CN115206695A - Preparation method of N-doped Zn-MOF derived carbon framework material and supercapacitor - Google Patents
Preparation method of N-doped Zn-MOF derived carbon framework material and supercapacitor Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method of an N-doped Zn-MOF derived carbon skeleton material and a supercapacitor. The preparation method of the N-doped Zn-MOF derived carbon framework material comprises the following steps: 1) Reacting a zinc source and an organic ligand in a solvent to obtain Zn-MOF; 2) Calcining Zn-MOF at 700-950 ℃ under a protective atmosphere to obtain Zn-MOF-C; 3) And mixing Zn-MOF-C and urea, and calcining at 700-900 ℃ to obtain the N-doped Zn-MOF derived carbon framework material Zn-MOF-CN. The N-doped Zn-MOF derived carbon skeleton material is of a layered structure consisting of graphene nanosheets, is large in specific surface area and hierarchical porosity, contains N atom doping, and has excellent capacitance performance, and the prepared super capacitor also has excellent capacitance performance.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method of an N-doped Zn-MOF derived carbon skeleton material and a supercapacitor.
Background
From the viewpoint of charge storage mechanism, supercapacitors are divided into three categories: electric Double Layer Capacitors (EDLCs), pseudocapacitors (PCs) and hybrid capacitors. Among them, EDLCs are widely used due to their high power density, stable cycle life, low cost and maintenance-free characteristics. Porous carbon-based materials, such as Activated Carbon (AC), carbon Nanotubes (CNTs), and reduced graphene oxide (rGO), have been widely studied as electrodes in EDLCs due to their large specific surface area, good pore structure, and high electrical conductivity. Nevertheless, the commercial carbon electrodes in EDLCs still do not provide high specific capacitance and further improvements are needed to meet the ever expanding energy demands of modern society. The capacitance performance of the EDLCs type carbon material is determined by the synergistic effect of four key factors of high conductivity, high specific surface area, graded porosity and heteroatom doping. The four important factors described above exhibit strong interactions but each is sometimes incompatible. Thus, designing and developing carbon materials with high performance capacitance for EDLCs remains a significant challenge.
MOFs have attracted considerable attention as attractive precursors for the preparation of porous carbon electrode materials for EDLCs. Li et al (Li Z. -X., yang B. -L., zou K. -Y., et al. Novel pore carbon nano sheet derived from a 2D Cu-MOF: ultra high porosity and excellent porosity in the supercapacitor cell [ J. ]]Carbon,2019,144, 540-548) preparation of porous Carbon nanoplate 2D Cu-MOF by carbonization and activation at 0.5 ag -1 In 6M KOH solution, a maximum of 260.5 Fg is provided -1 The specific capacitance of (c). Duan et al (Duan h. -h., bai c. -h., li J. -y., et al. Temperature-Dependent dynamics of presensors: metal-Organic Framework-Derived Porous Carbon for High-Performance Electrochemical Double-Layer catalysts [ J]Inorganic Chemistry 2019,58 (4): 2856-2864) reported a cabbage-like porous carbon derived from two-dimensional Cu-MOF, exhibiting 196F g -1 The specific capacitance of (c). In summary, carbon materials are currently availableThe capacitance performance of the capacitor needs to be improved, and the capacitor cannot provide high specific capacitance to meet the increasingly expanding energy demand of the modern society.
Disclosure of Invention
The invention aims to provide a preparation method of an N-doped Zn-MOF derived carbon framework material, which has the advantages of large specific surface area, large hierarchical porosity, N atom doping and excellent capacitance performance.
A second object of the present invention is to provide a supercapacitor having excellent capacitive properties.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of preparing an N-doped Zn-MOF derived carbon framework material, comprising the steps of:
1) Reacting a zinc source and an organic ligand in a solvent, carrying out solid-liquid separation, and drying the solid to obtain Zn-MOF;
2) Calcining Zn-MOF at 700-950 ℃ under a protective atmosphere to obtain Zn-MOF-C;
3) Mixing Zn-MOF-C and urea, and calcining at 700-900 ℃ in a protective atmosphere to obtain an N-doped Zn-MOF derived carbon framework material Zn-MOF-CN; the mass ratio of the Zn-MOF-C to the urea is 1.
