CN113707467A - MOF-derived ZnO @ C cubic electrode material, and preparation method and application thereof - Google Patents
MOF-derived ZnO @ C cubic electrode material, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 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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Abstract
The invention relates to the technical field of electrode materials of super capacitors, in particular to a ZnO @ C cubic block electrode material derived from MOF, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing DMF and absolute ethyl alcohol according to a certain proportion to form a reaction solvent, and performing ultrasonic treatment to uniformly mix the reaction solvent; sequentially adding zinc acetate, terephthalic acid and polyvinylpyrrolidone into a reaction solvent, and ultrasonically stirring until the zinc acetate, the terephthalic acid and the polyvinylpyrrolidone are dissolved to obtain a mixed solution; putting the mixed solution into a reaction container, reacting at the temperature of 120-160 ℃ for 12-24h, naturally cooling, washing and drying to obtain a ZnO @ C precursor derived from MOF; and placing the precursor in a tube furnace, carrying out heat treatment at the temperature of 600-800 ℃ for 2-4h, and naturally cooling to room temperature to obtain the electrode material. The ZnO @ C cubic block-shaped material derived from the MOF is uniform and controllable in morphology, shows higher specific capacity and electrochemical stability when being used as an electrode material, and can meet the requirements of preparing high-performance supercapacitor electrode materials and devices.
Description
Technical Field
The invention relates to the technical field of electrode materials of super capacitors, in particular to a ZnO @ C cubic electrode material derived from MOF, and a preparation method and application thereof.
Background
As a novel energy storage device, the super capacitor has the advantages of high charge-discharge rate, high power density, long cycle life and the like. However, the low energy density thereof limits the wide use of the supercapacitor compared to other types of energy storage devices, and thus, the preparation of high-capacity electrode materials is one of the effective methods for solving the low energy density. The zinc oxide material used as the electrode material of the super capacitor has the advantages of rich redox activity, rich resources, environmental friendliness, high theoretical specific capacity and the like, and is paid much attention to and researched. However, the zinc oxide prepared at present generally has the problems of low conductivity, single appearance, easy generation of dendrite and the like, and thus, the capacity is too low and the performance is attenuated quickly in the charging and discharging process. Therefore, it is necessary to prepare a zinc oxide electrode material with simple synthesis method, low cost, special appearance and better electrochemical performance.
The method for preparing the zinc oxide material with the nano structure and capable of realizing better electrochemical performance mainly comprises the following steps: hydrothermal method (solvothermal method), coprecipitation method, electrochemical deposition method, sol-gel method, and the like. However, the preparation methods have the problems of complex process, impure products, higher experimental requirements, higher cost and unsuitability for large-scale production; in addition, the zinc oxide material prepared by the related method has the defects of large particle size, small specific surface area, uneven appearance and the like.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a ZnO @ C cubic electrode material derived from MOF, a preparation method and application thereof. The prepared ZnO @ C electrode material derived from the MOF is in micro-nano-scale particles, and the particle size is uniform without agglomeration. In addition, the electrode material is used as one of electrode materials of the super capacitor, and has good application potential. The zinc oxide-based electrode material can be used as a super capacitor negative electrode and has good energy storage characteristics in a negative voltage window.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of a ZnO @ C cubic block electrode material derived from MOF comprises the following steps:
step S1: mixing DMF and absolute ethyl alcohol according to a certain proportion to form a reaction solvent, and performing ultrasonic treatment to uniformly mix the reaction solvent;
step S2: sequentially adding a certain amount of zinc acetate, terephthalic acid and polyvinylpyrrolidone into the reaction solvent obtained in the step S1, and ultrasonically stirring until the zinc acetate, the terephthalic acid and the polyvinylpyrrolidone are dissolved to obtain a mixed solution;
step S3: filling the mixed solution obtained in the step S2 into a reaction container, reacting for 12-24h at the temperature of 120-160 ℃, and obtaining a ZnO @ C precursor derived from MOF after naturally cooling, washing and drying;
step S4: and (4) placing the precursor obtained in the step S3 in a tubular furnace, carrying out heat treatment at the temperature of 600-800 ℃ for 2-4h, and naturally cooling to room temperature to obtain the MOF-derived ZnO @ C cubic electrode material.
Further, the preparation method is as described above, and in step S1, the volume ratio of DMF and absolute ethyl alcohol is 3-7: 2.
Further, in the preparation method as described above, in step S1, the time of ultrasound is 20-40 min; in step S2, ultrasonic agitation is performed at a temperature of 60 ℃ for 1-3 hours.
Further, in the above preparation method, step S2, the molar ratio of zinc acetate to terephthalic acid is 1-3: 1.
