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C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage
Journal of Alloys and Compounds xxx (xxxx) xxx
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In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage Junbin Liu a, 1, Yixing Fang a, 1, Lingxing Zeng a, c, *, Jianxi Liu c, Lihong Xu a, Jieling Luo a, Baoquan Huang a, c, **, Qingrong Qian a, c, Mingdeng Wei b, Qinghua Chen a, c, d a
Engineering Research Center of Polymer Green Recycling of Ministry of Education, College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, Fujian, 350007, China Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, Fuzhou University, Fuzhou, Fujian, 350002, China c Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian, 350007, China d Fuqing Branch of Fujian Normal University, Fuqing, Fujian, 350300, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 30 July 2019 Received in revised form 17 October 2019 Accepted 19 October 2019 Available online xxx
Constructing hetero-phase nanocomposite uniformly distributed in the carbon network has been recognized as an effective approach to enhance e transfer and Liþ diffusion kinetics. In this work, an effective route is devised to fabricate the ZnOeMoO2/C composite by using the MoeZn-MOFs precursor as self-template, in which ultra-small ZnO and MoO2 nanoparticles uniformly distributed in the carbon network. As a result, the ZnOeMoO2/C composite exhibits good electrochemical properties when used as an anode in lithium ion batteries, which can be ascribe to its unique hetero-phase nanostructure and electric field at surface and interfaces. It delivers a high specific capacity of 860 mA h g1 after 150 cycles at 0.1 A g1, long-term cycle stability (601 mA h g1 after 450 cycles at 2 A g1) and superior rate performance. These results demonstrate that the ZnOeMoO2/C can be a promising anode material for LIBs. © 2019 Elsevier B.V. All rights reserved.
Keywords: Hetero-phase ZnO MoO2 Lithium-ion batteries Anode
1. Introduction In recent years, a range of energy and environmental issues have forced us to develop clean renewable energy such as solar energy, wind energy, biomass energy and so on [1e4]. However, these renewable energy require energy storage equipment for use in ever-growing mobile electronic devices due to the influences of weather and geographical environment [5e8]. Among energy storages devices, lithium-ion batteries (LIBs) have been widely used in the past few decades [9e13]. On the other hand, commercial anode material graphite cannot meet the growing demand of LIBs for energy density and long cycle life due to its low theoretical specific capacity (372 mA h g1) [14,15]. As a consequence, this
* Corresponding author. Engineering Research Center of Polymer Green Recycling of Ministry of Education, College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, Fujian, 350007, China. ** Corresponding author. Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian, 350007, China. E-mail addresses: [email protected] (L. Zeng), [email protected] (B. Huang). 1 These authors contributed equally to this work.
requires us to develop the anode materials of LIBs with higher specific capacity and longer cycle life [16e18]. In this regard, zinc oxide (ZnO), an abundant, nontoxic and ecofriendly semiconductor, is regarded as promising anode materials of LIBs due to its high theoretical capacity of 978 mA h g1 [19,20]. However, the dramatic volume expansion and inherently low conductivity of ZnO lead to inferior cycling stability and rate performance, hindering its practical application in energy storage [21,22]. To circumvent these barriers, some effective methods were carried to improve the electrochemical performance of ZnO, including downsizing the particle size to the nanoscale [23e25], constructing a porous or hollow structure [26], and compositing with supporting or conducting matrix [27,28]. As is known to all, MOFs has become an attractive template for the derivatization of various nanostructured materials for LIBs [29e35], including ZnO-based materials [36,37]. For instance, Park et al. reported a novel and robust core-shell structured ZnO-based composite is prepared via the controlled growth of zeolitic imidazolate frameworks (ZIF-8) on the surface of ZnO nanoparticles, exhibited a reversible capacity of 500 mA h g1 after 300 cycles at 1 A g1 [38]. The excellent electrochemical properties of ZnO can be
https://doi.org/10.1016/j.jallcom.2019.152728 0925-8388/© 2019 Elsevier B.V. All rights reserved.
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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attributed to the frameworks of ZIF-8, which confines the volume expansion and aggregation during the process of lithiation/delithiation [39]. However, improving the electrochemical performance of ZnO-based materials remains a huge challenge. On the other hand, molybdenum dioxide (MoO2) has a low electrical resistivity and delivers high reversible capacity for LIBs [40e42]. Physically loading small nanoparticles onto the nanocarbon conductive material can routinely avoid electroactive component aggregation, while the random distribution and faint adhesion may lead to poor electrochemical performance. More recently, constructing hetero-phase nanocomposite uniformly distributed in the carbon network has attracted great attention, which can accelerate the diffusion of ions and electrons owing to the existence of electric field at the surface and interfaces of hetero-phase [43e45]. The heterointerfaces of hetero-phase nanocomposite can form a builtin potential between the coupled nanocrystals with different band gaps, which can reduce ion-diffusion resistance and facilitate the transport of electrons. In addition, due to the excellent interfacial effect, the heterostructure can improve the surface reaction kinetics [46,47]. Nevertheless, the synthesis of such structure isn’t easy and the high rate performance is still challenge. Herein, we reported a facile strategy that zinc acetate as metal ion source, phosphomolybdic acid as heterogeneous metal source, 2-methylimidazole as ligand, N, N-dimethylformamide as organic solvent, and the ZnOeMoO2/C composites were synthesised by self-assembly reaction and calcination procedure. The obtained samples possess hollow microsphere structure, and ultra-small nanoparticles of ZnO and MoO2 are effectively encapsulated within the carbon network. Owing to the merits of its structure, it has a high specific capacity and long-term cycling properties. As a result, when employed to an anode material for LIBs, the ZnOeMoO2/C composites exhibited a high capacity of 860 mA h g1 at 0.1 A g1 after 150 cycles and long-term service life at high current density (601 mA h g1 at 2 A g1 after 450 cycles). Moreover, it also shows a superior rate performance. 