The preparation method of the N-doped Zn-MOF derived carbon skeleton material comprises the steps of firstly constructing accordion-shaped prism nanorod Zn-MOF by using a zinc source and an organic ligand, then carbonizing and calcining to obtain a layered structure consisting of graphene nanosheets, and finally carrying out N doping by using urea to obtain the N-doped Zn-MOF derived carbon skeleton material which has high specific surface area, hierarchical porosity and rich active sites and can provide excellent capacitance performance. The urea is used as a nitrogen source to provide N atoms for N doping, and can be used as an activating agent and a pore-enlarging agent to permeate into the layers of the Zn-MOF-C nanorods and etch away some carbon atoms to increase the interlayer spacing, and the appropriate amount of urea can be used to increase the specific surface area and the pore diameter of the N-doped Zn-MOF derived carbon skeleton material Zn-MOF-CN, so that micropores and mesopores in the Zn-MOF-CN coexist, and the hierarchical porosity of the Zn-MOF-CN is improved; in addition, the gasification expansion of urea can lead the edges of the layered carbon structure of Zn-MOF-CN to be crushed into tiny graphene-like nano sheets, further increase the specific surface area of Zn-MOF-CN and provide abundant active sites.
Preferably, the zinc source in the step 1) is zinc acetate dihydrate, and the organic ligand is curcumin; the mass ratio of the zinc source to the ligand is 6-12.
Preferably, the reaction in the step 1) is carried out for 4-5 h at room temperature, and then the temperature is raised to 60-90 ℃ for 48-96 h.
In order to promote the formation of the Zn-MOF material, preferably, the solvent in step 1) is a mixed solvent of dimethylacetamide and anhydrous ethanol; the volume ratio of the dimethylacetamide to the absolute ethyl alcohol is 3.
Preferably, in the step 2), the calcination time is 2 to 5 hours.
In order to ensure the doping amount of the N atoms and prevent the collapse of the carbon pore structure, preferably, in the step 3), the mass ratio of the Zn-MOF-C to the urea is 1.
Preferably, in the step 3), the calcination time is 2-5 h.
A super capacitor comprises a super capacitor electrode and electrolyte, wherein the electrode material of the super capacitor electrode is an N-doped Zn-MOF derived carbon framework material prepared by the preparation method.
The N-doped Zn-MOF derived carbon framework material has high specific surface area, hierarchical porosity and rich active sites, so that the super capacitor disclosed by the invention has excellent capacitance performance.
Preferably, the supercapacitor is a button-type symmetrical supercapacitor, and the electrolyte is electrolyte.
Preferably, the super capacitor is a flexible micro super capacitor based on interdigital electrodes, and the electrolyte is made of polyvinyl alcohol and H 3 PO 4 And water.
The N-doped Zn-MOF derived carbon framework material has certain flexibility and still has stable capacitance performance under different denaturation conditions, so the N-doped Zn-MOF derived carbon framework material has good application prospect in miniaturized electronic products.
Drawings
FIG. 1 is a chemical structure analysis of Zn-MOF and related materials, wherein (a) is XRD pattern of Zn-MOF, zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3, and (b) is Raman spectrum pattern of Zn-MOF, zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN 3;
FIG. 2 shows the pore structures of Zn-MOF-C and Zn-MOF-CN, wherein, (a) N being Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3 2 An adsorption/desorption isotherm, and (b) is the pore size distribution of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN 3;
FIG. 3 is an SEM image and a TEM image of Zn-MOF, wherein (a, b) is an SEM image of Zn-MOF, and (c, d, e) is a TEM image of Zn-MOF;
FIG. 4 is a Fe-SEM image of Zn-MOF-C;
FIG. 5 is a Fe-SEM picture of Zn-MOF-CN, wherein (a, b) is a Fe-SEM picture of Zn-MOF-CN1, (c, d) is a Fe-SEM picture of Zn-MOF-CN2, and (e, f) is a Fe-SEM picture of Zn-MOF-CN 3;
FIG. 6 is a TEM, HRTEM and EDS map of Zn-MOF-CN, wherein (a, b, c) are a TEM, HRTEM and EDS map of Zn-MOF-CN1, (d, e, f) are a TEM, HRTEM and EDS map of Zn-MOF-CN2, and (g, h, i) are a TEM, HRTEM and EDS map of Zn-MOF-CN 3;
FIG. 7 is an electrochemical characterization of different electrode materials in a three-electrode system, wherein (a) is Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, and Zn-MOF-CN3 at 5mV s -1 The CV curve (b) is Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 at 0.25Ag -1 The time of the curve is represented by (C) a CV curve of Zn-MOF-CN2 under different scanning rates, (d) a GCD curve of Zn-MOF-CN2 under different current densities, (e) specific capacitances of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 under different current densities, and (f) an AC impedance diagram of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN 3;
