse. Metal-organic frameworks (MOFs) are an emerging class of crystalline materials, and their derivatives are expected as alternative high-capacity anodes, resulting from the merits of easy functionalization and pore engineering. In this study, a novel porous Co-MOF-derived composite anode was prepared by the pyrolysis of nonporous Co-cyclooctatetrathiophene tetrapyridine (Co-COTTTP) template. The resulting porous carbon based composite anode demonstrated high specific capacity and long cycling stability in the assembled cells. Co-COTTTP-500 delivered a high reversible specific capacity of 1005.7 mAh g⁻¹ after 100 cycles at 0.1 A g⁻¹ and can be cycled steady for 800 cycles at 1 A g⁻¹, indicating the structure stability during cell operation. The comprehensive investigation of the framework structure and the composition of Co-COTTTP-derived composite anodes revealed that the exposed rich redox active sites, appropriate degree of graphitization, and heteroatom doping in the composites effectively enhanced the electrochemical performance of the composite anodes. In summary, this study provides a feasible strategy to prepare high-performance MOF-derived anodes, contributing to the fabrication of high-energy-density lithium-ion batteries.

Metal-organic frameworks (MOFs) have emerged as promising anode material alternatives for lithium-ion batteries (LIBs) over the past several decades, owing to their exceptional attributes such as a substantial specific surface area, permanent porosity, and tunable periodic structure.^[1–3] The intricate and well-defined pore structures of MOFs facilitate the formation of ion permeation networks and alleviate the huge volumetric changes of the anodes during lithiation or de-lithiation processes.^{[4, 5]} Additionally, the redox reaction within the electrode can be attributed to the valence-state changes occurring in the metal active centers of MOFs, and the degree of this change determines the transferable electron count, granting MOFs superior theoretical specific capacity compared to traditional graphite-based anodes.^[6]

Despite the significant advantage of MOF electrodes applied in LIBs, the intrinsic low conductivity and significant irreversible capacity still maintain huge challenges when applying high-performance MOF anodes.^{[7, 8]} Several reported research has developed a series of effective strategies to enhance the electrical conductivity and electrochemical stability of MOF/MOF-derived anodes, including selection of suitable organic ligands, doping, and pyrolysis.^{[9, 10]} Incorporating ligands with unsaturated bonds, conjugated aromatic rings and heteroatoms doping has been proven a feasible way to improve the reversible storage of lithium ions and enhance the electrochemical performance of MOF anodes.^{[4, 11]} The MOF derivatives with porous nanostructures can be obtained by the feasible way of pyrolysis or chemical treatment for MOF templates, in which the MOF derivative anodes not only inherit the high specific surface area, huge pore volume, and unique backbone structure of the original MOFs but also possess enhanced electrical/ion conductivity.^[12] Additionally, MOFs-derived anodes exhibited extended Li⁺ storage capacity and accelerated charge transfer, originating from a uniform pore size distribution, high electrical conductivity, abundant active sites, nano-cavities and open channels for small molecules by pyrolysis process in an inert atmosphere, thereby holding promise for advanced LIBs.^[13] Nitrogen/sulfur-rich structure endows the MOF anodes with more active sites capable of reacting with Li⁺ and facilitates the internal charge and ion transfer.^[14] Generally speaking, MOF-derived porous anode materials with superior redox and electrochemical stability are obtained for LIBs through high-temperature pyrolysis.

The electrochemical performance of the MOF-derived anodes is dependent on pyrolysis temperature and atmosphere, involving the aggregation behavior of metal nanoparticles within MOF derivatives.^[15] Contrary to the structural collapse impeding the insertion of lithium ions during charging and resulting in specific capacity decay at an extremely high pyrolysis temperature, the insufficient pyrolysis temperature adversely affects the degree of carbon graphitization, impacting the electrical conductivity of the resulting composite materials.^[16] Therefore, finding appropriate pyrolysis conditions is significant to develop high-performance MOF-derived anodes and explore the structure-activity relationship for LIBs.