2. Experimental section 2.1. Synthesis of MoeZn-MOFs MoeZn-MOFs was fabricated through self-assembly reaction route. Firstly, 0.3 g of phosphomolybdic acid and 1 mmol of zinc acetate were added in 40 mL of N, N-dimethylformamide, stirring magnetically to obtain uniform solution donated as A. Then, 4 mmol of 2-methylimidazole were homogeneous dispersing in 40 mL of N, N-dimethylformamide donated as B. Finally, the B solution was poured slowly into A and stirred for 24 h at room temperature, followed by washing and centrifuged with ethanol several times and dried at 70 C under vacuum for 12 h to harvest the as-prepared MoeZn-MOFs. 2.2. Synthesis of ZnOeMoO2/C MoeZn-MOFs was calcined in a tube furnace at different temperature (500 C, 600 C, 700 C) for 6 h with a heating rate of 2 C min1 under the nitrogen flow, denoted as ZMO/C-500, ZMO/C600, ZMO/C-700, respectively. 2.3. Structural characterization The crystal structure of collected samples were investigated by a Bruker D8 diffractometer with Cu-Ka radiation (l ¼ 0.15406 nm) over a range of 10e80 . The field-emission scanning electron microscope (Hitachi 8100) and transmission electron microscope (FEI F20 S-TWIN) were carried to analyze the morphologies and
microstructures of the electrode materials. The Agilent 725 ICP-OES was used to confirm the ratios of Zn/Mo elements. Confocal Raman microspectrometer (DXR2xi) with an Ar ion laser at the excitation wavelength of 532 nm were used to collect Raman spectra of the samples. The surface area and pore size distributions were characterized by BELSORP-mini type BET analyzer. The elemental composition and valence state of as-obtained samples were measured by X-ray photoelectron spectroscopy (ESCALAB 250) equipped with a monochromatic Al Ka (1486.7 eV) X-ray source. To confirm the amount of carbon in the nanocomposites, thermogravimetric analysis (TGA) was performed (TGA Q50, TA, America) in air atmosphere. 2.4. Electrochemical measurements To prepare the working electrode, the active materials (80 wt%), acetylene black (10 wt%) and poly (vinylidene fluoride) binder (10 wt%) were dispersed in N-methyl-2-pyrrolidone (NMP) to form a sticky slurry, which was then coated onto a copper foil and dried in vacuum at 90 C overnight to evaporate the solvent. 1 M LiPF6 dissolved in ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) (1:1:1, in vol%) was used as the electrolyte. The metallic lithium foil served as counter electrode, when assembled to the coin cells (CR2025-type) in an argon-filled glove box (H2O and O2 < 0.1 ppm). The galvanostatic chargedischarge curves and cycling performance, over the voltage range of 0.01e3.0 V, were recorded by Land CT-2001A tester. The electrochemical workstation (Ivium, Netherlands) was employed to measured cyclic voltammograms (CV) within the voltage window of 0.01e3.0 V and electrochemical impedance spectroscopy (EIS) at the frequency range of 102 to 105 Hz. 3. Results and discussion The ZnOeMoO2/C was synthesised through self-assembly reaction and a calcination process, illustrated in Fig. 1. Firstly, MoeZnMOFs was fabricated via introducing zinc acetate as metal ion source, phosphomolybdic acid as heterogeneous metal source, 2methylimidazole as ligand, N, N-dimethylformamide as organic solvent. Secondly, ZnOeMoO2/C was collected after annealing process by using the MoeZn-MOFs as self-template. The crystal structures and phases of ZMO/C-500, ZMO/C-600, ZMO/C-700 were investigated by X-ray diffraction (XRD), as presented in Fig. 2. The XRD pattern of the ZMO/C-500 shows inconspicuous diffraction peaks, indicating the weak crystallinity. The XRD diffraction peaks of ZMO/C-600 at 31, 34 , 36 , 47 and 63 can be matched well to the (100), (002), (101), (102) and (103) planes of ZnO (JCPDS card no. 79e0207), while the other diffraction peaks at 2q ¼ 25 , 36 and 53 , corresponding to (110), (020) and (220) planes of MoO2 (JCPDS card no. 78e1073) [48], respectively. It indicates that there are crystalline phases of ZnO and MoO2 in ZMO/C-600 with a good crystallinity. However, the characteristic peak of ZnO is weakened in the XRD patterns of the ZMO/C-700. The results of molar ratios of Zn/Mo in composites are shown in Table S1, characterized by Inductively Coupled Plasma-Optical Emission Spectrometry (ICPOES). The molar ratios of ZnO and MoO2 in ZMO/C-600 and ZMO/C700 are around 1: 1.56 and 1: 2.03, respectively. The above results suggest that the Zn-species partially escaped due to excessive temperature under the confined framework [49,50]. Thus, it can be confirmed that molybdenum source is successfully incorporated in the customized cavities of ZIF-8. To analysis the morphology of samples, the SEM and TEM characterizations were carried out (Fig. 3). It can be seen that the introduction of phosphomolybdic acid is no longer the traditional ZIF-8 polyhedral structure, but a unique microsphere structure
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 1. Schematic illustration of the synthetic route for ZMO/C composites.
Fig. 2. XRD patterns of ZMO/C-500, ZMO/C-600 and ZMO/C-700 composites.