Further, in the preparation method as described above, step S2, the molar concentration of the zinc acetate mixed solution is 0.1-0.2 mmol/mL.
Further, in the above-mentioned preparation method, step S2, the polyvinylpyrrolidone is PVP-K15, PVP-K30 or PVP-K60.
Further, in the above-mentioned preparation method, step S2, the mass concentration of the polyvinylpyrrolidone in the mixed solution is 0.01-0.03 g/ml.
Further, in the above-mentioned preparation method, in step S3, drying is carried out in a vacuum drying oven at a drying temperature of 60-80 deg.C for a drying time of 12-24 h.
A MOF-derived ZnO @ C cubic block electrode material is prepared according to the preparation method.
Application of the MOF-derived ZnO @ C cubic block electrode material to the battery cathode of a supercapacitor.
The invention has the beneficial effects that:
1. the invention has the advantages of rich raw material sources, environmental protection, safety, no pollution, simple preparation process, low cost and good application prospect of the super capacitor.
2. According to the MOF-derived ZnO @ C prepared by the one-step solvothermal method and the simple heat treatment process, in the process, due to the fact that the hydrolysis reaction of zinc ions and terephthalic acid has a strong coordination function, the cubic MOF-5 is generated, the microstructure of the MOF-5 has a very high surface area and high porosity of a stable three-dimensional framework structure, the generated product is uniform in appearance, the cubic block microscopic size is about 500-1000 nm, the agglomeration phenomenon is avoided, the specific surface area is large, more active sites can be provided, more redox reactions can be achieved, and therefore a suitable preparation route is provided for efficiently preparing the high-performance supercapacitor negative electrode material.
2. The ZnO @ C derived from the MOF prepared by the invention has a cubic block structure with the diameter of micro-nano level, and the special structure of the MOF can provide a higher specific surface area, so that the contact area of an electrode material and electrolyte can be increased, and the rapid transmission of ions is facilitated. Meanwhile, a ZnO @ C cubic block structure derived from the MOF structure has a supporting effect of a metal framework and is not easy to collapse or agglomerate in the charge-discharge cycle process, so that the ZnO @ C cubic block structure has high specific capacitance and good cycle stability when used as a supercapacitor electrode material.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron microscope photograph of the MOF-derived ZnO @ C (heat treated at 600 ℃ C., denoted as ZnO @ C-600) cubic blocks at different magnifications of the supercapacitor anode material obtained in example 1.
FIG. 2 shows the electrochemical performance of the supercapacitor anode material ZnO @ C-600 obtained in example 1 in a three-electrode system: (a) a CV curve; (b) CD curve.
FIG. 3 shows that the negative electrode material ZnO @ C-600 of the supercapacitor obtained in example 1 is added to 1Ag-1Current density of (a).
FIG. 4 is a scanning electron microscope photograph of the MOF-derived ZnO @ C (heat treated at 800 ℃ C., denoted as ZnO @ C-800) cubes at different magnifications of the supercapacitor anode material obtained in example 2.
FIG. 5 shows the electrochemical performance of the supercapacitor anode material ZnO @ C-800 obtained in example 2 in a three-electrode system: (a) a CV curve; (b) CD curve.
FIG. 6 shows that the negative electrode material ZnO @ C-800 of the supercapacitor obtained in example 2 is in the range of 1Ag-1Current density of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
2.2g (10mmol) of zinc acetate, 0.83g (5mmol) of terephthalic acid and 1.51g of polyvinylpyrrolidone K30 are respectively weighed and dispersed in 70mL of mixed solution consisting of 50mL of DMF and 20mL of absolute ethyl alcohol, the mixed system is placed in an ultrasonic water tank for ultrasonic treatment for 30min after being stirred on a magnetic stirring table to accelerate the dissolution of the solute, and then the mixed system is placed on the magnetic stirring table again for stirring for 1h, so that the zinc acetate, the terephthalic acid and the polyvinylpyrrolidone K30 can be better dispersed and completely dissolved in the solute. Putting 70mL of mixed solution into 2 polytetrafluoroethylene reaction kettle linings with the volume of 100mL on average, putting the mixture into a forced air constant-temperature drying oven to react for 24 hours at the temperature of 120 ℃, naturally cooling the mixture to the room temperature after the reaction is finished, and reacting the mixture with DMF (dimethyl formamide) and absolute ethyl alcohol in a ratio of (5: 2, centrifuging and washing the reaction product for 5 times, collecting the washed product, placing the product in a vacuum drying oven, and vacuum-drying for 12h at 60 ℃ to obtain the precursor of ZnO @ C derived from the MOF. And then, placing the precursor in a tube furnace, calcining for 3h at 600 ℃ at the heating rate of 5 ℃/min in the atmosphere of argon, and naturally cooling to room temperature to obtain the MOF-derived ZnO @ C supercapacitor electrode material, which is recorded as ZnO @ C-600.