In our study, a new MOF template, Co-COTTTP (COTTTP, cyclooctatetrathiophene tetrapyridine), was self-assembled with the organic ligand of COTTTP by a solvent diffusion method. Each COTTTP ligand contains four S atoms and four N atoms, providing S, N-rich active sites that enhance the lithium storage capacity of the MOF-derived anodes, while also offering a plentiful supply of pyridine nitrogen for increased metal anchoring and the promotion of M-N-C active sites. Subsequently, we obtained heteroatom-doped porous carbon composite with cobalt oxides active sites by direct pyrolysis using Co-COTTTP as a template and named Co-COTTTP-400/500/600. These materials maintain the regular pores and nitrogen-rich structure inherited from the template Co-COTTTP polysulfide. The heat treatment improves electrical conductivity and permeability, facilitating rapid transport and embedding/de-embedding of Li⁺ ions, and ultimately enhancing the lithium storage capacity of the anodes. The abundant presence of heteroatoms in the resulting porous carbon based composite not only contributes to increasing the charge density of the material, promoting the transfer of charges and ions, and improving the structural stability, but also facilitates the formation of new nanopores, which can greatly improve the electrode activity. Compared to Co-COTTTP, pyrolysis significantly enhances the specific surface area of the material, facilitating electrolyte solution wettability and providing additional active sites for Li⁺ embedding insertion/de-embedding insertion. The as-prepared MOF-derivated anodes using the aforementioned method exhibit enhanced lithium storage performance, characterized by improved specific capacity, long cycle stability, and excellent multiplicityrate performance. Notably, the Co-COTTTP-500 sample demonstrates a remarkable capacity of 1005.7 mAh·g^− 1 after 100 cycles at a current density of 0.1 A·g^− 1. The electrochemical performance verifies the rationality of structure design and pyrolysis process, providing guidelines for further investigation of high-performance MOF-derivated anodes.

Synthesis of COTTTP.

The COTTTP ligand was prepared according to the reported method.^[17]

Synthesis of Co-COTTTP

Co(NO₃)₂·6H₂O (10 mg, 0.034 mmol) was dissolved in 1.5 mL EtOH and COTTTP (3 mg, 0.005 mmol) was dissolved in 1 mL CH₂Cl₂. The diffusion method was employed, with the ligand solution (COTTTP in CH₂Cl₂) as the lower layer and the metal salt solution (Co(NO₃)₂·6H₂O in EtOH) as the upper layer. A mixed solution of 1 mL of CH₂Cl₂ and EtOH in a 1:1 volume ratio was used as the buffer layer. After allowing the reaction to proceed for 10 days at room temperature, orange crystals (Figure S1) were obtained with a yield of 70%. Molecular formula (include solvent): C₃₇H₂₄Cl₂CoN₆O₇S₄. FT-IR (cm^− 1): 3327 s, 3070 m, 2970 m, 2888 vw, 2454 vw, 1652 w, 1607 vs, 1542 w, 1509 s, 1497 vw, 1455 vw, 1417 vw, 1384 m, 1317 vs, 1222 s, 1178 vw, 1127 w, 1085 w, 1067 m, 1044 vs, 1018 vs, 972 m, 935 w, 877 s, 861 vw, 823 s, 764 w, 729 w, 712 w, 675 m, 644 m, 618 m, 575 m.

Synthesis of Co-COTTTP-400.

Carbonization was carried out in a tube furnace using the synthesized Co-COTTTP as precursor. Under nitrogen atmosphere, the temperature was increased to 400°C at a ramp rate of 2°C·min^− 1 and held for 2 h. The resulting material after carbonization was named Co-COTTTP-400. FT-IR (cm^− 1): 3323 m, 1641 vw, 1588 s, 1458 vw, 1407 w, 1305 vw, 1108 w, 1063 w, 987 vw, 833 vw, 814 s, 762 vw, 663 vw, 633 vw, 610 vw, 572 vw.

Synthesis of Co-COTTTP-500.