FIG. 8 is the electrochemical characterization of the button-type symmetrical supercapacitor, wherein (a) is the CV curve of the Zn-MOF-CN2 button-type symmetrical supercapacitor at different scan rates, (b) is the GCD curve of the Zn-MOF-CN2 button-type symmetrical supercapacitor at different current densities, and (C) is Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-Specific capacitance of the MOF-CN3 symmetrical supercapacitor under different current densities, (d) is a Ragon graph of the Zn-MOF-CN2 button type symmetrical supercapacitor related to energy-power density, and (e) is a Ragon graph of the Zn-MOF-CN2 button type symmetrical supercapacitor at 2Ag -1 A lower cycle stability performance plot;
FIG. 9 is an electrochemical characterization of a flexible micro supercapacitor, wherein (a) is a digital image of interdigitated MSCs of the flexible micro supercapacitor, (b) is CV curves of the Zn-MOF-CN2 flexible micro supercapacitor at different scan rates, (c) is a GCD curve of the Zn-MOF-CN2 flexible micro supercapacitor at different current densities, and (d) is the area and volume specific capacitance of the Zn-MOF-CN2 flexible micro supercapacitor at different current densities;
FIG. 10 is an electrochemical test of flexible micro-supercapacitors under bending and parallel/series conditions, wherein (a) is the CV curve of Zn-MOF-CN2 flexible micro-supercapacitors at different bending angles, and (b) is the CV curve at 20mV s -1 CV curves of two Zn-MOF-CN2 flexible micro supercapacitors connected in series and in parallel at a scanning rate;
fig. 11 is a charge-discharge cycle performance test and an energy density test of the flexible micro supercapacitor, wherein (a) is a constant-current charge-discharge cycle performance graph of the Zn-MOF-CN2 flexible micro supercapacitor, and (b) is a Ragon graph (lighting LED graph) of the Zn-MOF-CN2 flexible micro supercapacitor.
Detailed Description
The technical solution of the present invention will be further described with reference to the accompanying drawings and the detailed description.
1. Examples of methods of making N-doped Zn-MOF derived carbon framework materials of the invention
Example 1
The preparation method of the N-doped Zn-MOF derived carbon framework material of the embodiment specifically comprises the following steps:
1) Curcumin (600 mg) and zinc acetate dihydrate (540 mg) were added to a mixed solvent of dimethylacetamide (40 mL) and absolute ethanol (10 mL), stirred at room temperature for 4 hours, and then the solution was heated in a pressure bottle in a 75 ℃ oil bath for 72 hours; finally, the resulting suspension was centrifuged and washed several times with DMF, then dried under vacuum at 60 ℃ overnight to give Zn-MOF.
2) Placing Zn-MOF into porcelain boat, in tube furnace under nitrogen atmosphere for 40mL min -1 The temperature rise rate in the calcining process is 2 ℃ for min -1 The temperature is increased to 900 ℃ and kept for 2h. And after calcination, naturally cooling to room temperature in a nitrogen atmosphere to obtain Zn-MOF derived carbon (Zn-MOF-C).
3) 0.5g of Zn-MOF-C and urea are mixed in a mortar according to the proportion of 1. And after calcination, naturally cooling to room temperature in a nitrogen atmosphere to obtain the N-doped Zn-MOF derived carbon skeleton material named as Zn-MOF-CN1.
Example 2
The preparation method of the N-doped Zn-MOF derived carbon skeleton material of the embodiment is different from that of the embodiment 1 in that: step 3) 0.5g of Zn-MOF-C and urea were mixed in a mortar in the ratio of 1. Finally obtaining the N-doped Zn-MOF derived carbon framework material which is named as Zn-MOF-CN2.
Example 3
The preparation method of the N-doped Zn-MOF derived carbon framework material of this example is different from example 1 in that: 3) 0.5g of Zn-MOF-C and urea were mixed in a mortar in a ratio of 1. Finally obtaining the N-doped Zn-MOF derived carbon skeleton material which is named as Zn-MOF-CN3.
2. Embodiments of the inventive ultracapacitor
Example 4
The supercapacitor of the embodiment is a button-type symmetrical supercapacitor, and the preparation process thereof is as follows: 80wt% Zn-MOF-CN, 10wt% carbon black and 10wt% polyvinylidene fluoride were mixed and dispersed in 200. Mu.L of N-methyl-2-pyrrolidone. The obtained uniform slurry is coated on the surface of the foamed nickel to be used as a working electrode. Two working electrodes coated with active substances with the same mass are selected, a polypropylene film is used as a diaphragm to separate the two electrodes, the electrolyte is 6M KOH solution, and the two working electrodes are assembled into a symmetrical button-type device (shell type number CR 2032) under the pressure of 20 MPa.
