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Ordered Macro-Microporous Metal-Organic Framework Single Crystals and Their Derivatives for Rechargeable Aluminum-Ion Batteries Hu Hong, Jinlong Liu, Huawen Huang, Christian Atangana Etogo, Xianfeng Yang, Buyuan Guan, and Lei Zhang J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b06957 • Publication Date (Web): 30 Aug 2019 Downloaded from pubs.acs.org on August 30, 2019
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Journal of the American Chemical Society
Ordered Macro-Microporous Metal-Organic Framework Single Crystals and Their Derivatives for Rechargeable Aluminum-Ion Batteries Hu Hong,† Jinlong Liu,‡ Huawen Huang,† Christian Atangana Etogo,† Xianfeng Yang,§ Buyuan Guan, ‖ and Lei Zhang*,† †School
China
of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R.
‡Department §Analytical
of Engineering, University of Cambridge, Cambridge CB3 0FA, United Kingdom
and Testing Centre, South China University of Technology, Guangzhou 510640, P. R. China
‖State
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, P. R. China KEYWORDS: hierarchical porous structure, metal-organic framework, single crystal, MOF-derived material, aluminum-ion battery
ABSTRACT: Constructing ordered hierarchical porous structures while maintaining their overall crystalline order is highly desirable but remains an arduous challenge. Herein, we successfully achieve the growth of single-crystalline metalorganic frameworks (MOFs) in three-dimensional (3D) ordered macroporous template voids by saturated solution-based double-solventassisted strategy with precise control over the nucleation process. The as-prepared single-crystalline ordered macro-microporous Co-based MOFs (SOM ZIF-67) exhibits an ordered macro-microporous structure with robust single crystalline nature. Moreover, SOM ZIF-67 can serve as precursor to derive 3D ordered macroporous cobalt diselenide@carbon (3DOM CoSe2@C) through a facile carbonization-selenization treatment. The as-derived 3DOM CoSe2@C can well preserve the 3D ordered macroporous structure of the precursor. More importantly, CoSe2 nanoparticles could be uniformly confined in the conductive ordered macroporous carbon framework, affording regularly interconnected microporous channels and large surface area. As a result, when evaluated as a cathode material for aluminum-ion batteries, the ordered macroporous structure could not only effectively facilitate the diffusion of largesized chloroaluminate anions, but also increase contact area with electrolyte and provide more exposed active sites, thereby exhibiting superior reversible rate capacity (86 mA h g−1 at 5.0 A g−1) and remarkable cycling performance (125 mA h g−1 after 1000 cycles at 2.0 A g−1).
INTRODUCTION Porous materials are of vital importance in various applications such as catalysis, separation and energy.1,2 In particular, crystalline porous materials, including zeolites, metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have received more attention because their uniform pore size and ordered pore distribution often lead to performance improvements.25 Unfortunately, these materials are restricted with the characteristics of their pore size usually concentrated in the micropore range (< 2 nm), thereby bringing a great barrier to their diffusional applications.3,67 Introducing macro- or mesopores to fabricate hierarchically ordered macro/meso-microporous structure is an effective way to achieve efficient mass transport as well as produce
sufficiently exposed active surface in porous frameworks.813 Meanwhile, regarding the overall structural stability, it is extremely preferable to endow hierarchically ordered macro/meso-microporous framework with long-range crystalline order nature, yet this still remains a formidable challenge. Recently, we reported for the first time macro-microporous Zn-based MOF single crystals via a double-solvent–induced nucleation strategy to control nucleation process and allow homogeneous growth of MOFs within threedimensional (3D) ordered superpolymer spheres voids followed by template removal, which displayed ordered hierarchical porous structure with improved mass diffusion and single crystalline nature.14 In spite of these advantages, Zn-based MOFs have limited utilities in electrochemistry, on account of the completely filled d-
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orbital of zinc ion that is adverse to exchange electrons.15 Hence, it is highly desired to explore other transitionmetal-based MOF single crystals with macro-microporous structure for pervasive applications. 17