Carbonization was carried out in a tube furnace using the synthesized Co-COTTTP as precursor. Under nitrogen atmosphere, the temperature was increased to 500°C at a ramp rate of 2°C·min^− 1 and held for 2 h. The resulting material after carbonization was named Co-COTTTP-500. FT-IR (cm^− 1): 3327 m, 1580 m, 1394 vw, 1099 m, 982 vw, 813 w, 664 vw, 608 vw.

Synthesis of Co-COTTTP-600.

Carbonization was carried out in a tube furnace using the synthesized Co-COTTTP as precursor. Under nitrogen atmosphere, the temperature was increased to 600°C at a ramp rate of 2°C·min^− 1 and held for 2 h. The resulting material after carbonization was named Co-COTTTP-600. FT-IR (cm^− 1): 3748 vw, 3277 w, 1530 m, 1079 s.

The preparation of Co-COTTTP-derived composite anodes.

The procedures for preparing Co-COTTTP-derived composite anodes and lithium-ion batteries are detailed in the supporting information.

Structures and basic properties of Co-COTTTP

Single crystal X-ray diffraction (SCXRD) analysis for Co-COTTTP reveals that it is a 3D MOF crystallizing in the C2/c space group of the monoclinic crystal system (Fig. 1a, Tables S1-S2). The asymmetric unit includes a Co²⁺, two half-ligand COTTTP, one coordinated water, one coordinated NO₃⁻, one free NO₃⁻, and one CH₂Cl₂ molecule, forming a charge-balanced stabilizing framework (Figure S2). Each COTTTP ligand coordinated with four Co atoms via the N atoms on the pyridines. (Figure S3). The coordination environment around the Co atom is hexa-coordinated, with four nitrogen atoms from four COTTTP ligands and two oxygen atoms from one water molecule and one nitrate ion (Fig. 1b). The one-dimensional structure of Co-COTTTP is formed by the cis-trans bonding of adjacent Co atoms by COTTTP (Figure S4). Co-N bond lengths were 2.138–2.152 Å and Co-O bond lengths were 2.150–2.181 Å, comparable to those reported Co-MOFs.^[18–22] The one-dimensional chains are staggered and ordered along the three crystal axes to form a three-dimensional lattice structure (Figures S5-S7). Simultaneously, rhombic apertures of the same size were formed in the b-axis direction, each containing two Co atoms and four S atoms with a size of 14.8 × 14.7 Å² (Fig. 1c). The flexible COTTTP ligand and the presence of a large cavity allow the assembly of neighboring individual 3D networks to form a 2-fold interpenetrated framework (Figs. 1d and S8). This sulfur-rich pore contributes to its excellent lithium storage capacity. Topologically, the structure of Co-COTTTP can be reduced to a 2-fold interpenetrated pts topology by simplifying the ligand COTTTP to a 4-connected tetrahedron and the Co atoms to 4-connected nodes (Fig. 1a).

The experimental powder X-ray diffraction (PXRD) pattern of Co-COTTTP shown in Fig. 2a is in better agreement with the simulated one which suggests the phase purity of Co-COTTTP. Furthermore, the PXRD experimental results of Co-COTTTP after immersion in different organic solvents for 12 h verified that Co-COTTTP shows good chemical stability (Figure S9). Co-COTTTP was also able to maintain the framework structure when immersed in pH 3–11 solutions for 3 h, respectively, which proves that Co-COTTTP possesses good acid-base stability (Fig. 2b). The IR spectra of Co-COTTTP and the COTTTP ligand are shown in Fig. 2c. Co-COTTTP shows a sharp absorption peak at 1603 cm^− 1, which is a characteristic peak of the C = N group and is caused by a deformation vibration within the pyridine ring. The C = N peak of the complex Co-COTTTP is red-shifted by 13 cm^− 1 compared to the COTTTP ligand, which proves the coordination of the pyridine group in the complex. In addition, Co-COTTTP shows a weak peak at 1387 cm^− 1 which is presumed to be the characteristic vibration of NO₃⁻.