Example 5
The supercapacitor of the embodiment is a flexible micro supercapacitor based on an interdigital electrode, and the preparation process is as follows: preparation of Zn-MOF-CN2 Dispersion (0.5 mg. ML) -1 ) Directly preparing a miniature supercapacitor electrode by mask-assisted filtration; transferring the obtained interdigital electrode to a flexible polyethylene terephthalate (PET) substrate, connecting the edge of the interdigital electrode with a copper strip with the help of conductive silver paste, and then connecting the interdigital electrode with a copper strip by using 1g of PVA and 1g of H 3 PO 4 And 10mL of deionized water was added to the interdigitated electrodes and the miniature supercapacitor was dried in air for 24h.
3. Examples of the experiments
Experimental example 1: chemical structure and composition of materials
The chemical structures of Zn-MOF, zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 were analyzed by XRD, and the results are shown in FIG. 1 (a). The Zn-MOF prepared by the invention shows characteristic peaks consistent with the reported Zn-MOF at 2 theta =9.5 degrees, 10.6 degrees, 14.3 degrees, 21.7 degrees and 24 degrees. The Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 after being calcined and doped with nitrogen show wide diffraction peaks at 23 degrees and have unobvious diffraction peaks at 42.5 degrees, and the broad diffraction peaks respectively belong to (002) crystal faces and (101) crystal faces of carbon (JCPDS No. 41-1487).
The results of analyzing Zn-MOF, zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 by Raman spectroscopy are shown in FIG. 1 (b). The Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 of the invention all show obvious D band (1340 cm) -1 ) And band G (1580 cm) -1 ) This is due to the defective graphitic carbon structure and the C-C bond sp 2 The vibration of (2). Intensity ratio of two bands in Raman spectrum (I) D /I G ) The degree of graphitization may be reflected. I of the inventive non-N-doped Zn-MOF-C sample D /I G The content of the active carbon is 1.095, and N-doped samples Zn-MOF-CN 1I of Zn-MOF-CN2 and Zn-MOF-CN3 D /I G 1.118, 1.131 and 1.135 respectively. In contrast, I after nitrogen doping D /I G The values increase significantly, which means that more defects and more active sites are advantageous for supercapacitor applications.
Experimental example 2: pore structure of material
Respectively carrying out N on Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 2 The adsorption/desorption isotherm test showed the results shown in fig. 2 (a). The Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 all show the characteristics of I-type and IV-type isothermal adsorption and desorption curves. At very low pressures (P/P) 0 <0.05 Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3 all showed a sharp increase in adsorption capacity, indicating the presence of abundant micropores. However, the Zn-MOF-C samples showed a narrower H3 hysteresis loop, while all the N-doped samples Zn-MOF-CN showed a wider H3 hysteresis loop. At moderate relative pressure (P/P) 0 = 0.4-0.9), a hysteresis loop can be found, confirming the presence of abundant mesopores. The significant increase in mesopores demonstrates that urea, as an N-doped nitrogen source, can act as an activation and pore-expanding agent for porous carbon. As shown in the figure 2b of the drawings, pore size distribution curves show micropores of Zn-MOF-CN samples<2 nm) and mesopores (2-50 nm). The above analysis shows that all Zn-MOF-CN samples of the invention are hierarchically porous. The micropores may provide a large specific surface area and thus a high specific capacitance, and the mesopores may serve as "highways" to facilitate rapid transport of electrolyte ions into the interior of the carbon material. These structural features will all contribute to the high specific capacitance and excellent rate capability of the Zn-MOF-CN sample of the invention.
Furthermore, the specific surface area of the Zn-MOF-C of the invention was 730.8m 2 g -1 The specific surface areas of Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 obtained after N doping are 1149.3m respectively 2 g -1 、1163.9m 2 g -1 And 1129m 2 g -1 Consistent with the trend of increasing and decreasing pore size, the effect of urea as an activator and pore-expanding agent was again demonstrated. The above results also show that appropriate use of urea can increase surface area and pore size, which is beneficial to electrochemical performance of the supercapacitor. And excessive use may cause collapse of the carbon pore structure, resulting in a reduction in specific surface area.