(Fig. 3a). Besides, as depicted in Fig. 3bed more porous and hollow structures gradually appear with the increase of calcination temperature, which is ascribed to the evaporation of residual organic solvents. In addition, the TEM image (Fig. 3e) clearly illustrate the detailed structure of ZMO/C-600 is a hollow microsphere, which is in good accordance with the SEM image (Fig. 3c). From the high resolution TEM images of ZMO/C-600 (Fig. 3f), it can be seen obviously ultra-small dark contrast and amorphous area of sample, suggesting the effectively encapsulating of nanoparticles in composite. The lattice fringes of 0.342 and 0.282 nm match well with the (011) plane of MoO2 and (100) planes of ZnO particles, respectively. These suggest that the nanoparticles of ZnO and MoO2 were scattered in the hollow carbon spheres, indicating that the carbon formed in situ by ZIF-8 effectively encapsulated the active substance and inhibited the volume expansion during charging and discharging. As can be seen from Fig. 3g, Zn, Mo, O, C and N elements are distributed homogeneously in the hollow porous microsphere. In order to investigate the surface chemical state of ZMO/C-600,
which was subjected to analyzed by X-ray photoelectron spectrometer (XPS) (Fig. 4). The composite is composed of Zn, Mo, O, C and N elements are observed in Fig. 4a. Moreover, Fig. 4b of Zn 2p spectrum shows that the characteristic peaks centered at 1022 and 1045 eV, corresponding to Zn 2p3/2 and Zn 2p5/2, confirming the presence of Zn2þ [51,52]. The Mo 3d high-resolution XPS spectrum (Fig. 4c) exhibits four peaks of Mo4þ 3d5/2, Mo6þ 3d5/2, Mo4þ 3d3/2 and Mo6þ 3d3/2 at 229.2, 232.3, 230.1 and 235.5 eV [53], respectively. Among them, the primary peaks are located at around 229.2 and 230.1 eV, suggesting the presence of Mo4þ in MoO2 [54]. In addition, the two Mo6þ orbitals are ascribed to the inevitable oxidation of MoO2 during the test [55]. As shown in Fig. 4d, the O 1s spectrum consists of two peaks at 530.5 and 531.6 eV, indicating the existence of lattice oxygen and surface adsorption oxygen [56]. On the other hand, Fig. 4e contains three peaks at 284.5, 285.5 and 288.4 eV, corresponding to CeC, CeOH/CeOeMo, and C]O bonds, respectively [57]. As depicted in Fig. 4f, the N 1s XPS spectrum exhibited three peaks at around 396.8, 398.5 and 399.6 eV, corresponding to pyridinic N, pyrrolic N and graphitic N, respectively [58]. In addition, it can be seen from Fig. S1a of Raman spectrum, the peaks at 990, 817, 661, 333, 280 cm1 were the characteristic peaks of MoO2 [59]. And the peak at 435 cm1 was ascribe to the E2 mode of ZnO [60]. It means that the ZnOeMoO2/C composite is successfully fabricated. The N2 adsorption-desorption isotherms of precursor and ZMO/C-600 was shown in Fig. S1b with a distinct hysteresis loop, explaining that typical characteristics of mesoporous structure [61e64]. Besides, the specific surface area and pore volume of precursor were 736 m2 g1 and 0.52 cm3 g1, respectively. For comparison, the specific surface area and pore volume of ZMO/C-600 were 167 m2 g1 and 0.39 cm3 g1, respectively. To further confirmed the amount of carbon, the thermogravimetric analysis (TGA) was employed (Fig. S2), and the content of carbon in ZMO/C-600 is ca. 24.11% via calculations. It can be seen that the electrochemical performance of ZMO/C600 as the anode material of LIBs is shown in Fig. 5. For the cyclic voltammetry (CV) curve at a scan rate of 0.2 mV s1 (Fig. 5a), the appearance of a sharp reduction peak at around 0.11 V, in the initial cycle, is attributed to the formation of a solid electrolyte interface film (SEI film), which is an irreversible reaction occurring at the
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 3. SEM images of (a) precursors, (b) ZMO/C-500, (c) ZMO/C-600 and (d) ZMO/C700 composites; TEM images of (e, f) ZMO/C-600 composite and (g) the corresponding elemental mapping results for Zn (blue), Mo (purple), O (red), C (green) and N (yellow). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
interface of the electrolyte, and is a major factor leading to loss of capacity. Then, a series of cathodic peaks in 0.01e0.75 V are associated with the reduction of ZnO to Zn, accompanied by the gradual transformation of Zn to LixZn alloy [65]. In the first anodic scan, a small broad peak was observed at around 0.65 V corresponds to the multi-step Li removal process of LixZn alloy [66]. Apparently, two pair of peaks at 1.26/1.49 V and 1.52/1.70 V are related to lithium insertion/desertion in MoO2 [67e69]. Hence, the redox of ZMO/C600 can be based on following reaction: MoO2 þ x Liþ þ x e 4 LixMoO2 (0 < x < 1)
(1)
MoO2 þ 4 Liþ þ 4 e 4 Mo þ 2 Li2O
(2)
ZnO þ 2 Liþ þ 2 e 4 Zn þ Li2O
(3)
Zn þ x Liþ þ x e 4 LixZn
(4)