The present example employs a one-step solvothermal method and a simple heat treatment process. And washing and drying the obtained white precipitate, and then further performing heat treatment to obtain a target product, wherein the experimental steps are simple, the repeatability is high, and the controllability is good. The obtained ZnO @ C-600 has a cubic block structure, is uniform in appearance (figure 1), is about 500-1000 nm in size, has a high specific surface area due to the special structure of the MOF, is good in dispersity, stable in structure and not prone to collapse, has more active sites, can improve the electrochemical reaction kinetics of the electrode material, shortens an ion transmission path, and is beneficial to the realization of high capacity and circulation stability of the electrode material.
The ZnO @ C-600 supercapacitor electrode material obtained in the embodiment is applied to an energy storage system as follows: and assembling a three-electrode system and testing the super-capacitance performance of the three-electrode system. The prepared ZnO @ C-600 is used as an active substance, conductive carbon black (SP) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, and the mass ratio is 80: 10: 10 to a total of 100mg, and a certain amount of dispersant N-methylpyrrolidone (NMP) was added to prepare an electrode slurry. Stirring the slurry at 60 deg.C for 12h, uniformly mixing, taking 15ul electrode slurry with a liquid-transfering gun, and coating on graphite paper substrate (1cm × 2cm) with a coating area of about 1cm2And then placing the electrode in a blast constant temperature drying oven to be dried for 12 hours at the temperature of 90 ℃ to obtain the working electrode.
In the system, Ag/AgCl is used as a reference electrode, Pt is used as a counter electrode, ZnO @ C-600 is used as a working electrode, 3M KOH is used as electrolyte, and the electrochemical performance of the ZnO @ C-600 electrode material in a three-electrode system is tested (figure 2). FIG. 2(a) shows a loading of 0.56mg/cm2The Cyclic Voltammetry (CV) curve of the electrode sheet of the electrode material shows that ZnO @ C-600 has the behavior of a battery-type material, because the redox reaction occurs in the electrode material, and the typical pseudocapacitance performance is reflected. As shown in fig. 2(b) which is a constant current charge-discharge (CD) curve of the electrode sheet, 2A g-1The specific capacitance of the ZnO @ C-600 electrode at the current density of (1) is 158.4F g-1Indicating that the electrode material has a higher specific capacitance. At 10A g-1The specific capacitance of the ZnO @ C-600 electrode material can still reach 106F g at the current density of (1)-1The capacity retention rate was 70%. As shown in fig. 3, 1A g was used-1Current density of electrode plate to perform constant current charge-discharge circulationThe test shows that after 4000 circles of test, the retention rate of the discharge specific capacity can still reach 89.1%, and the coulombic efficiency is always kept about 190.6%, which shows that the material has better rate charge and discharge performance and better cycle stability.
Example 2
2.2g (10mmol) of zinc acetate, 0.83g (5mmol) of terephthalic acid and 1.51g of polyvinylpyrrolidone K30 are respectively weighed and dispersed in 70mL of mixed solution consisting of 50mL of DMF and 20mL of absolute ethyl alcohol, the mixed system is placed in an ultrasonic water tank for ultrasonic treatment for 30min after being stirred on a magnetic stirring table to accelerate the dissolution of the solute, and then the mixed system is placed on the magnetic stirring table again for stirring for 1h, so that the zinc acetate, the terephthalic acid and the polyvinylpyrrolidone K30 can be better dispersed and completely dissolved in the solute. Putting 70mL of mixed solution into 2 polytetrafluoroethylene reaction kettle linings with the volume of 100mL on average, putting the mixture into a forced air constant-temperature drying oven to react for 24 hours at the temperature of 120 ℃, naturally cooling the mixture to the room temperature after the reaction is finished, and reacting the mixture with DMF (dimethyl formamide) and absolute ethyl alcohol in a ratio of (5: 2, collecting the washed product, placing the product in a vacuum drying oven, and performing vacuum drying at 60 ℃ for 12h to obtain a ZnO @ C precursor derived from the MOF, then placing the precursor in a tubular furnace, calcining at 800 ℃ for 3h at the heating rate of 5 ℃/min in the argon atmosphere, and naturally cooling to room temperature to obtain the ZnO @ C supercapacitor electrode material derived from the MOF, wherein the ZnO @ C supercapacitor electrode material is marked as ZnO @ C-800.