The solid-state UV-vis-NIR absorption spectrum in Figure S10 showed that Co-COTTTP had a large main absorption band in the range of 200–600 nm, which was mainly derived from the n-π* and π-π* electronic leaps of the COTTTP ligand.^[17] The appearance of a broad absorption band in the 900–1100 nm range may be attributed to the d-d transition or metal-to-ligand charge transfer (MLCT).^[23–25] The bandgap width of Co-COTTTP is calculated from the Tauc plot to be 2.20 eV, which shows the nature of the semiconductor material (Figure S11). The thermogravimetric analysis (TGA) data of Co-COTTTP (Fig. 2d) revealed that there was only 2.1% solvent loss up to 280°C, after which it started to decompose gradually. Based on this, we selected 400, 500, and 600°C as the carbonization temperatures, respectively.

Microstructure studies of Co-COTTTP-400/500/600

The MOF-derived materials, denoted as Co-COTTTP-400/500/600, were precisely prepared by controlling the pyrolysis temperature in N₂ atmosphere using Co-COTTTP as a precursor, following the procedure illustrated in Fig. 3a.

To gain a comprehensive understanding of the framework structures of Co-COTTTP-400/500/600, a series of measurements were carried out. First, the absence of PXRD patterns for Co-COTTTP-400/500/600 in comparison to crystalline Co-COTTTP suggests that Co-COTTTP-400/500/600 exists in an amorphous state (Fig. 3b). These findings are consistent with TGA results of Co-COTTTP which indicate the decomposition of the organic skeleton above 300°C (Figure S12). Second, the nearly unchanged morphologies of Co-COTTTP-400/500/600 relative to Co-COTTTP in scanning electron microscopy (SEM) images suggest a similar rigid framework for COTTTP-400/500/600 (Figure S13). Additionally, SEM elemental mapping of COTTTP-400/500/600 reveals uniform dispersion of C, N, O, S, and Co atoms within the skeleton without significant agglomeration (Fig. 3d, Figures S14-15). At last, N₂ adsorption was conducted to examine the microstructure and specific surface areas of COTTTP-400/500/600. The N₂ isotherms of Co-COTTTP-400/500/600 exhibited type II curves (Fig. 3c), indicating the presence of a microporous structure in these materials. Compared to Co-COTTTP (Figure S16) Co-COTTTP-400, Co-COTTTP-500, and Co-COTTTP-600 displayed increased surface areas of 0.64, 29.76, and 77.44 m²·g^− 1, respectively. These findings suggest that pyrolysis of Co-COTTTP at 400/500/600°C contributes to larger specific surface areas, which not only enhances the Li⁺ embedding/de-embedding rate but also facilitates electrolyte solution penetration.