It should be noted that there is almost no change in the subsequent cycle, indicating the superior reversibility of ZMO/C-600 electrode. Fig. 5b exhibits the galvanostatic charge-discharge profiles of ZMO/C-600 electrode at a current density of 0.1 A g1. The first discharge and charge capacity of ZMO/C-600 were 1537 mA h g1 and 860 mA h g1, respectively. Therefore, the material’s initial Coulomb efficiency is 55%, and these irreversible capacity decay are caused by the formation of SEI film [70,71]. Subsequently, the profiles overlap well with each other, suggesting the excellent structural and electrochemical stability of ZMO/C-600 [72], which is in good agreement with the CV curves. Fig. 5c shows the cycle performance of ZMO/C-500, ZMO/C-600 and ZMO/C-700 composites electrodes at a current density of 0.1 A g1. As can be seen, the ZMO/C-600 present reversible capacity of 860 mA h g1 after 150 cycles at 0.1 A g1. However, the ZMO/C-500 and ZMO/C-700 shows a remarkably inferior cycling performance, delivering a lower discharge capacity of 416 and 531 mA h g1 after 150 cycles. It can be confirmed that at appropriate calcination temperature, the formation of ZnO and MoO2 with higher crystallinity is beneficial to the de-intercalation of lithium ions. Simultaneously, the volume expansion, during charging and discharging, of the ZnO and MoO2 nanoparticles were limited by the encapsulated carbon formed under the optimized calcination conditions makes them have higher specific capacity and cyclic stability [73]. Notably, the ZMO/C-600 electrode maintains a specific capacity of 601 mA h g1 after 450 cycles at a large current density of 2.0 A g1 (Fig. 5d), and a high coulombic efficiency of almost 100%, suggesting it has excellent coulombic efficiency and cyclic performance. By comparison, the rate performance of the ZMO/C-600 was superior to the ZMO/C-500 and the ZMO/C-700. At current densities of 0.1, 0.2, 0.5, 1.0 and 2.0 A g1, the reversible capacity of the ZMO/C-600 electrode is shown in Fig. 5e as 802, 705, 609, 561 and 500 mA h g1, respectively. When the current density switched back to 0.1 A g1, the capacity of the ZMO/C-600 was back to 860 mA h g1, suggesting the good structure stability of the ZMO/C-600 electrode during cycling [74]. For a more comprehensive understanding of the relationship between the performance and structure of ZnOeMoO2/C materials, we employed electrochemical impedance spectra (EIS) to characterize the above three electrodes. Apparently, all the Nyquist plots (Fig. 5f) consist of a single depressed semicircle in the high-medium frequency region and an inclined line at low frequency. As we all known, the diameter of the semicircle indicates the charge-transfer resistance (Rct) at the interface between electrodes and electrolytes, and the slope of the straight line indicates that Warburg impedance, related to ion diffusion behavior [75e77]. Then, it can be inferred that the ZMO/C-600 electrode material has smaller charge transfer impedance [78,79]. Besides, the slope of the ZMO/C-600 in the low-frequency region is more inclined, indicating that the migration and diffusion in the Liþ electrode is smoother and faster [80,81]. Table 1 compares the electrochemical performance of ZMO/C600 electrode with some previously reported ZnO-based materials for LIBs, which suggesting ZMO/C-600 composite is a promising anode for high performance of LIBs. This can be attributed to the following factors (Fig. 6): (i) The ZMO/C-600 composite exhibits hollow microsphere with porous structure, and ultra-small nanoparticles of ZnO and MoO2 are effectively encapsulated within the carbon network. (ii) In the repeated charge-discharge process, the porous hollow microsphere structure can effectively restrain the agglomeration of the ZnO and MoO2 nanoparticles and provide more active sites. (iii) The uniformly distributed hetero-phase nanocomposite, which can accelerate the diffusion of ions and electrons owing to the existence of electric field at the surface and interfaces of hetero-phase.
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 4. XPS spectra of the ZMO/C-600 composite: a) survey spectrum, b) Zn 2p spectrum, c) Mo 3d spectrum, d) O 1s spectrum and e) C 1s spectrum and f) N 1s spectrum.
Fig. 5. (a) Cyclic voltammentry curves of ZMO/C-600 electrode at a scan rate of 0.2 mV s1. (b) The charge and discharge profiles of ZMO/C-600 electrode at a current density of 0.1 A g1 between 0.01 and 3.0 V. (c) The cycling performance of ZMO-C-500, ZMO-C-600 and ZMO-C-700 electrodes at the current density of 0.1 A g1. (d) The cycling performance of ZMO-C-600 electrodes at the current density of 2 A g1, (e) the rate capability at different current densities between 0.1 and 2 A g1 for LIBs and (f) EIS spectra of ZMO/C-500, ZMO/C-600 and ZMO/C-700 electrodes before and after 50 cycles at the current density of 0.5 A g1.
Table 1 Comparisons of selected performance metrics of Zn-based LIBs anode electrodes. Electrode materials
Cycling capacity (mA h g1)
Rate capability (mA h g1)
Year/Ref.
ZnO-QDs@CMS
1015 (80 565 (350 617 (200 464 (500 500 (300 490 (100 445 (500 860 (150 601 (450
216 (4.0 A/g)
2019/[20]
160 (4.0 A/g)
2019/[23]
284 415 230 500
2019/[38] 2014/[66] 2016/[65] This work
GeOx/ZnO/C ZnO@C ZnOeG ZnO@GAs ZMO/C
cycles/0.05 A/g) cycles/1 A/g) cycles/0.2 A/g) cycles/1.0 A/g) cycles/1.0 A/g) cycles/0.1 A/g) cycles/1.6 A/g) cycles/0.1 A/g) cycles/2.0 A/g)
(2.0 A/g) (1.0 A/g) (10.0 A/g) (2.0 A/g)
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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https://doi.org/10.1016/j.jallcom.2019.152728. References
Fig. 6. Schematic illustration of the excellent structure stability in ZMO-C-600 composite.