Experimental example 3: apparent morphology analysis of materials
1) Analysis of Zn-MOF appearance
The apparent morphology of Zn-MOF of the present invention was analyzed by SEM and TEM and the results are shown in FIG. 3. The Zn-MOF of the present invention exhibits accordion-like prismatic nanorod structures, but of varying lengths and widths, with multiple layers stacked together with some of the fragments layered on the surface of the pillars. The TEM image further shows the accordion shape of the Zn-MOF of the invention, and the magnified TEM image shows a porous sawtooth-like structure, where the light color implies a high porosity of the Zn-MOF.
2) Analysis of the apparent morphology of Zn-MOF-C
The apparent morphology of Zn-MOF-C of the invention is analyzed by SEM, and the result is shown in FIG. 4. Compared with Zn-MOF, the Zn-MOF-C provided by the invention has little change in morphology, still presents the morphology of accordion-shaped prismatic nanorod after high-temperature calcination, and shows the stability of Zn-MOF structure.
3) Analysis of apparent morphology of Zn-MOF-CN
The apparent morphologies of Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 of the present invention were analyzed by SEM, and the results are shown in FIG. 5. As can be seen from FIG. 5 (a, b), zn-MOF-CN1 shows a more clear layered structure, indicating that urea should act as a chemical activator. Urea has been reported to enhance the "in situ etching" of the activator to form porosity. Therefore, during the N doping process, urea penetrates into the interlayer of Zn-MOF-C nanorods and etches away some carbon atoms, resulting in larger interlayer spacing and clearer layered structure. Comparing SEM images of Zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3, it can be seen that when the Zn-MOF-C/urea ratio is changed (from 1. It can be shown that an increase in the amount of urea facilitates the activation and etching of the layered carbon structure, resulting in a clearer layered structure and a larger interlayer spacing. However, excessive use of urea can lead to disruption of the layered structure.
4) Structure and elemental composition of Zn-MOF-CN
The structures and elemental compositions of Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 of the present invention were further determined by using TEM and EDS mapping images, and the results are shown in FIG. 6. As can be seen from figures 6 (a-i), zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 have a plurality of tiny graphene nano sheets positioned at the thin edge, the nanorods are shown to be composed of many tiny graphene nanoplatelets. The presence of graphene nanoplatelets can be demonstrated by the d-space of 0.34nm, the 0.34nm lattice of the graphene nanoplatelets can be clearly seen in HR-TEM images of Zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3 samples shown in fig. 6 (c, f, i), consistent with Raman (fig. 1 b) results. Peng et al (Peng H., ma G., sun K., et al. A face and rapid preparation of high purity crushed nitro-gene-amplified graphene-like nano sheets for high-performance supercapacitors [ J ]. Journal of Materials Chemistry A,2015,3 (25): 13210-13214) synthesized a highly collapsed nitrogen-doped graphene-like nanosheet using a macroporous resin. They propose that urea gasification expansion enhances the graphene-like nanoplatelet architecture during high temperature thermal treatment. Therefore, the layered carbon structure of Zn-MOF-CN is expanded and broken into tiny graphene-like nano sheets through gasification of urea. EDS mapping of Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 samples proves that N elements are uniformly distributed on Zn-MOF-CN nanorods, which indicates that N doping is successful. EDS mapping results confirmed a uniform distribution of N and O elements on the carbon matrix.
Experimental example 4: electrochemical testing and characterization of materials
1) Electrochemical testing of electrodes of different materials
The specific capacitance of the working electrode was calculated from the charge-discharge curve as follows:
80wt% Zn-MOF-CN, 10wt% carbon black and 10wt% polyvinylidene fluoride were mixed and dispersed in 200. Mu.L of N-methyl-2-pyrrolidone. The obtained uniform slurry is coated on the surface of the foamed nickel to be used as a working electrode. The prepared working electrode is dried for 12h at 80 ℃ in vacuum. Meanwhile, hg/HgO and Pt sheets were used as reference and counter electrodes, respectively. Electrochemical measurements were tested in a three electrode cell using an electrochemical workstation (CHI 760E) at ambient temperature, with an electrolyte of 6M KOH. In addition, a constant current charge-discharge (GCD) test was performed using the CT2001ALAND Cell test system. Specific capacitance (C) 1 ，F g -1 ) Test-based GCD curve measurement according to equation (1):
wherein I, m, Δ t, and Δ V represent a discharge current (a), an active material mass (g), a discharge time(s), and a voltage drop (V).