High-quality ordered macroporous materials are mainly synthesized through hard-template approaches.1820 So far, the controllable growth of crystalline porous materials in 3D ordered superpolymer template is considered as the most effective way to produce target macro-microporous materials.8,11,21 Generally, the formation of crystalline MOFs includes four stages: nucleation, crystallization, growth and stationary period.22 Constructing hierarchical pores within MOFs using template method usually suffers from rapid nucleation and further growth of polycrystalline MOFs in the template voids.19 Accordingly, the biggest challenge in preparing ordered macromicroporous MOF single crystals hinges on the control of their nucleation processes within highly ordered 3D templates, especially to inhibit nucleation before filling into ordered voids.23 The main factors affecting the nucleation process include concentration, temperature, solvent and additives.2426 Of note, regulating the concentration of supersaturated solution has been employed as a common way to precisely tune the nucleation process.27 Specifically, as the concentration of the precursor solution increases, the crystal seed will be covered by excessive ligand to isolate the connection within metal ions, which often contributes to the prolongation of nucleation time.23,28 In our previous work, we achieved suppression of the nucleation process by adjusting the concentration of ZnII and imidazole ligands.14 Nevertheless, compared with ZnII, the coordination abilities between first-row transition metal ions (e.g., FeII, CoII, NiII and CuII) and ligands are much stronger because their incomplete d-orbital could provide enough electron vacancies to accommodate long pair electrons from the ligands, which means that they have faster nucleation rate under the same conditions.15,29 For this reason, the nucleation process of transition-metalbased MOFs is very difficult to manipulate. As a result, it is more challenging to regulate macro-microporous MOF single crystals based on these metal centers, leaving substantial opportunities to develop complex MOF structures for a wide range of applications. As known, MOFs also have been extensively studied as precursors or templates to develop a new class of advanced functional nanomaterials.30,31 In view of their thermal and chemical instability, MOFs can be easily transformed into nanocomposites including metal compounds (e.g., metal oxides, sulfides, and selenides) and carbon materials.3032 During their pyrolysis processes, the decomposition of organic ligands could not only alleviate overgrowth and agglomeration of metalcontaining clusters, but also promotes the encapsulation of active components within carbon matrix.3335 Furthermore, MOF-derived materials are capable of inheriting the morphologies of their primitive MOFs under suitable thermal transformation conditions.3032,35 Hence, 3D ordered macroporous metal/carbon-based
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particles can be produced by thermal treatment of ordered macroporous MOF single crystals. Among various potential applications, 3D ordered macroporous architecture shows a bright prospect as a promising electrode structure for rechargeable batteries.3639 It has been demonstrated that hierarchically porous structure with ordered interconnected macro-/meso-/micropores can promote the penetration of electrolytes, leading to fast motion of bulky ions throughout the framework.3640 Besides, the hybrid pore wall can also stabilize underlying transition-metal-based nanoparticles with high electrochemical activity, against agglomeration and keep electrically connected to other grains in conductive carbon matrix.36,40 All these features may assure superior rate and cycling performances. Therefore, enhanced electrochemical properties are generally expected from 3D ordered macroporous electrodes. Herein, we report for the first time single-crystalline Co-based MOFs with ordered macro-microporous structure (denoted as SOM ZIF-67). To be specific, a saturated precursor solution was filled into the 3D ordered superpolymer spheres template interstices followed by ZIF-67 crystallization induction. The novel saturated solution-based double-solventassisted strategy is conducive to controlling the nucleation process by both inhibiting and inducing nucleation (Figure S1). SOM ZIF67 was obtained after template removal with the morphology of a symmetrical tetrakaidecahedron perfectly matching the orientation of the ordered macropores. Subsequently, SOM ZIF-67 was employed as the precursor to synthesize 3D ordered macroporous cobalt diselenide@carbon (3DOM CoSe2@C). The asprepared 3DOM CoSe2@C is composed of CoSe2 nanoparticles uniformly confined in the conductive 3D ordered macroporous carbon skeleton, which can facilitate large-sized chloroaluminate anions (AlxCly−) diffusion and electrolyte penetration. When tested as a cathode material for aluminum-ion batteries (AIBs), the resulting 3DOM CoSe2@C exhibited remarkable rate performance and long cycling stability.