4. Conclusions In summary, we demonstrated a facile strategy to introduce phosphomolybdic acid, as a heterogeneous metal source, in the ZIF8 self-assembly process and fabricated a ZnOeMoO2/C hollow microsphere composite at a suitable calcination temperature. SEM and TEM analyses revealed the morphology of the ZnOeMoO2/C is hollow microsphere, the ultra-small ZnO and MoO2 nanoparticles uniformly distributed in the carbon network. The unique heterophase hollow porous structure is very beneficial to accelerate the diffusion of lithium ions and the transport of electrons. Furthermore, the carbon layer derived from ZIF-8 can effectively limit the growth of ZnO and MoO2 to inhibit the volume expansion during charging and discharging. As a result, the ZMO/C-600 composite showed superior capacity (860 mA h g1 after 150 cycles at 0.1 A g1) and long-term cycle stability (601 mA h g1 is achieved at 2 A g1 even after 450 cycles) when it was used as an anode material for LIBs. Overall, the ZMO/C-600 with unique hollow porous structure and hetero-phase is a promising anode material for LIBs, which also provides a proper structural design route for other electrode materials. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements This work was financially supported by National Natural Science Foundation of China (NSFC 51502036, 21605020 and U1505241), National Key Research and Development Program of China (2016YFB0302303), the New Century Talent Project of Fujian Province and Natural Science Foundation of Distinguished Young Scholars for Fujian Province (2019J06015). Appendix A. Supplementary data Supplementary data to this article can be found online at
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In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage Junbin Liu a, 1, Yixing Fang a, 1, Lingxing Zeng a, c, *, Jianxi Liu c, Lihong Xu a, Jieling Luo a, Baoquan Huang a, c, **, Qingrong Qian a, c, Mingdeng Wei b, Qinghua Chen a, c, d a
Engineering Research Center of Polymer Green Recycling of Ministry of Education, College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, Fujian, 350007, China Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, Fuzhou University, Fuzhou, Fujian, 350002, China c Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian, 350007, China d Fuqing Branch of Fujian Normal University, Fuqing, Fujian, 350300, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 30 July 2019 Received in revised form 17 October 2019 Accepted 19 October 2019 Available online xxx
Constructing hetero-phase nanocomposite uniformly distributed in the carbon network has been recognized as an effective approach to enhance e transfer and Liþ diffusion kinetics. In this work, an effective route is devised to fabricate the ZnOeMoO2/C composite by using the MoeZn-MOFs precursor as self-template, in which ultra-small ZnO and MoO2 nanoparticles uniformly distributed in the carbon network. As a result, the ZnOeMoO2/C composite exhibits good electrochemical properties when used as an anode in lithium ion batteries, which can be ascribe to its unique hetero-phase nanostructure and electric field at surface and interfaces. It delivers a high specific capacity of 860 mA h g1 after 150 cycles at 0.1 A g1, long-term cycle stability (601 mA h g1 after 450 cycles at 2 A g1) and superior rate performance. These results demonstrate that the ZnOeMoO2/C can be a promising anode material for LIBs. © 2019 Elsevier B.V. All rights reserved.
Keywords: Hetero-phase ZnO MoO2 Lithium-ion batteries Anode
1. Introduction In recent years, a range of energy and environmental issues have forced us to develop clean renewable energy such as solar energy, wind energy, biomass energy and so on [1e4]. However, these renewable energy require energy storage equipment for use in ever-growing mobile electronic devices due to the influences of weather and geographical environment [5e8]. Among energy storages devices, lithium-ion batteries (LIBs) have been widely used in the past few decades [9e13]. On the other hand, commercial anode material graphite cannot meet the growing demand of LIBs for energy density and long cycle life due to its low theoretical specific capacity (372 mA h g1) [14,15]. As a consequence, this
* Corresponding author. Engineering Research Center of Polymer Green Recycling of Ministry of Education, College of Environmental Science and Engineering, Fujian Normal University, Fuzhou, Fujian, 350007, China. ** Corresponding author. Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian, 350007, China. E-mail addresses: [email protected] (L. Zeng), [email protected] (B. Huang). 1 These authors contributed equally to this work.
requires us to develop the anode materials of LIBs with higher specific capacity and longer cycle life [16e18]. In this regard, zinc oxide (ZnO), an abundant, nontoxic and ecofriendly semiconductor, is regarded as promising anode materials of LIBs due to its high theoretical capacity of 978 mA h g1 [19,20]. However, the dramatic volume expansion and inherently low conductivity of ZnO lead to inferior cycling stability and rate performance, hindering its practical application in energy storage [21,22]. To circumvent these barriers, some effective methods were carried to improve the electrochemical performance of ZnO, including downsizing the particle size to the nanoscale [23e25], constructing a porous or hollow structure [26], and compositing with supporting or conducting matrix [27,28]. As is known to all, MOFs has become an attractive template for the derivatization of various nanostructured materials for LIBs [29e35], including ZnO-based materials [36,37]. For instance, Park et al. reported a novel and robust core-shell structured ZnO-based composite is prepared via the controlled growth of zeolitic imidazolate frameworks (ZIF-8) on the surface of ZnO nanoparticles, exhibited a reversible capacity of 500 mA h g1 after 300 cycles at 1 A g1 [38]. The excellent electrochemical properties of ZnO can be