To obtain more detailed information about the composition of Co-COTTTP-400/500/600, several characterization techniques including FT-IR, Raman spectroscopy, HR-TEM, and XPS were performed. First, FT-IR analysis revealed the gradual reduction in characteristic vibration of C = N in the COTTTP ligand, indicating the decomposition of the ligand (Figure S17). The absence of peaks corresponding to organic vibrations suggests the formation of N, O, and S-doped carbon materials. Second, Raman spectra (Fig. 3f) were used to quantitatively study graphitization, by analyzing the intensity ratio of the D-band (located at 1334 cm^− 1, reflecting the carbon defects in the lattice) to the G-band (located at 1573 cm^− 1, reflecting the ordered lattice structure of the carbon material). The values of ID/IG of Co-COTTTP-400/500/600 were 0.47, 0.79, and 0.97, respectively, indicating that higher pyrolysis temperatures result in a greater abundance of defect sites. Third, TEM images along with EDX mapping demonstrated the presence of inorganic compounds consisting of Co and O within the N, O, S-doped graphene (Figures S18-21). Additionally, high-resolution TEM analysis of Co-COTTTP-500 (Figs. 3g-h) revealed the existence of Co₃O₄ nanoparticles, as evidenced by lattice fringes observed at spacings of 0.28 Å, 0.24 Å, and 0.21 Å, corresponding to the (220), (311), and (200) crystallographic planes of Co₃O₄ and CoO, respectively.^[26–31] Notably, the largest Co₃O₄ nanoparticle with a size of 24 nm was found in Co-COTTTP-500, suggesting that a pyrolysis temperature of 500°C is optimal for the aggregation of large Co₃O₄ nanoparticles, potentially enhancing the Li⁺ storage capacity and electrode performance. In order to obtain electronic configuration and local coordination information of Co-COTTTP-500, X-ray absorption spectroscopy (XAS) data of Co-K edge were collected. According to the X-ray absorption near edge structure (XANES) curve of Co-COTTTP-500 sample (Fig. 3i), weak front edge peaks can be observed, which indicates the existence of tetrahedral configuration in the coordination environment of Co atoms. Fourier transformed R-space in the extended X-ray absorption structure (EXAFS) region of Co-COTTTP-500 shows a significant peak at 1.55 Å, which is related to the coordination characteristics of Co-O, while the weaker peak at 2.35 Å represents the coordination characteristics of Co-Co (Fig. 3j). In order to further clarify the coordination atoms, the Co-O K-edge wavelet transform was used to indicate that the K position has coordination characteristics close to Co-O and Co-Co (Fig. 3k). Using Artemis to fit the EXAFS of the sample for quantitative analysis of the coordination environment, the coordination number of Co-O and Co-Co scatterings fitted by Co-COTTTP-500 was 4.5 and 1.2, respectively, indicating that Co-COTTTP-500 is a structure similar to Co₃O₄ with a small amount of CoO (Figures S22-23, Table S3). At last, X-ray photoelectron spectroscopy (XPS) was employed to investigate the elemental composition and valence states of Co-COTTTP-400/500/600. The presence of C, O, N, S, and Co elements in the XPS spectra is consistent with the elemental mapping results obtained from SEM/TEM. In the Co 2p spectrum (Fig. 4c), additional peaks located at 785.5 eV and 796.6 eV, presumed to be characteristic peaks of Co(III) in Co₃O₄, were observed.^[32–35] In the S 2p spectrum (Fig. 4b), the new characteristic peaks appearing at 168.5 eV and 169.7 eV were assigned to C-SO_X-C, which demonstrates the formation of sulfur oxides.^[36–38] It can be clearly seen that new characteristic peaks appeared at 400.4 eV and 404.5 eV for graphite N and pyridine N oxides (Fig. 4d).^{[35, 39–41]} The results of XPS testing confirmed the presence of sulfur oxides and graphitic nitrogen, thereby validating the successful synthesis of N, O, S-doped graphene materials from cobalt-based MOFs (Fig. 4a, Figures S14-15).

Furthermore, we also conducted solid-state UV-vis-NIR tests on Co-COTTTP-400/500/600 (Fig. 3e). After high-temperature pyrolysis, the Co-COTTTP derivatives all exhibit the typical black morphology of carbon materials, and their absorption ranges appear to be significantly broader than those of Co-COTTTP, which also makes them more absorbent in a wider range of wavelengths. Among them, the absorption range of Co-COTTTP-400 is slightly narrower than that of Co-COTTTP-500/600, which may be attributed to the fact that high-temperature d pyrolysis can change the energy band structure and the layout state of electrons of the materials, which in turn extends their absorption range. Meanwhile, the band gap width of the Co-COTTTP derivatives gradually becomes narrower with increasing pyrolysis temperature (Figure S25), which also allows the electrons to easily jump from the valence band to the conduction band to form an electric current and improve the conductivity of the material.