RESULTS AND DISCUSSION Scheme 1. (a) Synthesis routine of 3DOM CoSe2@C. (b) Schematic of working mechanism for rechargeable Al/3DOM CoSe2@C cell, which illustrates the diffusion of large-sized AlxCly− and the electrolyte inside the interconnected macroporous network.
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The preparation procedure of 3DOM CoSe2@C is shown in Scheme 1a, which consists of three main steps. Firstly, a saturated methanolic solution containing 2methylimidazole and cobalt nitrate hexahydrate was filled into 3D ordered polystyrene spheres (PS) template voids, and then a mixed ammonia-methanol solution was employed to induce the formation of ZIF-67 crystalline phase to yield ZIF-67@PS. Afterwards, the PS template was removed in dimethylformamide (DMF) to obtain single-crystalline ordered macro-microporous ZIF-67 (SOM ZIF-67). Finally, the resultant SOM ZIF-67 was used as precursor and mixed with Se powder to synthesize 3D ordered macroporous cobalt diselenide@carbon (3DOM CoSe2@C) via thermal treatment in Ar atmosphere to realize simultaneous carbonization and selenization. Importantly, 3DOM CoSe2@C is composed of small CoSe2 nanoparticles confined in a conductive 3D ordered macroporous carbon skeleton with substantial exposed surface area, which is beneficial to the diffusion of largesized AlxCly− and electrolyte penetration,14 making it an ideal cathode material for AIBs (Scheme 1b).
(denoted as ZIF-67, Figure S4) that is entirely consistent with the simulated pattern in Figure 1c. No impurity phases have been detected, indicating that the as-formed SOM ZIF-67-190nm has good crystallinity. The N2 sorption isotherms of SOM ZIF-67-190nm and ZIF-67 (Figure 1d) reveal typical type-I isotherm characteristics, implying the presence of pores with size concentrated in the micropore range. Moreover, the Brunauer-EmmettTeller (BET) surface area and microspore volume of SOM ZIF-67-190nm are calculated to be 1467.2 m2 g−1 and 0.57 cm3 g−1, respectively, which are higher than 1321.3 m2 g−1 and 0.49 cm3 g−1 of ZIF-67. The larger surface area of SOM ZIF-67-190nm may be ascribed to the existence of interconnected macropores inside the material.14 From the inset in Figure 1d, it can be seen that the formation of the 3D ordered macroporous framework did not affect its microporous structure. Additionally, in order to better understand the morphology and structure of SOM ZIF67-190nm, the models of individual SOM ZIF-67-190nm in the directions of [110] and [100] zone axes are illustrated in Figure 1e and 1i, respectively. Corresponding FESEM images of SOM ZIF-67-190nm (Figure 1f, j) clearly show sharp edges and a tetrahedral morphology that matches perfectly with the ordered macroporous orientation. Also, its transmission electron microscopy (TEM) images (Figure 1g, k) unfold high regularity of macroporous channels. These results gathered from both FESEM and TEM in different directions demonstrate that SOM ZIF67-190nm tetrakaidecahedron has eight (111) facets and six (100) facets. Besides, selected-area electron diffraction (SAED) patterns of SOM ZIF-67-190nm (Figure 1h, l) corresponding to [110] and [100] zone axes further confirm its single crystalline nature.
Figure 1. Morphological and structural characterizations of SOM ZIF-67-190nm. (a, b) Representative FESEM images of SOM ZIF-67-190nm at different magnifications. (c) XRD patterns of SOM ZIF-67-190nm and ZIF-67, along with XRD pattern of simulated ZIF-67 for reference. (d) N2 adsorptiondesorption isotherms of SOM ZIF-67-190nm and ZIF-67 (inset shows corresponding micropore distributions). Microstructure characterizations of an individual SOM ZIF67-190nm in the [110] zone axis: (e) schematic illustration, (f) FESEM image, (g) TEM image and (h) SAED pattern. Microstructure characterizations of an individual SOM ZIF67-190nm in the [100] zone axis: (i) schematic illustration, (j) FESEM image, (k) TEM image and (l) SAED pattern. The typical SOM ZIF-67 was synthesized using PS template with a diameter size of 190 nm (Figure S2, denoted as SOM ZIF-67-190nm). Field-emission scanning electron microscopy (FESEM) images of SOM ZIF-67190nm (Figure 1a, b and Figure S3) unveil its welldefined tetrakaidecahedron morphology with uniform size. The crystallographic structure of SOM ZIF-67-190nm was analyzed by X-ray diffraction (XRD), which exhibits the same diffraction pattern with conventional ZIF-67
Figure 2. Morphological and structural characterizations of 3DOM CoSe2@C-190nm. (a–c) FESEM images of 3DOM CoSe2@C-190nm at different magnifications. (d, e) TEM images of 3DOM CoSe2@C-190nm. (f) HRTEM image of 3DOM CoSe2@C-190nm. (g) HAADF-STEM image and corresponding EDX elemental mappings of Co, Se, C and N.