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attributed to the frameworks of ZIF-8, which confines the volume expansion and aggregation during the process of lithiation/delithiation [39]. However, improving the electrochemical performance of ZnO-based materials remains a huge challenge. On the other hand, molybdenum dioxide (MoO2) has a low electrical resistivity and delivers high reversible capacity for LIBs [40e42]. Physically loading small nanoparticles onto the nanocarbon conductive material can routinely avoid electroactive component aggregation, while the random distribution and faint adhesion may lead to poor electrochemical performance. More recently, constructing hetero-phase nanocomposite uniformly distributed in the carbon network has attracted great attention, which can accelerate the diffusion of ions and electrons owing to the existence of electric field at the surface and interfaces of hetero-phase [43e45]. The heterointerfaces of hetero-phase nanocomposite can form a builtin potential between the coupled nanocrystals with different band gaps, which can reduce ion-diffusion resistance and facilitate the transport of electrons. In addition, due to the excellent interfacial effect, the heterostructure can improve the surface reaction kinetics [46,47]. Nevertheless, the synthesis of such structure isn’t easy and the high rate performance is still challenge. Herein, we reported a facile strategy that zinc acetate as metal ion source, phosphomolybdic acid as heterogeneous metal source, 2-methylimidazole as ligand, N, N-dimethylformamide as organic solvent, and the ZnOeMoO2/C composites were synthesised by self-assembly reaction and calcination procedure. The obtained samples possess hollow microsphere structure, and ultra-small nanoparticles of ZnO and MoO2 are effectively encapsulated within the carbon network. Owing to the merits of its structure, it has a high specific capacity and long-term cycling properties. As a result, when employed to an anode material for LIBs, the ZnOeMoO2/C composites exhibited a high capacity of 860 mA h g1 at 0.1 A g1 after 150 cycles and long-term service life at high current density (601 mA h g1 at 2 A g1 after 450 cycles). Moreover, it also shows a superior rate performance. 2. Experimental section 2.1. Synthesis of MoeZn-MOFs MoeZn-MOFs was fabricated through self-assembly reaction route. Firstly, 0.3 g of phosphomolybdic acid and 1 mmol of zinc acetate were added in 40 mL of N, N-dimethylformamide, stirring magnetically to obtain uniform solution donated as A. Then, 4 mmol of 2-methylimidazole were homogeneous dispersing in 40 mL of N, N-dimethylformamide donated as B. Finally, the B solution was poured slowly into A and stirred for 24 h at room temperature, followed by washing and centrifuged with ethanol several times and dried at 70 C under vacuum for 12 h to harvest the as-prepared MoeZn-MOFs. 2.2. Synthesis of ZnOeMoO2/C MoeZn-MOFs was calcined in a tube furnace at different temperature (500 C, 600 C, 700 C) for 6 h with a heating rate of 2 C min1 under the nitrogen flow, denoted as ZMO/C-500, ZMO/C600, ZMO/C-700, respectively. 2.3. Structural characterization The crystal structure of collected samples were investigated by a Bruker D8 diffractometer with Cu-Ka radiation (l ¼ 0.15406 nm) over a range of 10e80 . The field-emission scanning electron microscope (Hitachi 8100) and transmission electron microscope (FEI F20 S-TWIN) were carried to analyze the morphologies and
microstructures of the electrode materials. The Agilent 725 ICP-OES was used to confirm the ratios of Zn/Mo elements. Confocal Raman microspectrometer (DXR2xi) with an Ar ion laser at the excitation wavelength of 532 nm were used to collect Raman spectra of the samples. The surface area and pore size distributions were characterized by BELSORP-mini type BET analyzer. The elemental composition and valence state of as-obtained samples were measured by X-ray photoelectron spectroscopy (ESCALAB 250) equipped with a monochromatic Al Ka (1486.7 eV) X-ray source. To confirm the amount of carbon in the nanocomposites, thermogravimetric analysis (TGA) was performed (TGA Q50, TA, America) in air atmosphere. 2.4. Electrochemical measurements To prepare the working electrode, the active materials (80 wt%), acetylene black (10 wt%) and poly (vinylidene fluoride) binder (10 wt%) were dispersed in N-methyl-2-pyrrolidone (NMP) to form a sticky slurry, which was then coated onto a copper foil and dried in vacuum at 90 C overnight to evaporate the solvent. 1 M LiPF6 dissolved in ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) (1:1:1, in vol%) was used as the electrolyte. The metallic lithium foil served as counter electrode, when assembled to the coin cells (CR2025-type) in an argon-filled glove box (H2O and O2 < 0.1 ppm). The galvanostatic chargedischarge curves and cycling performance, over the voltage range of 0.01e3.0 V, were recorded by Land CT-2001A tester. The electrochemical workstation (Ivium, Netherlands) was employed to measured cyclic voltammograms (CV) within the voltage window of 0.01e3.0 V and electrochemical impedance spectroscopy (EIS) at the frequency range of 102 to 105 Hz. 3. Results and discussion The ZnOeMoO2/C was synthesised through self-assembly reaction and a calcination process, illustrated in Fig. 1. Firstly, MoeZnMOFs was fabricated via introducing zinc acetate as metal ion source, phosphomolybdic acid as heterogeneous metal source, 2methylimidazole as ligand, N, N-dimethylformamide as organic solvent. Secondly, ZnOeMoO2/C was collected after annealing process by using the MoeZn-MOFs as self-template. The crystal structures and phases of ZMO/C-500, ZMO/C-600, ZMO/C-700 were investigated by X-ray diffraction (XRD), as presented in Fig. 2. The XRD pattern of the ZMO/C-500 shows inconspicuous diffraction peaks, indicating the weak crystallinity. The XRD diffraction peaks of ZMO/C-600 at 31, 34 , 36 , 47 and 63 can be matched well to the (100), (002), (101), (102) and (103) planes of ZnO (JCPDS card no. 79e0207), while the other diffraction peaks at 2q ¼ 25 , 36 and 53 , corresponding to (110), (020) and (220) planes of MoO2 (JCPDS card no. 78e1073) [48], respectively. It indicates that there are crystalline phases of ZnO and MoO2 in ZMO/C-600 with a good crystallinity. However, the characteristic peak of ZnO is weakened in the XRD patterns of the ZMO/C-700. The results of molar ratios of Zn/Mo in composites are shown in Table S1, characterized by Inductively Coupled Plasma-Optical Emission Spectrometry (ICPOES). The molar ratios of ZnO and MoO2 in ZMO/C-600 and ZMO/C700 are around 1: 1.56 and 1: 2.03, respectively. The above results suggest that the Zn-species partially escaped due to excessive temperature under the confined framework [49,50]. Thus, it can be confirmed that molybdenum source is successfully incorporated in the customized cavities of ZIF-8. To analysis the morphology of samples, the SEM and TEM characterizations were carried out (Fig. 3). It can be seen that the introduction of phosphomolybdic acid is no longer the traditional ZIF-8 polyhedral structure, but a unique microsphere structure
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 1. Schematic illustration of the synthetic route for ZMO/C composites.
Fig. 2. XRD patterns of ZMO/C-500, ZMO/C-600 and ZMO/C-700 composites.