Transformation of MOF precursors to Co-COTTTP-400/500/600 anodes for lithium-ion batteries

Benefiting from high porosity, large surface area, and modifiable functional groups, composite materials derived from MOFs consisting of porous carbon and metallic oxide can serve as high-performance anode materials for lithium-ion batteries. The cyclic voltammetry (CV) curves of Co-COTTTP-500 anodes present reduction peaks at 1.52 and 0.41 V in the first cathodic scan, and these peaks might originate from the insertion of Li⁺ into the framework of Co-COTTTP-500 and the formation of solid electrolyte interface (SEI) ^42,43 (Figure S26). Meanwhile, the initial discharge curve at a current density of 0.1 A/g is consistent with the result (Figure S27). The peak at 0.99 V in the anodic scan is ascribed to the extraction of Li⁺ from the framework of Co-COTTTP-500. One couple of redox peaks (0.88/0.99 V) remain almost unchanged in the subsequent three cycles, corresponding to the highly reversible insertion/extraction of Li⁺ into/from Co-COTTTP-500. In addition, the redox peaks of the Co-COTTTP-400/500/600 anodes occur at almost the same potential, indicating that they undergo an identical lithium storage process even with different pyrolysis temperatures (Figure S28). Nevertheless, different carbonization temperatures can cause differences in the distribution of carbon materials and metal cobalt compounds in derivatives, resulting in differences in electrochemical performance. The capacitive behavior of the Co-COTTTP-500 anode was thoroughly investigated, with kinetics analyzed using CV measurements. Figure 5a clearly illustrates CV curves at varying scan rates ranging from 0.1 to 2.0 mV s^− 1. These profiles maintain a remarkably similar shape across different scan rates. Typically, the scan rate (v) and the measured current (i) conform to a specific relationship as outlined in previous studies.^{[44, 45]}

$$\:i=a{v}^{b}$$

$$\:logi=b\bullet\:logv+loga$$

The empirical parameters are denoted by a and b. As indicated in prior studies, signifies diffusion-controlled behavior, whereas a value of 1 represents ideal capacitive behavior.^[44] Utilizing the aforementioned formula, and by fitting a linear regression between logi and logv, we can calculate the b-values. Figure 5b illustrates that the slope of the fitted line is approximately 0.773 (b-values) at 1.93 V, indicative of rapid kinetics arising from the pseudocapacitive effect.

In addition, Fig. 5c exhibits the detailed cycling performance of Co-COTTTP-500 anode, the initial specific capacity of 2430.6, 712.3, 501, 387.4, 264.4 mAh g^− 1 at 0.1, 0.5, 1.0, 2.0, 5.0 A g^− 1 is achieved, respectively. The corresponding charge-discharge profiles of Co-COTTTP-400/500/600 at different current densities are displayed in Figure S29. The samples that have not undergone carbonization and those subjected to carbonization temperatures of 400 and 600°C demonstrate inadequate rate cycling performance and limited cycle stability. The galvanostatic cycling stability of the Co-COTTTP-500 anode reveals a high reversible specific capacity of 1005.7 mAh g^− 1 after 100 cycles at 0.1 A g^− 1 (Fig. 5d). Even increasing the current rate to 1 A g^− 1 and prolonging the cycling time to 800 cycles, they can still deliver a high capacity of 549.1 mAh g^− 1 (Fig. 5e). The above results indicate that Co-COTTTP-500 has excellent lithium storage capacity and electrochemical stability, and can be used as high performance for lithium-ion batteries (Table S5).

To comprehensively elucidate the enduring stability of Co-COTTTP-500 anodes through a rigorous examination, the FTIR and XPS of the electrode sample cycling 800 cycles were conducted. The results of the FT-IR curve (Figure S30) show that there is no obvious change in functional groups, indicating the integrity structural of anodes even after extensive cycling. Additionally, the XPS testing (Figure S31) corroborated the preservation of the elemental valence states, which were found to be in alignment with the initial measurements. Collectively, these findings underscore the exceptional cycling stability of Co-COTTTP-500, affirming its stability and reliability in practical applications.

