CN109872880B - Preparation method of humic acid layer sheet-based bimetallic MOFs composite powder - Google Patents
Preparation method of humic acid layer sheet-based bimetallic MOFs composite powder Download PDFInfo
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Abstract
The invention discloses a preparation method of humic acid layer sheet-based bimetallic MOFs composite powder, which comprises the following steps: dissolving sodium humate in deionized water, and filtering to obtain a suspension A; adding nickel nitrate hexahydrate and cobalt nitrate hexahydrate into deionized water to obtain a solution B; mixing the suspension A and the solution B, performing ultrasonic treatment, performing hydrothermal reaction, and performing ultrasonic treatment to obtain a suspension C; dispersing tetra-4, 4' -biphenyldicarboxylic acid in deionized water, and dropwise adding a sodium hydroxide aqueous solution to obtain a solution D; fifthly, dripping the solution D into the suspension C, and carrying out hydrothermal reaction; sixthly, cooling the product to room temperature, performing centrifugal separation, and drying to obtain the humic acid layer sheet-based bimetallic MOFs composite powder. The humic acid lamina base bimetal MOFs composite powder prepared by the invention has the advantages that MOFs grow on the humic acid lamina in a two-dimensional nanosheet form, and when the composite powder is used as an electrode material, the composite powder has high specific capacitance, good rate characteristic and good circulation stability.
Description
Technical Field
The invention belongs to the technical field of crossing of energy storage materials and synthetic chemistry, and particularly relates to a preparation method of humic acid layer chip-based bimetal MOFs composite powder.
Background
Metal-Organic Frameworks (MOFs) are network crystalline framework structures formed by connecting transition Metal ions and oxygen-containing or nitrogen-containing Organic ligands through coordination bonds. MOFs have the characteristics of large specific surface, adjustable pores, various structures and the like, and have potential application prospects in the fields of catalysis, optics, gas adsorption, energy storage and the like. The MOFs have good electrochemical activity, and more active sites can be obtained by controlling the structure and the porosity of the metal organic framework material. Therefore, the MOFs not only have the characteristics of porosity and large specific surface of the carbon material, but also can play a role in energy storage of electric double layer capacitors; and variable-valence transition metal ions can be selected as central ions to play the role of pseudocapacitance energy storage. Research shows that MOFs often have high specific capacitance and are expected to become a novel energy storage material. However, MOFs have poor conductivity, dispersibility and capacitive stability, which limits their applications in the electrochemical field. The graphene is a two-dimensional carbon material, is a honeycomb-shaped single-layer carbon film formed by sp2 hybridized carbon atoms, has excellent performances of large specific surface, high conductivity and the like, and can meet the requirements of a super capacitor on high energy density and high power density of an electrode material. Researches show that the MOFs are loaded on the surface of a graphene sheet, and the method is a method for effectively improving the conductivity, the dispersibility and the capacitive performance of the MOFs. However, graphene is usually prepared by Hummers chemical oxidation method, which has the problems of complicated synthesis process and serious environmental pollution, so that the application of graphene is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of humic acid layer sheet-based bimetal MOFs composite powder aiming at the defects of the prior art. The method comprises the steps of firstly treating a sodium humate aqueous solution loaded with nickel-cobalt ions by adopting an ultrasonic-hydrothermal combined method to obtain a humic acid layer slice, then growing MOFs on the surface of the humic acid layer slice in situ by adopting a hydrothermal method, and finally obtaining the humic acid layer slice base MOFs with high complexing degree connected through coordination bonds.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of humic acid layer chip-based bimetal MOFs composite powder is characterized by comprising the following steps:
dissolving sodium humate in deionized water, and filtering to obtain a suspension A;
step two, adding nickel nitrate hexahydrate and cobalt nitrate hexahydrate into deionized water, and uniformly stirring to obtain a solution B; the sum of the mass of the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate is 2.6-4.0 times of the mass of the sodium humate in the step one;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 35-45 min, then carrying out hydrothermal reaction for 10-12 h at the temperature of 150-190 ℃, and carrying out ultrasonic treatment for 15-25 min after the material after the hydrothermal reaction is cooled to room temperature to obtain a suspension C;
dispersing 4, 4' -biphenyldicarboxylic acid in deionized water, and then dropwise adding a sodium hydroxide aqueous solution to obtain a solution D; the mass of the 4, 4' -biphenyl dicarboxylic acid is 0.5-1.1 times of that of the sodium humate in the step one;
step five, dripping the solution D in the step four into the suspension C in the step three while stirring, and then carrying out hydrothermal reaction for 9-12 h at the temperature of 150-190 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate obtained after the centrifugal separation, and drying to obtain the brown black humic acid layer sheet-based bimetallic MOFs composite powder.