(Fig. 3a). Besides, as depicted in Fig. 3bed more porous and hollow structures gradually appear with the increase of calcination temperature, which is ascribed to the evaporation of residual organic solvents. In addition, the TEM image (Fig. 3e) clearly illustrate the detailed structure of ZMO/C-600 is a hollow microsphere, which is in good accordance with the SEM image (Fig. 3c). From the high resolution TEM images of ZMO/C-600 (Fig. 3f), it can be seen obviously ultra-small dark contrast and amorphous area of sample, suggesting the effectively encapsulating of nanoparticles in composite. The lattice fringes of 0.342 and 0.282 nm match well with the (011) plane of MoO2 and (100) planes of ZnO particles, respectively. These suggest that the nanoparticles of ZnO and MoO2 were scattered in the hollow carbon spheres, indicating that the carbon formed in situ by ZIF-8 effectively encapsulated the active substance and inhibited the volume expansion during charging and discharging. As can be seen from Fig. 3g, Zn, Mo, O, C and N elements are distributed homogeneously in the hollow porous microsphere. In order to investigate the surface chemical state of ZMO/C-600,
which was subjected to analyzed by X-ray photoelectron spectrometer (XPS) (Fig. 4). The composite is composed of Zn, Mo, O, C and N elements are observed in Fig. 4a. Moreover, Fig. 4b of Zn 2p spectrum shows that the characteristic peaks centered at 1022 and 1045 eV, corresponding to Zn 2p3/2 and Zn 2p5/2, confirming the presence of Zn2þ [51,52]. The Mo 3d high-resolution XPS spectrum (Fig. 4c) exhibits four peaks of Mo4þ 3d5/2, Mo6þ 3d5/2, Mo4þ 3d3/2 and Mo6þ 3d3/2 at 229.2, 232.3, 230.1 and 235.5 eV [53], respectively. Among them, the primary peaks are located at around 229.2 and 230.1 eV, suggesting the presence of Mo4þ in MoO2 [54]. In addition, the two Mo6þ orbitals are ascribed to the inevitable oxidation of MoO2 during the test [55]. As shown in Fig. 4d, the O 1s spectrum consists of two peaks at 530.5 and 531.6 eV, indicating the existence of lattice oxygen and surface adsorption oxygen [56]. On the other hand, Fig. 4e contains three peaks at 284.5, 285.5 and 288.4 eV, corresponding to CeC, CeOH/CeOeMo, and C]O bonds, respectively [57]. As depicted in Fig. 4f, the N 1s XPS spectrum exhibited three peaks at around 396.8, 398.5 and 399.6 eV, corresponding to pyridinic N, pyrrolic N and graphitic N, respectively [58]. In addition, it can be seen from Fig. S1a of Raman spectrum, the peaks at 990, 817, 661, 333, 280 cm1 were the characteristic peaks of MoO2 [59]. And the peak at 435 cm1 was ascribe to the E2 mode of ZnO [60]. It means that the ZnOeMoO2/C composite is successfully fabricated. The N2 adsorption-desorption isotherms of precursor and ZMO/C-600 was shown in Fig. S1b with a distinct hysteresis loop, explaining that typical characteristics of mesoporous structure [61e64]. Besides, the specific surface area and pore volume of precursor were 736 m2 g1 and 0.52 cm3 g1, respectively. For comparison, the specific surface area and pore volume of ZMO/C-600 were 167 m2 g1 and 0.39 cm3 g1, respectively. To further confirmed the amount of carbon, the thermogravimetric analysis (TGA) was employed (Fig. S2), and the content of carbon in ZMO/C-600 is ca. 24.11% via calculations. It can be seen that the electrochemical performance of ZMO/C600 as the anode material of LIBs is shown in Fig. 5. For the cyclic voltammetry (CV) curve at a scan rate of 0.2 mV s1 (Fig. 5a), the appearance of a sharp reduction peak at around 0.11 V, in the initial cycle, is attributed to the formation of a solid electrolyte interface film (SEI film), which is an irreversible reaction occurring at the
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 3. SEM images of (a) precursors, (b) ZMO/C-500, (c) ZMO/C-600 and (d) ZMO/C700 composites; TEM images of (e, f) ZMO/C-600 composite and (g) the corresponding elemental mapping results for Zn (blue), Mo (purple), O (red), C (green) and N (yellow). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
interface of the electrolyte, and is a major factor leading to loss of capacity. Then, a series of cathodic peaks in 0.01e0.75 V are associated with the reduction of ZnO to Zn, accompanied by the gradual transformation of Zn to LixZn alloy [65]. In the first anodic scan, a small broad peak was observed at around 0.65 V corresponds to the multi-step Li removal process of LixZn alloy [66]. Apparently, two pair of peaks at 1.26/1.49 V and 1.52/1.70 V are related to lithium insertion/desertion in MoO2 [67e69]. Hence, the redox of ZMO/C600 can be based on following reaction: MoO2 þ x Liþ þ x e 4 LixMoO2 (0 < x < 1)
(1)
MoO2 þ 4 Liþ þ 4 e 4 Mo þ 2 Li2O
(2)
ZnO þ 2 Liþ þ 2 e 4 Zn þ Li2O
(3)
Zn þ x Liþ þ x e 4 LixZn
(4)
It should be noted that there is almost no change in the subsequent cycle, indicating the superior reversibility of ZMO/C-600 electrode. Fig. 5b exhibits the galvanostatic charge-discharge profiles of ZMO/C-600 electrode at a current density of 0.1 A g1. The first discharge and charge capacity of ZMO/C-600 were 1537 mA h g1 and 860 mA h g1, respectively. Therefore, the material’s initial Coulomb efficiency is 55%, and these irreversible capacity decay are caused by the formation of SEI film [70,71]. Subsequently, the profiles overlap well with each other, suggesting the excellent structural and electrochemical stability of ZMO/C-600 [72], which is in good agreement with the CV curves. Fig. 5c shows the cycle performance of ZMO/C-500, ZMO/C-600 and ZMO/C-700 composites electrodes at a current density of 0.1 A g1. As can be seen, the ZMO/C-600 present reversible capacity of 860 mA h g1 after 150 cycles at 0.1 A g1. However, the ZMO/C-500 and ZMO/C-700 shows a remarkably inferior cycling performance, delivering a lower discharge capacity of 416 and 531 mA h g1 after 150 cycles. It can be confirmed that at appropriate calcination temperature, the formation of ZnO and MoO2 with higher crystallinity is beneficial to the de-intercalation of lithium ions. Simultaneously, the volume expansion, during charging and discharging, of the ZnO and MoO2 nanoparticles were limited by the encapsulated carbon formed under the optimized calcination conditions makes