Notably, Co-COTTTP-500 exhibits satisfactory specific capacity and cycle stability compared to Co-COTTTP-400/600. In general, low-temperature carbonization of higher nitrogen precursors results in highly nitrogen-doped carbon materials. However, their poor graphitization and lower nitrogen-to-oxygen ratio can make them less conductive. Increasing the carbonization temperature will help to enhance the electrical conductivity, which will facilitate the rapid transfer of electrons and Li⁺, but the high temperature will reduce the total nitrogen content and decrease the reactivity at the same time. Co-COTTTP-400 has more nitrogen content but lower graphitization and relatively poorer electrical conductivity, so it is less active as an anode material for lithium-ion batteries. Simultaneously, Co-COTTTP-400 has a low specific surface area due to incomplete pyrolysis at a low temperature, which is not conducive to Li⁺ transport and electrolyte penetration, and therefore exhibits a low capacity. Both Co-COTTTP-500 and Co-COTTTP-600 exhibit high specific capacity, although Co-COTTTP-500 has a higher specific capacity as well as extended calendar life, attributed to the appropriate pyrolysis temperature which endows it with larger cobalt oxide active sites, giving it a stronger Li⁺ affinity and hence a higher specific capacity. However, the higher temperatures can remove part of the organic components of the ligand, but they also reduce the total nitrogen content of the material, which partially reduces the reactivity and is unfavorable for Li⁺ migration. Thus, the appropriate carbonization temperature is crucial for improving the electrochemical performance of MOF-derived anodes.

In summary, high-performance Co-COTTTP-derived anodes were synthesized successfully by the pyrolysis of Co-COTTTP template. Benefiting from the intrinsic ligand advantages, the degree of graphitization, and N doping in the carbonization process, satisfactory redox active sites were constructed in the final products, N, O, and S doped graphitic carbon compositing with cobalt oxides. In merits of the abundant active sites, the Co-COTTTP-derived anodes demonstrated outstanding electrochemical performance, exhibiting a high reversible specific capacity of 1005.7 mAh g^− 1 after 100 cycles at 0.1 A g^− 1, besides, the long cycling performance indicating the structural stability of anodes. The systematic characterization and analysis indicated that the enhanced electrochemical performance of resulting composites profited from the framework and composition of the MOFs. This study presents a way to investigate the effects of ligand structure and carbonization-derived hybridization strategies on improving the electrochemical performance of batteries and proposes a feasible strategy for constructing high-performance anode materials.

Author Contributions

Conflicts of interest

The authors declare no competing financial interest.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant no. 22171136, 22301135 and 52202138), and the Natural Science Foundation of Jiangsu Province (BK20220928 and BK20200472). “the Fundamental Research Funds for the Central Universities” (30921011102, 30922010301) and the startup funding from Nanjing University of Science and Technology (AE89990, AE89991/376). The Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX23_0502). The authors thank the staff from the BL17B beamline of the National Facility for Protein Science in Shanghai (NFPS) at the Shanghai Synchrotron Radiation Facility for assistance during data collection.

Author Contribution

G. Zhang, J. Su and B. Xu conceived the idea of this study and designed the experiments. W. Zhang and Y. Zhong performed the sample synthesis and material characterizations. W. Zhang and Y. Meng designed and synthesized MOFs used in the experiment. Y. Zhong performed the electrochemical tests. W. Zhang, Y. Zhong, Z. Shen, Y. Wang, B. Xu, J. Su and G. Zhang analyzed the data and discussed the results. Y. Wang conducted theoretical calculations for this research system. W. Zhang and Y. Zhong wrote the manuscript. G. Zhang, J. Su and B. Xu revised the manuscript and supervised this project. All the authors participated the writing of the manuscript and have approved the final version of the manuscript.

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Scheme 1 is available in the Supplementary Files section.

No competing interests reported.

ESICoCOTTTPanodeadvancedcompositeandhybridmaterials.pdf
TOC.png
Scheme1.png
Scheme 1. Synthesis route of COTTTP.

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Cyclooctatetrathiophene Based MOF-Derived Porous Materials as High- Performance Anode for Lithium-Ion Batteries

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1. Introduction

2. EXPERIMENTAL SECTION

3. RESULTS AND DISCUSSION

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References

Scheme

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Supplementary Files

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