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The as-prepared SOM ZIF-67-190nm was converted to 3DOM CoSe2@C-190nm by a one-step selenizationcarbonization process (see EXPERIMENTAL SECTION for more details), and its morphology was characterized by FESEM and TEM. FESEM images of 3DOM CoSe2@C190nm (Figure 2a and 2b) show that it preserves well the tetrahedral morphology and highly ordered macroporous structure after calcination. These interconnected macropores may provide large channels for expedite macromolecules diffusion within the material. A magnified FESEM image of 3DOM CoSe2@C-190nm (Figure 2c) manifests its rough surface and the size of the macropore after calcination is reduced from 190 to 140 nm, which may be ascribed to the overall structural shrinkage caused by the transformation of organic ligands into carbon during calcination. The ordered macroporous framework can be further witnessed in the TEM image of an individual 3DOM CoSe2@C-190nm (Figure 2d). Furthermore, a magnified TEM image (Figure 2e) clearly reveals uniform distribution of CoSe2 nanoparticles in the ordered macroporous framework. Impressively, CoSe2 nanoparticles with an average size of 5 nm are completely embedded in the carbon skeleton as disclosed in HRTEM image (Figure 2f). The inset in Figure 2f unambiguously reveals lattice fringes with a spacing of about 0.26 nm, which can be attributed to (210) plane of cubic CoSe2 phase, further proving the successful formation of CoSe2.
Figure 3. Structural and chemical information. (a) XRD patterns of 3DOM CoSe2@C-190nm and CoSe2@C. (b) XPS results: survey spectra, high-resolution spectra of (c) Co 2p, (d) Se 3d and (e) C 1s of 3DOM CoSe2@C-190nm and CoSe2@C. (f) N2 adsorption-desorption isotherms of 3DOM CoSe2@C-190nm and CoSe2@C.
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The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image and corresponding elemental mappings of 3DOM CoSe2@C190nm (Figure 2g) show an even distribution of Co, Se, C, and N elements in the 3D ordered macroporous skeleton. For comparison, CoSe2@C were synthesized via the same annealing method, which displays a bulk solid structure with in-situ confined CoSe2 within a carbonaceous framework exempt of interconnected macropores (Figure S5, 6). The phase composition and crystal structure of 3DOM CoSe2@C-190nm and CoSe2@C were analyzed by XRD, and the results are given in Figure 3a. All the diffraction peaks can be indexed to cubic phase CoSe2 (JCPDS card no. 065-3327) with no additional impurity peaks and crystalline state, suggesting the formation of CoSe2 with high crystallinity. The Raman spectra of 3DOM CoSe2@C-190nm and CoSe2@C show obvious D and G bands of carbon, which reflect the presence of defect carbon and graphitic carbon, respectively (Figure S7). The CoSe2 mass content in 3DOM CoSe2@C-190nm and CoSe2@C composites were determined by thermogravimetric analysis (Figure S8), and calculated to be around 83.5 and 85.8 wt.%, respectively, indicating that they have similar CoSe2 content. X-ray photoelectron spectroscopy (XPS) were applied to analyze chemical state and environment of these two samples, as displayed in Figure 3b–e and Figure S9. The survey XPS spectrum testifies the existence of Co, Se, C, N, and O element (Figure 3b).41 The high-resolution Co 2p spectrum exhibits six main peaks at ~778.4, ~781.1, ~785.4, ~793.3, ~797.1, and ~802.5 eV (Figure 3c). Among them, the binding energy at ~778.4 and ~793.3 eV correspond to Co 2p3/2 and Co 2p1/2, respectively, resulting from Co–Se and Se–Co–Se bonds.4243 The strong peak at ~781.1 and ~797.1 eV could be attributed to Co 2p3/2 and Co 2p1/2 of CoO that originated from partial oxidation of CoSe2 in the air atmosphere, and their satellite peaks (denoted as Sat.) appear at ~785.4 and ~802.5 eV.41,42,44 The Se 3d spectrum can be deconvoluted into five bands, corresponding to Se 3d5/2 at ~ 54.3 eV, Se 3d3/2 at ~ 56.0 eV, Co 3p3/2 at ~ 58.8 eV, Co 3p1/2 at ~ 60.6 eV, and SeO2 at ~ 63.1 eV (Figure 3d), in line with the existence of Co–Se bands.33 Figure 3e shows the high-resolution C 1s spectrum that can be fitted into four peaks, where C–N bond at ~286.0 eV can prove the self-doping of N element in the carbon network owing to the decomposition of