Due to the large specific surface area, the large hierarchical porosity and the doped N atoms of the Zn-MOF-CN, the Zn-MOF-CN sample has huge potential application as an electrode of a super capacitor. To evaluate the potential application of the prepared porous carbon samples as supercapacitor electrodes, the electrochemical performance of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, zn-MOF-CN3 electrodes was first tested in an electrode system in a three-electrode 6M KOH solution using CV, GCD and EIS, and the results are shown in fig. 7.
As shown in FIG. 7 (a), CV curves of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 electrodes are all approximately rectangular, reflecting good symmetry and capacitance characteristics. The Zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 electrodes show larger response current than the Zn-MOF-C electrodes, which shows that the specific surface area is increased and the specific capacitance is improved after nitrogen doping. Of the three doping ratios, the Zn-MOF-CN2 electrode shows the largest response current. As described above, the appropriate increase of the amount of urea can increase the specific surface area, enhance N doping and larger pore size, thereby improving the performance of the supercapacitor, but when the amount of urea is too large, the carbon pore structure is broken down, which means that the surface area is reduced and the pore size is smaller, thereby causing the performance of the supercapacitor to be degraded. As shown in figure 7 (b) of the drawings, the specific capacitances of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2 and Zn-MOF-CN3 are 193 Fg in this order -1 、208F g -1 、261F g -1 And 233F g -1 . The Zn-MOF-CN2 electrode showed the longest GCD time, which is consistent with the largest CV curve area. As shown in fig. 7 (c), all CV curves of Zn-MOF-CN2 at different scan rates exhibited similar approximately rectangular profiles with no significant distortion, indicating rapid charge transport capability and excellent rate capability. FIG. 7 (d) shows that Zn-MOF-CN2 ranges from 0.25 to 20Ag -1 All show highly symmetric GCD curves at the current density, and show excellent capacitor performance and good electrochemical reversibility.
Fig. 7 (e) shows the specific capacitance of different electrodes at different current densities. Wherein Zn-MOF-CN2 electrode at 0.25ag -1 The capacitance is as high as 293.3 Fg at the current density of -1 . When the current density increased to 20ag -1 At this time, the specific capacitance still reached 187 Fg -1 The capacity retention was about 63.6%, showing its good rate capability. These values are significantly higher than Zn-MOF-C, zn-MOF-CN1 and Zn-MOF-CN3. The specific capacitance values of the Zn-MOF-CN2 electrodes were comparable to, or even higher than, other carbon materials reported previously (Table 1). EIS tests were used to measure the kinetic behavior of carbon materials, as shown in FIG. 7 (f), the equivalent series resistances of Zn-MOF-C, zn-MOF-CN1, zn-MOF-CN2, and Zn-MOF-CN3 were 2.90, 1.55, 1.29, and 1.39 Ω, respectively. It can be seen that the ac impedance plots for all electrodes have a smaller half-arc in the high frequency region and a nearly vertical line in the low frequency region, which means that the series of materials has a smaller charge transfer resistance and better capacitive behavior. Considering its optimized N-doping content, specific surface area and pore size distribution, the Zn-MOF-CN2 sample shows the best capacitive performance.
TABLE 1 specific capacitance values of the different electrodes
Reference documents:
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[3]Duan H.-H.,Bai C.-H.,Li J.-Y.,et al.Temperature-Dependent Morphologies of Precursors:Metal–Organic Framework-Derived Porous Carbon for High-Performance Electrochemical Double-Layer Capacitors[J].Inorganic Chemistry,2019,58(4):2856-2864.
[4]Gu Y.,Miao L.,Yin Y.,et al.Highly N/O co-doped ultramicroporous carbons derived from nonporous metal-organic framework for high performance supercapacitors[J].Chinese Chemical Letters,2021,32(4):1491-1496.
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2) Electrochemical performance of button type symmetrical supercapacitor
The electrochemical performance test voltage window range of the button type symmetrical super capacitor is 0-1V. The specific capacitance, the energy density and the power density of the button type symmetrical super capacitor are calculated according to the charging and discharging curves as follows:
wherein, C 2 Is (F g) -1 ) Is based on the specific capacitance of a Zn-MOF-CN symmetrical super capacitor; i (A) is current; Δ t(s) is the discharge time; m (mg) is the total mass of the active substance; Δ V (V) is the voltage window; e (Wh kg) -1 ) Is the energy density; p (W kg) -1 ) Is the power density.