The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder is characterized in that in the first step, the volume of deionized water is 0.9-1.2 times of the mass of sodium humate, wherein the volume is mL, and the mass is mg.
The preparation method of the humic acid layer sheet-based bimetallic MOFs composite powder is characterized in that the mass ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate in the second step is (0.5-2): 1.
The preparation method of the humic acid layer sheet-based bimetallic MOFs composite powder is characterized in that in the second step, the volume of the deionized water is 0.11-0.17 times of the sum of the mass of the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate, wherein the unit of the volume is mL, and the unit of the mass is mg.
The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder is characterized in that the frequency of ultrasonic treatment in the third step is 40 KHz-60 KHz, and the power is 150W-200W.
The preparation method of the humic acid layer chip-based bimetallic MOFs composite powder is characterized in that in the fourth step, the concentration of the sodium hydroxide aqueous solution is 0.2mol/L, and the molar ratio of sodium hydroxide to 4, 4' -biphenyldicarboxylic acid is (2-4): 1.
The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder is characterized in that the volume of deionized water in the fourth step is 1.25-2.5 times of the mass of 4, 4' -biphenyldicarboxylic acid, wherein the volume is mL, and the mass is mg.
The preparation method of the humic acid layer sheet-based bimetallic MOFs composite powder is characterized in that the drying in the sixth step is freeze drying.
Humic Acid (HA) is a natural macromolecule, and consists of alkyl/aryl skeletons which are crosslinked by oxygen-containing functional groups such as carboxyl, hydroxyl, ketone, quinone and the like. It is considered to be a natural graphene oxide because of its physical and chemical structure, surface polarity and activity, which are very close to those of graphene oxide. In addition, humic acid contains abundant carboxyl, so that the humic acid shows strong coordination capacity with transition metal ions, good hydrophilicity and certain surface activity. Meanwhile, a certain amount of active free radicals are also arranged on the humic acid macromolecules. The sodium salt of humic acid can be dissolved in water, but the solubility is extremely low, the filtrate filtered by qualitative filter paper usually exists in the form of coexistence of colloidal fluid and suspension, and an obvious lamellar stacking structure is shown in a microscopic form. According to the invention, sodium humate is selected as a raw material, and through hydrothermal treatment, on one hand, condensation polymerization and aromatization are generated among macromolecules of humic acid, so that the humic acid is converted into a structure closer to graphene; on the other hand, the humic acid lamina is stripped to a certain degree.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts an ultrasonic-hydrothermal combined method to treat the sodium humate aqueous solution loaded with nickel cobalt ions. The strong electrostatic repulsion and thermal diffusion driving force generated by hydrothermal treatment and high-energy cavitation generated by ultrasonic treatment realize the stripping of the humate. Meanwhile, the humic acid macromolecules contain rich carboxyl, hydroxyl and active free radicals, so that the humic acid macromolecules can be converted into a structure closer to graphene through condensation polymerization, aromatization and other processes under hydrothermal treatment.
2. According to the invention, a humic acid lamina is selected as a carrier, and the growth of MOFs is guided by the specific surface activity of the humic acid lamina and the strong coordination action of the humic acid lamina and transition metal ions, so that the MOFs grow on the humic acid lamina in a two-dimensional nanosheet form, and the humic acid lamina-based bimetal MOFs composite powder with high complexing degree and connected by coordination bonds is finally formed.
3. When the humic acid layer chip-based bimetallic MOFs composite powder prepared by the invention is used as an electrode material, the humic acid layer chip-based bimetallic MOFs composite powder has high specific capacitance, good rate characteristic and good cycling stability. At a current density of 5 A.g-1The lower specific capacitance can reach 762F g-1The solution remained 457F g after 3000 times of circulation-1Even at 100A · g-1Can still work under the current density of the capacitor, and the specific capacitance reaches 410 F.g-1。
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
Fig. 1 is an SEM image of humic acid layer base bimetal MOFs composite powder prepared in example 1 of the present invention, with a magnification of 2000 times.
Fig. 2 is an SEM image of humic acid layer base bimetal MOFs composite powder prepared in example 1 of the present invention, with a magnification of 5000 times.
Fig. 3 is an SEM image of humic acid layer base bimetal MOFs composite powder prepared in example 1 of the present invention, the magnification is 10000 times.
Fig. 4 is an XRD chart of humic acid layer piece-based bimetal MOFs composite powder prepared in example 1 and example 2 of the present invention and raw material sodium humate.
Fig. 5 is a raman spectrogram of humic acid layer base bimetal MOFs composite powder prepared in example 1 and example 2 of the present invention and raw material sodium humate.
Fig. 6 is a cyclic voltammetry curve of humic acid layer base bimetal MOFs composite powder prepared in example 1 of the present invention at different sweep rates.