N-containing ligand.41,43 This Ndoped carbon matrix favors electron transport to enhance the conductivity of the carbon network.45 The selfincorporation of N in the carbon matrix is also evidenced by the N 1s spectrum (Figure S9).41,43 Based on these results, we can conclude that there is no difference between 3DOM CoSe2@C-190nm and CoSe2@C in chemical bonding state. Unlike their precursors, the N2 sorption isotherms of 3DOM CoSe2@C-190nm and CoSe2@C show type-IV isotherm feature, revealing the existence of mesopores (Figure 3f). Their BET surface areas are calculated to be around 182.8 and 104.1 m2 g−1, respectively. Intriguingly, the much larger BET surface area of CoSe2@C-190nm than CoSe2@C is likely stemmed
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from the well-preserved hierarchical porous structure especially ordered macropores after annealing. In addition, 270 nm and 400 nm of SOM ZIF-67 (denote as SOM ZIF-67-270nm and SOM ZIF-67-400nm) were synthesized employing PS templates with different diameters (Figure S10–13). Likewise, they can also be successfully transformed into 3DOM CoSe2@C with different macroporous pore sizes and maintain the original macroporous structure (denoted as 3DOM CoSe2@C-270nm and 3DOM CoSe2@C-400nm respectively, Figure S14, 15).
Figure 4. Electrochemical performances of 3DOM CoSe2@C and CoSe2@C for AlBs. (a) Charge-discharge curves of 3DOM CoSe2@C-190nm and CoSe2@C at a current density of 1.0 A g−1. (b) CV curves of 3DOM CoSe2@C-190nm and CoSe2@C at a scan rate of 10 mV s−1. (c) Rate performances of 3DOM CoSe2@C sample and CoSe2@C at various current densities. (d) Ragone plots of 3DOM CoSe2@C-190nm, CoSe2@C and other representative cathode materials for AIBs. (e) Longterm cycling stability and coulombic efficiencies of 3DOM CoSe2@C-190nm and CoSe2@C at a current density of 2.0 A g−1. AIBs are considered to be a promising next-generation energy storage device because of its high theoretical gravimetric capacity (2981 mA h g−1) and low price.46,47 In the earlier research stages, AIBs suffered from unsatisfactory performances mainly due to the sluggish Al3+ migration in common electrolytes as a result of the high solvation effect associated with its three positive charges.4648 The solvation issue of Al3+ in AIBs was not solved properly until the discovery of ionic liquid electrolytes, in which AlCl4 and Al2Cl7 referred as
chloroaluminate anions AlxCly instead of Al3+ are the electrochemical reacting species.48,49 This new stratagem triggered a renewed interest in AIBs, as evidenced by the increasing number of related publications.4955 However, the large size of AlxCly poses a problem to its rapid diffusion into the host materials.47,48 In this aspect, it is highly desirable to construct hierarchically porous structure electrode material with confined active material to overcome the above deficiencies. As a proof of concept, 3DOM CoSe2@C was used as a cathode electrode for AIBs. Galvanostatic charge-discharge tests were employed to assess the electrochemical performance of 3DOM CoSe2@C and CoSe2@C electrodes. As depicted in Figure 4a, charge-discharge curve of 3DOM CoSe2@C-190nm in the voltage range 0.05 to 2.2 V versus Al3+/Al shows that the initial discharge capacity of 3DOM CoSe2@C-190nm reaches 400 mA h g−1 at a current density of 1.0 A g−1, while CoSe2@C only delivers 330 mA h g−1. Both samples display two charge platforms at 1.0 and 2.1 V, accompanied with two discharge platforms at 0.9 and 1.8 V. In the cyclic voltammetry (CV) curves (Figure 4b), there are two reduction peaks at 0.9 and 1.8 V and two oxidation peaks at 1.0 and 2.1 V, in accordance with the charge/discharge voltage platforms. Notably, 3DOM CoSe2@C-190nm shows stronger peak intensities than CoSe2@C at the same voltage, verifying that 3DOM CoSe2@C-190nm possesses higher electrochemical reaction activity. This is probably due to the larger surface area originating from the interconnected macropores within the material architecture, offering abundant exposed active sites to increase the reaction kinetics. Note that 3D ordered macroporous carbon (3DOM/C) here is mainly served as a conductive substrate and its contribution to the overall electrode is quite limited (Figure S16 and Figure S17). The rate