To further characterize the electrochemical performance of the Zn-MOF-CN2 electrode, a button symmetric supercapacitor was assembled using 6M KOH electrolyte, and the electrochemical performance of the button symmetric supercapacitor was analyzed, and the results are shown in fig. 8. As can be seen from FIG. 8 (a), the scanning rate is in the range of 5 to 200mV s -1 The CV curve exhibits a typical rectangular shape in the range of 0 to 1V, indicating a rapid electrochemical response in the electrolyte solution. Even at high scan rates, the CV shape was mirror symmetric, indicating high reversibility of the sample. Further GCD is used for controlling the current density to be 0.25-20 Ag -1 To evaluate the energy and power density of the button symmetric supercapacitor as shown in fig. 8 b. All GCD curves show a typical linear discharge curve, indicating a low internal resistance, corresponding to the above-mentioned EIS measurements shown in fig. 7 (f). The capacitance value of the button-type symmetrical supercapacitor is calculated according to equation (2) and is shown in fig. 8 (c). The symmetrical device of Zn-MOF-CN2 electrode shows 126.5 Fg -1 (at 0.25A g -1 Time) and 106.4 Fg -1 (at 20A g) -1 Time), has a very high capacity retention (84.11%). These values are also significantly higher than those of Zn-MOF-C Zn-MOF-CN1 and Zn-MOF-CN3 electrodes.
Fig. 8d shows a Ragone plot of the correlation of the button symmetric supercapacitor with energy-power density. When the current density is 0.25ag -1 The hour Zn-MOF-CN2 button type symmetrical super capacitor is 250W kg -1 Shows a power density of 17.57Wh kg -1 High energy density. In addition, when the current density is 20Ag -1 When the power density is increased to 20kW kg -1 The energy density of the button type symmetrical super capacitor is kept at 14.78 Whhkg -1 . To further demonstrate its potential in supercapacitors, zn-MOF-CN2 button symmetric supercapacitors were at 2Ag -1 As shown in fig. 8 e. At 400After 00 GCD cycles, the Zn-MOF-CN2 button type symmetrical supercapacitor still maintains over 94.45 percent of initial specific capacitance, and the Zn-MOF-CN2 is proved to be an ideal candidate material of the button type supercapacitor.
3) Electrochemical performance of flexible micro-supercapacitor
The electrochemical performance test of the micro super capacitor is carried out on a CHI 760E electrochemical workstation, and the potential window is 0-1V. The area specific capacitance, the volume specific capacitance, the energy density and the power density of the flexible micro super capacitor are calculated according to a charge-discharge curve as follows:
wherein, C A Is (mF cm) -2 ) Is the area specific capacitance; j (mA cm) -2 ) Is the current density; Δ t(s) is the discharge time; c V Is (F cm) -3 ) Is the volume specific capacitance; d (mm) is the thickness of the device; e A (μWh cm -2 ) Is the areal energy density; p A (μW cm -2 ) Is the area power density.
The rapid development of portable/wearable electronics has placed new demands on flexible, intelligent, and sustainable energy storage devices. Due to the advantages of high power density, fast charge/discharge rates, and long life, micro Supercapacitors (MSCs) have shown great potential as essential power sources for miniaturized electronic applications. In order to determine the performance of Zn-MOF-CN2 as a flexible electrode material, an organic filter membrane is adoptedAs a base material, with H 3 PO 4 PVA gel is a solid electrolyte. The flexible interdigital electrode is prepared by the aid of vacuum filtration of the mold, the electrochemical performance of the button type symmetrical supercapacitor is analyzed, and the result is shown in figure 9.
As can be seen from fig. 9 (a), the flexible interdigital device is composed of four positive electrodes and four negative electrodes. In order to evaluate the electrochemical performance of the prepared flexible micro super capacitor, the electrochemical performance is 1-50 mV s -1 And a voltage window of 0-1V, the results of the CV test were as shown in FIG. 9 (b), even at 50mV s -1 Shows only a slight change in CV curve at high scan rates, indicating fast transport of electrolyte ions and excellent rate capability. This may be attributed to the high specific surface area, hierarchical porosity and rich active sites of the Zn-MOF-CN2 electrode material. At 20-100 mu A cm -2 GCD testing was performed at various current densities within the range to further evaluate the capacitive performance of Zn-MOF-CN2 based flexible MSCs, as shown in fig. 9 (c), all GCD curves are symmetrical, approximately triangular, indicating excellent rate performance. The area specific capacitance was calculated from the GCD curve, as shown in FIG. 9d, for Zn-MOF-CN 2-based flexible MSCs at a current density of 20 μ A cm -2 When it is expressed at 42mF cm -2 High area specific capacitance and 1.5F cm -3 Volume to capacitance. Even if the current density is increased to 100 μ A cm -2 When the area specific capacitance of the Zn-MOF-CN 2-based flexible MSCs can still be kept at 15.8mF cm -2 The volume specific capacitance is kept at 0.6F cm -3 This indicates that the Zn-MOF-CN 2-based flexible MSCs have excellent rate capability.