The present example employs a one-step solvothermal method and a simple heat treatment process. Compared with the embodiment 1, the synthesis method is similar, the finally obtained precursor is subjected to heat treatment temperature regulation, the experimental steps are simple, and good repeatability and controllability are achieved. The obtained ZnO @ C-800 has a relatively obvious cubic structure (figure 3).
The ZnO @ C-800 obtained in the embodiment is used as a supercapacitor electrode material, a three-electrode system is assembled, and the supercapacitor performance of the three-electrode system is tested. Preparing electrode slurry, namely taking ZnO @ C-800 cubic blocks as active substances, taking conductive carbon black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the materials in a mass ratio of 80: 10: 10, 100mg in total, dispersing agent NMP is added and stirred evenly.Stirring at 60 deg.C for 12 hr, coating 15ul of electrode slurry on graphite paper substrate (1cm × 2cm, coating area about 1 cm)2) And drying the mixture in an oven at 90 ℃ for 12 h. The electrochemical performance of the ZnO @ C-800 electrode material was tested using an Ag/AgCl electrode as a reference electrode, Pt as a counter electrode, and 3M KOH as an electrolyte (FIG. 3). FIG. 3(a) shows a loading of 0.88mg/cm2The Cyclic Voltammetry (CV) curve of the ZnO @ C-800 electrode reflects that the electrode material undergoes redox reaction and has the behavior of a typical pseudocapacitance material. Fig. 3(b) shows a constant current charge/discharge (CD) curve of the electrode sheet. At a current density of 2A g-1The specific capacitance of the ZnO @ C-800 electrode is 107.4F g-1. At 15A g-1The specific capacitance of the ZnO @ C-800 electrode is 78F g under the current density-1Electrode capacity retention ratio of 2A g-1The specific capacitance is 72.6%. As shown in FIG. 6, the electrode sheet was subjected to constant current charge-discharge cycle test at 1Ag-1The discharge specific capacity retention rate is 90.67% and the coulombic efficiency is kept about 140% after 2800 circles of test, which shows that the material has better rate capability and better electrochemical stability.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A preparation method of a ZnO @ C cubic block electrode material derived from MOF is characterized by comprising the following steps:
step S1: mixing DMF and absolute ethyl alcohol according to a certain proportion to form a reaction solvent, and performing ultrasonic treatment to uniformly mix the reaction solvent;
step S2: sequentially adding a certain amount of zinc acetate, terephthalic acid and polyvinylpyrrolidone into the reaction solvent obtained in the step S1, and ultrasonically stirring until the zinc acetate, the terephthalic acid and the polyvinylpyrrolidone are dissolved to obtain a mixed solution;
step S3: filling the mixed solution obtained in the step S2 into a reaction container, reacting for 12-24h at the temperature of 120-160 ℃, and obtaining a ZnO @ C precursor derived from MOF after naturally cooling, washing and drying;
step S4: and (4) placing the precursor obtained in the step S3 in a tubular furnace, carrying out heat treatment at the temperature of 600-800 ℃ for 2-4h, and naturally cooling to room temperature to obtain the MOF-derived ZnO @ C cubic electrode material.
2. The method of claim 1, wherein: in step S1, the volume ratio of DMF to absolute ethyl alcohol is 3-7: 2.
3. The method of claim 1, wherein: in step S1, the ultrasonic treatment time is 20-40 min; in step S2, ultrasonic agitation is performed at a temperature of 60 ℃ for 1-3 hours.
4. The method of claim 1, wherein: in step S2, the molar ratio of the zinc acetate to the terephthalic acid is 1-3: 1.
5. The method of claim 1, wherein: in step S2, the molar concentration of the zinc acetate mixed solution is 0.1-0.2 mmol/mL.
6. The method of claim 1, wherein: in step S2, the polyvinylpyrrolidone is PVP-K15, PVP-K30 or PVP-K60.
7. The method of claim 1, wherein: in step S2, the mass concentration of the polyvinylpyrrolidone in the mixed solution is 0.01-0.03 g/ml.
8. The method of claim 1, wherein: in step S3, drying is carried out in a vacuum drying oven at 60-80 deg.C for 12-24 h.
9. A MOF-derived ZnO @ C cubic block electrode material, characterized in that: the production method according to any one of claims 1 to 8.
10. Use of a MOF-derived ZnO @ C cubic electrode material, wherein the electrode material according to claim 9 is applied to a battery negative electrode of a supercapacitor.
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| CN114566394A (en) * | 2022-04-28 | 2022-05-31 | 兰州大学 | Preparation method and application of iodine ion doped modified Fe-MOF bulk electrode material |
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