capability of all the samples are displayed in Figure 4c. Impressively, 3DOM CoSe2@C-190nm can deliver reversible capacities of 177, 123, 101, 93, and 86 mA h g–1 at 1.0, 2.0, 3.0, 4.0, and 5.0 A g–1, respectively, and the corresponding charge/discharge curves at various current densities are shown in Figure S18. When the current density reverts to 1.0 A g−1, 3DOM CoSe2@C-190nm could restore a capacity of 168 mA h g−1. These results are much better than CoSe2@C, which could be ascribed to its 3D ordered macroporous structure towards more efficient electrolyte penetration and largesized AlxCly− diffusion. It is worth noting that 3DOM CoSe2@C-270nm and 3DOM CoSe2@C-400nm exhibit enhanced rate performance similar to that of 3DOM CoSe2@C-190nm, suggesting that increasing the sizes of PS templates to construct even larger microporous structure has insignificant effect on further enhancement of mass transfer. The fast capacity fading at initial cycles for these sam-ples could be attributed to the irreversible decomposi-tion of active substances.54 The Ragone plot of 3DOM CoSe2@C-190nm, along with some representative transition metal sulfides, selenides and graphite-based materials, is given in Figure 4d.4953,55,56 Obviously, 3DOM CoSe2@C-190nm stands out in terms of both energy density and power density, owing to its high voltage
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platform and specific capacity among these reported electrode materials. The long-term cycling performance of 3DOM CoSe2@C-190nm electrode was investigated at a current density of 2.0 A g−1 for 1000 cycles as shown in Figure 4e. After a slow capacity decay in the initial cycles, a specific capacity of 168 mA h g−1 can be remained after 200 cycles. Prolonging the cycling up to 1000 cycles, it still affords a reversible capacity of 125 mA h g−1 with steady coulombic efficiency closed to 96%, attesting a superior long-term operation durability. To our knowledge, this is the best long-term cyclability at high current density among all reported transition-metal dichalcogenide and metal oxides cathode materials for AIBs so far (Table S1). By contrast, the specific capacity of CoSe2@C sustains rapid decay to 58 mA h g−1 in the first 100 cycles and gradually declines to 45 mA h g−1 during the prolonged testing up to 1000 cycles. Therefore, such outstanding cycling performance of 3DOM CoSe2@C-190nm electrode mainly originates from conductive 3D interconnected macroporous channels and even confinement of small CoSe2 nanoparticles, which could not only promote the large-sized AlxCly− and electrolyte diffusion but also alleviate pulverization during charge/discharge.54 Furthermore, CV curves at various scan rates of 3DOM CoSe2@C-190nm and CoSe2@C were carried out and their ionic diffusion coefficients were compared, revealing that 3DOM CoSe2@C-190nm has a higher diffusion coefficient, which can be attributed to its hierarchical porous structure with more active sites (see Figure S19 for more details). In addition, ex-situ XPS is used to investigate charge/discharge process as shown in Figure S20 and Figure S21. After charging process, the pristine peak of Co 2p3/2 at ~778.4 eV has disappeared, and a new peak corresponding to metallic Co is observed at ~777.7 eV, which is consistent with previous reports, indicating that this new system may conform to conversion mechanism.42,43,54 With the establishment of structural features and electrochemical properties, the remarkable aluminum storage performance of 3DOM CoSe2@C-190nm electrode can be assigned to the following factors. Firstly, interconnected ordered macroporous carbon framework not only provides wide channels for large-sized AlxCly− diffusion within the 3D architecture, but also increases contact area between the active materials and the electrolyte. Besides, the existence of ordered macropores can afford more microporous and mesoporous surface area, which leads to more exposed active sites, thereby resulting in remarkable rate performance. Last but not the least, the well confinement of small CoSe2 nanoparticles into the conductive hierarchical porous carbon matrix is advantageous to suppress the dissolution of CoSe2 during charge/discharge cycling, allowing for improving the long-term operation.