Further evaluation of the potential of Zn-MOF-CN2 for use in flexible electronic systems was based on the testing of Zn-MOF-CN2 flexible MSCs under both bending and parallel/series conditions. As shown in fig. 10 (a), the CV curves show high coincidence at different bending angles, demonstrating their stable capacitive behavior under deformation conditions. The inset of fig. 10a further demonstrates that Zn-MOF-CN2 based flexible MSCs can retain their normal structure and flexibility at different bending angles of 0 °, 30 °, 60 ° and 90 °, indicating excellent flexibility. As shown in FIG. 10 (b), the total specific capacitance and the operating voltage can be adjusted by connecting Zn-MOF-CN2 flexible MSCs in parallel or in series. When two Zn-MOF-CN2 flexible MSCs are connected in series, the voltage is doubled. And when two Zn-MOF-CN2 flexible MSCs are connected in parallel, the response current and the capacitance are doubled, and the excellent integration capability of the Zn-MOF-CN2 flexible MSCs is shown.
The MSCs devices based on Zn-MOF-CN2 were subjected to constant current charge and discharge cycling performance, and as a result, the devices retained 76.56% of the initial capacitance after 5000 cycles, as shown in fig. 11 (a). As can be seen from FIG. 11 (b), the Zn-MOF-CN2 based MSCs devices were 20, 25 and 50 μ W cm, respectively -2 At power densities of 5.8, 4 and 2.19. Mu. Wh cm -2 The energy density of (1). In order to more intuitively express the good electrochemical performance of the MSCs based on Zn-MOF-CN2, two MSCs are connected in series to light a red light-emitting diode (LED) lamp, so that the good energy storage performance is displayed. These results indicate the potential application of Zn-MOF-CN2 material in miniaturized electronic products.
Claims (10)
1. A preparation method of an N-doped Zn-MOF derived carbon framework material is characterized by comprising the following steps:
1) Reacting a zinc source and an organic ligand in a solvent, carrying out solid-liquid separation, and drying the solid to obtain Zn-MOF;
2) Calcining Zn-MOF at 700-950 ℃ under a protective atmosphere to obtain Zn-MOF-C;
3) Mixing Zn-MOF-C and urea, and calcining at 700-900 ℃ in a protective atmosphere to obtain an N-doped Zn-MOF derived carbon framework material Zn-MOF-CN; the mass ratio of the Zn-MOF-C to the urea is 1.
2. The method of preparing an N-doped Zn-MOF derived carbon framework material according to claim 1, wherein in step 1) the zinc source is zinc acetate dihydrate and the organic ligand is curcumin; the mass ratio of the zinc source to the ligand is 6.
3. The preparation method of the N-doped Zn-MOF derived carbon framework material according to claim 2, wherein the reaction in the step 1) is performed for 4-5 h at room temperature, and then the temperature is raised to 60-90 ℃ for 48-96 h.
4. The process for the preparation of an N-doped Zn-MOF derived carbon framework material according to any one of claims 1 to 3, wherein the solvent in step 1) is a mixed solvent of dimethylacetamide and anhydrous ethanol; the volume ratio of the dimethylacetamide to the absolute ethyl alcohol is 3.
5. The method for preparing an N-doped Zn-MOF derived carbon framework material according to claim 1, wherein in step 2), the calcination time is 2-5 h.
6. The method for preparing an N-doped Zn-MOF derived carbon framework material according to claim 1, wherein in the step 3), the mass ratio of Zn-MOF-C to urea is 1.
7. The method for preparing an N-doped Zn-MOF derived carbon framework material according to claim 1 or 6, wherein in step 3), the calcination time is 2-5 h.
8. A supercapacitor, comprising a supercapacitor electrode and an electrolyte, wherein the electrode material of the supercapacitor electrode is an N-doped Zn-MOF derived carbon skeleton material prepared by the preparation method of any one of claims 1 to 7.
9. The supercapacitor according to claim 8, wherein the supercapacitor is a button-type symmetrical supercapacitor and the electrolyte is an electrolyte.
10. The supercapacitor according to claim 8, wherein the supercapacitor is a flexible miniature supercapacitor based on interdigitated electrodes, and the electrolyte is made of polyvinyl alcohol, H 3 PO 4 And water.
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