them have higher specific capacity and cyclic stability [73]. Notably, the ZMO/C-600 electrode maintains a specific capacity of 601 mA h g1 after 450 cycles at a large current density of 2.0 A g1 (Fig. 5d), and a high coulombic efficiency of almost 100%, suggesting it has excellent coulombic efficiency and cyclic performance. By comparison, the rate performance of the ZMO/C-600 was superior to the ZMO/C-500 and the ZMO/C-700. At current densities of 0.1, 0.2, 0.5, 1.0 and 2.0 A g1, the reversible capacity of the ZMO/C-600 electrode is shown in Fig. 5e as 802, 705, 609, 561 and 500 mA h g1, respectively. When the current density switched back to 0.1 A g1, the capacity of the ZMO/C-600 was back to 860 mA h g1, suggesting the good structure stability of the ZMO/C-600 electrode during cycling [74]. For a more comprehensive understanding of the relationship between the performance and structure of ZnOeMoO2/C materials, we employed electrochemical impedance spectra (EIS) to characterize the above three electrodes. Apparently, all the Nyquist plots (Fig. 5f) consist of a single depressed semicircle in the high-medium frequency region and an inclined line at low frequency. As we all known, the diameter of the semicircle indicates the charge-transfer resistance (Rct) at the interface between electrodes and electrolytes, and the slope of the straight line indicates that Warburg impedance, related to ion diffusion behavior [75e77]. Then, it can be inferred that the ZMO/C-600 electrode material has smaller charge transfer impedance [78,79]. Besides, the slope of the ZMO/C-600 in the low-frequency region is more inclined, indicating that the migration and diffusion in the Liþ electrode is smoother and faster [80,81]. Table 1 compares the electrochemical performance of ZMO/C600 electrode with some previously reported ZnO-based materials for LIBs, which suggesting ZMO/C-600 composite is a promising anode for high performance of LIBs. This can be attributed to the following factors (Fig. 6): (i) The ZMO/C-600 composite exhibits hollow microsphere with porous structure, and ultra-small nanoparticles of ZnO and MoO2 are effectively encapsulated within the carbon network. (ii) In the repeated charge-discharge process, the porous hollow microsphere structure can effectively restrain the agglomeration of the ZnO and MoO2 nanoparticles and provide more active sites. (iii) The uniformly distributed hetero-phase nanocomposite, which can accelerate the diffusion of ions and electrons owing to the existence of electric field at the surface and interfaces of hetero-phase.
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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Fig. 4. XPS spectra of the ZMO/C-600 composite: a) survey spectrum, b) Zn 2p spectrum, c) Mo 3d spectrum, d) O 1s spectrum and e) C 1s spectrum and f) N 1s spectrum.
Fig. 5. (a) Cyclic voltammentry curves of ZMO/C-600 electrode at a scan rate of 0.2 mV s1. (b) The charge and discharge profiles of ZMO/C-600 electrode at a current density of 0.1 A g1 between 0.01 and 3.0 V. (c) The cycling performance of ZMO-C-500, ZMO-C-600 and ZMO-C-700 electrodes at the current density of 0.1 A g1. (d) The cycling performance of ZMO-C-600 electrodes at the current density of 2 A g1, (e) the rate capability at different current densities between 0.1 and 2 A g1 for LIBs and (f) EIS spectra of ZMO/C-500, ZMO/C-600 and ZMO/C-700 electrodes before and after 50 cycles at the current density of 0.5 A g1.
Table 1 Comparisons of selected performance metrics of Zn-based LIBs anode electrodes. Electrode materials
Cycling capacity (mA h g1)
Rate capability (mA h g1)
Year/Ref.
ZnO-QDs@CMS
1015 (80 565 (350 617 (200 464 (500 500 (300 490 (100 445 (500 860 (150 601 (450
216 (4.0 A/g)
2019/[20]
160 (4.0 A/g)
2019/[23]
284 415 230 500
2019/[38] 2014/[66] 2016/[65] This work
GeOx/ZnO/C ZnO@C ZnOeG ZnO@GAs ZMO/C
cycles/0.05 A/g) cycles/1 A/g) cycles/0.2 A/g) cycles/1.0 A/g) cycles/1.0 A/g) cycles/0.1 A/g) cycles/1.6 A/g) cycles/0.1 A/g) cycles/2.0 A/g)
(2.0 A/g) (1.0 A/g) (10.0 A/g) (2.0 A/g)
Please cite this article as: J. Liu et al., In situ fabrication of ZnOeMoO2/C hetero-phase nanocomposite derived from MOFs with enhanced performance for lithium storage, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2019.152728
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https://doi.org/10.1016/j.jallcom.2019.152728. References
Fig. 6. Schematic illustration of the excellent structure stability in ZMO-C-600 composite.
4. Conclusions In summary, we demonstrated a facile strategy to introduce phosphomolybdic acid, as a heterogeneous metal source, in the ZIF8 self-assembly process and fabricated a ZnOeMoO2/C hollow microsphere composite at a suitable calcination temperature. SEM and TEM analyses revealed the morphology of the ZnOeMoO2/C is hollow microsphere, the ultra-small ZnO and MoO2 nanoparticles uniformly distributed in the carbon network. The unique heterophase hollow porous structure is very beneficial to accelerate the diffusion of lithium ions and the transport of electrons. Furthermore, the carbon layer derived from ZIF-8 can effectively limit the growth of ZnO and MoO2 to inhibit the volume expansion during charging and discharging. As a result, the ZMO/C-600 composite showed superior capacity (860 mA h g1 after 150 cycles at 0.1 A g1) and long-term cycle stability (601 mA h g1 is achieved at 2 A g1 even after 450 cycles) when it was used as an anode material for LIBs. Overall, the ZMO/C-600 with unique hollow porous structure and hetero-phase is a promising anode material for LIBs, which also provides a proper structural design route for other electrode materials. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements This work was financially supported by National Natural Science Foundation of China (NSFC 51502036, 21605020 and U1505241), National Key Research and Development Program of China (2016YFB0302303), the New Century Talent Project of Fujian Province and Natural Science Foundation of Distinguished Young Scholars for Fujian Province (2019J06015). Appendix A. Supplementary data Supplementary data to this article can be found online at
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