CONCLUSIONS In summary, we have designed an ordered macromicroporous ZIF-67 single crystal by saturated solutionbased double-solvent–assisted strategy to precisely
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manipulate nucleation process. Specifically, a saturated ZIF-67 precursor solution was filled into the 3D ordered PS template interstices followed by ZIF-67 crystallization induction. The as-prepared SOM ZIF-67 possesses a highly ordered macro-microporous structure with robust single crystalline nature. Further, SOM ZIF-67 was employed as a precursor to prepare 3DOM CoSe2@C by one-step carbonization and selenization process as a cathode material for AIBs. The as-derived 3DOM CoSe2@C is composed of small CoSe2 nanoparticles uniformly confined in 3D ordered macroporous carbon framework, which is favourable to facilitate the diffusion of large-sized AlxCly− and electrolyte. Benefitting from the aforementioned features, the 3DOM CoSe2@C electrode displays outstanding rate performance and remarkable cycling stability compared to bulk CoSe2@C derived from conventional ZIF-67. 3D ordered macroporous materials with hierarchical structures as advanced materials presented in this work can pave a new avenue for diffusion-controlled applications such as catalysis, separation and energy storage.
EXPERIMENTAL SECTION Preparation of single-crystalline ordered macromicroporous ZIF-67. First, a dark purple saturated methanol solution containing cobalt (II) nitrate hexahydrate (Co(NO3)2‧6H2O, Kermel, AR, 0.4 g mL–1) and 2methylimidazole (Aladdin, AR, 1.0 g mL–1) was prepared. Then, a large piece of 3D PS template (3D PS template was synthesized by the method we reported previously14) was immersed into the prepared precursor solution for 10 min. Subsequently, the above solution was put into a vacuum drying oven undergoing vacuum degassing for 30 min to ensure that all PS voids are filled with precursor solution. The obtained purple PS template was transferred to a beaker and dried at 60 oC for 12 h. Further, the purple PS template was immersed into a mixed solution of 15 mL of methanol and 15 mL of ammonia, and degassed under vacuum for 10 min. In this process, the PS template rapidly broke into small fragments due to the growing pressure of ZIF-67 phase. After soaking for 12 h, the obtained fragments were taken out and dried at 50 oC overnight. Next, the fragments were washed by dimethylformamide (DMF) for several times to ensure that the PS was removed completely. Finally, the sample was washed with methylene chloride to wash off the DMF and dried at 50 oC for 12 h. Preparation of ZIF-67. For comparison, conventional ZIF-67 was also synthesized by using the following procedure. Typically, 50 mL of a methanolic solution containing 0.59 g of Co(NO3)2‧6H2O and 0.5 g of polyvinylpyrrolidone (Aladdin, PVP, Mw. 40000) was slowly added into 50 mL of a methanolic solution containing 0.663 g of 2methylimidazole. The as-obtained mixture was vigorously stirred for 1 min and let to rest at room temperature for 12 h. The precipitate was subsequently collected by
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repeatedly washing with ethanol for at least 3 times before drying at 50 oC overnight. Preparation of 3D ordered macroporous CoSe2@C. SOM ZIF-67 and Se powder (Aladdin, AR) were mixed at a mass ratio of 1: 2, and dispersed in a porcelain boat. The porcelain boat was heated to 350 oC at a ramp rate of 5 oC min–1 and maintained for 1 h followed by heating to 600 oC for 2 h to get 3DOM CoSe2@C. After that, the furnace was naturally cooled to room temperature. The entire process was carried out in Ar atmosphere, the flow rate was controlled at 40 mL min–1. For comparison, ZIF67 was employed as a precursor to synthesize CoSe2@C via the same method. Preparation of 3D ordered macroporous carbon SOM ZIF-67-190nm was dispersed in a porcelain boat without Se powder and annealed in the same manner as described above. The as-obtained sample was washed by 50 mL of 3 M H2SO4 and refluxed at 120 oC for 24 h. Finally, 3DOM/C was obtained by washing several times with deionized water and dried at 60 oC for 12 h. Material Characterizations. The morphology and structure were characterized by field-emission scanning electron microscopy (FESEM, HITACHI-SU8220, 10 kV) and transmission electron microscopy (TEM, JEM-2100F, 200 kV). X-ray diffraction (XRD) patterns were acquired by Bruker D8 Advance with Cu Kα radiation (40 kV, 40 mA). X-ray photoelectron spectroscopy (XPS) measurements were conducted on Xray microprobe of Thermo Escalab 250Xi with monochromatic Al Kα radiation. Raman spectra were collected using LabRAM Aramis with an excitation laser wavelength of λ = 532 nm. Thermal gravimetric analysis (TGA, NETZSCH, STA449F5) was carried out in air with a heating rate of 10 oC min–1. The specific surface area measurement was tested by Tristar nitrogen sorption instrument (Micrometrics Instrument Corporation, 3Flex) after 12 h degassing at 150 oC for SOM ZIF-67 and ZIF-67 and at 300 oC for 3DOM CoSe2@C and CoSe2@C. Electrochemical measurements. The electrochemical tests were carried out by assembling Swagelok-type cells at room temperature. The working electrode consisted of active material (60 wt.%), Ketjen black (30 wt.%) and polytetrafluoroethylene (PTFE, 10 wt.%). Tantalum foil was employed as the current collector and the electrodes were coated on a square flake with an edge length of 8 mm. The active mass loading on the electrode was about 1.0 mg cm−2. Aluminum foils were used as counter and reference electrodes, and Whatman glass microfiber filters (GF/F) were employed as the separators. The ionic liquid electrolyte was prepared by mixing 1-ethyl-3methylimidazolium chloride ([EMIm]Cl, 98%, Aladdin) and anhydrous aluminum chloride (AlCl3, 98%, Aladdin) with molar ratio of 1: 1.3 in an argonatmosphere glove box (H2O < 0.1 ppm, O2 < 0.1 ppm). Galvanostatic charge-discharge tests between 0.05 and 2.2 V versus Al3+/Al were performed on NEWARE battery testing system. Cyclic voltammetry (CV) measurements
were performed at a potential window of 0.05–2.2 V versus Al3+/Al by GAMRY 1000E workstation at a scan rate of 10 mV s–1. The electrochemical impedance spectroscopy (EIS) was collected at the same workstation in the frequency range from 105 to 10–2 Hz.
ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.xxxxxxx. Supplementary characterization and kinetic analysis of the electrochemical behaviour.
AUTHOR INFORMATION Corresponding Author *
[email protected] ORCID Jinlong Liu: 0000-0002-4726-0972 Lei Zhang: 0000-0002-6385-5773
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT This work was financially supported by the National Key Research and Development Program of China (2016YFA0202604), the Natural Science Foundation of China (21606088, 51621001)
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SYNOPSIS TOC Single-crystalline SOM ZIF-67 with highly ordered macro-microporous structure is successfully constructed by saturated solution-based double-solventassisted strategy. SOM ZIF-67 is used as a precursor to prepare 3DOM CoSe2@C through selenization at high temperature. The as-derived 3DOM CoSe2@C is composed of CoSe2 nanoparticles uniformly confined in the 3D ordered macroporous carbon skeleton. Benefiting from the unique hierarchical porous structure, 3DOM CoSe2@C as a cathode material for AIBs achieves remarkable rate performance and long cycling stability.
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