Fig. 7 is a constant current charge and discharge curve of the humic acid layer piece-based bimetal MOFs composite powder prepared in embodiment 1 of the present invention at different current densities.
Fig. 8 is a rate characteristic curve of humic acid layer base bimetal MOFs composite powder prepared in example 1 of the present invention.
Fig. 9 is a change curve of the specific capacitance of the humic acid layer piece-based bimetallic MOFs composite powder prepared in example 1 in the current density of 5A/g in the process of 3000 times charging and discharging.
Detailed Description
Example 1
The preparation method of the humic acid layer chip-based bimetallic MOFs composite powder specifically comprises the following steps:
step one, dissolving 22mg of sodium humate in 20mL of deionized water, and filtering by using qualitative filter paper to remove large particles to obtain a suspension A;
step two, adding 43.5mg of nickel nitrate hexahydrate and 43.5mg of cobalt nitrate hexahydrate into 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 40min, then carrying out hydrothermal reaction for 12h at 190 ℃, and carrying out ultrasonic treatment for 20min after the material after the hydrothermal reaction is cooled to room temperature (25 ℃) to obtain a suspension C; wherein the ultrasonic treatment frequency is 60KHz, and the power is 180W;
step four, dispersing 24mg of 4,4 '-biphenyldicarboxylic acid in 30mL of deionized water, then dropwise adding 1mL of 0.2mol/L sodium hydroxide aqueous solution, and stirring until the 4, 4' -biphenyldicarboxylic acid is completely dissolved to obtain a solution D;
step five, dripping the solution D in the step four into the suspension C in the step three while stirring, and then carrying out hydrothermal reaction for 12 hours at 190 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate after the centrifugal separation, and performing freeze drying to obtain the brown black humic acid layer piece-based bimetal MOFs composite powder, namely HA-NiCo-MOF-1.
Fig. 1, fig. 2 and fig. 3 are SEM images of humic acid layer base bimetal MOFs composite powder prepared in this example. Microscopically, the composite powder material is formed by loading two-dimensional lamellar MOFs on a humic acid lamellar. Fig. 4 is an XRD chart of the humic acid layer piece-based bimetallic MOFs composite powder and the raw material sodium humate prepared in this example. As can be seen from the figure, the sodium humate has a stronger diffraction peak near 25 degrees and a weaker diffraction peak near 45 degrees, which indicates that the sodium humate has a certain graphite microcrystalline structure and order degree. The humic acid layer piece-based bimetallic MOFs composite powder has a series of characteristic diffraction peaks of nickel-cobalt bimetallic MOFs at the positions of 6.1 degrees, 12.4 degrees, 15.3 degrees, 19.2 degrees, 29.1 degrees and 31.2 degrees. In addition, a weak diffraction peak still exists at 25 degrees, which indicates that humic acid in the composite powder retains the graphitization structural characteristics. Fig. 5 is a raman spectrogram of humic acid layer base bimetal MOFs composite powder and raw material sodium humate prepared in example 1 of the present invention. The raw material sodium humate mainly has two characteristic peaks: d peak (1370 cm)-1) And G peak (1601 cm)-1) Of which ID/IGIs 1.07, which shows that the sodium humate has certain ordered graphitized structural characteristics. Humic acid layer piece base bimetal MOFsThe composite powder also has weak D peak, and G peak is 1609cm by 4, 4' -biphenyldicarboxylic acid in MOFs-1Strong characteristic peak coverage at (c). The humic acid layer piece base bimetal MOFs composite powder is 800-3100 cm-1The range shows a series of characteristic peaks corresponding to the characteristic peaks of the 4, 4' -biphenyldicarboxylic acid ligand. In addition, at 413cm-1、627cm-1The characteristic peaks correspond to the stretching vibration peaks of Ni-O and Co-O respectively, which shows that the 4, 4' -biphenyldicarboxylic acid does form a complex with nickel cobalt ions.
Example 2
The preparation method of the humic acid layer chip-based bimetallic MOFs composite powder specifically comprises the following steps:
step one, dissolving 22mg of sodium humate in 22mL of deionized water, and filtering by using qualitative filter paper to remove large particles to obtain a suspension A;
step two, adding 48.4mg of nickel nitrate hexahydrate and 24.2mg of cobalt nitrate hexahydrate into 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 45min, then carrying out hydrothermal reaction for 11h at 150 ℃, and carrying out ultrasonic treatment for 25min after the material after the hydrothermal reaction is cooled to room temperature (25 ℃), thus obtaining a suspension C; wherein the ultrasonic treatment frequency is 50KHz, and the power is 200W;
dispersing 18mg of 4,4 '-biphenyldicarboxylic acid in 30mL of deionized water, then dropwise adding 1mL of 0.2mol/L sodium hydroxide aqueous solution, and stirring until the 4, 4' -biphenyldicarboxylic acid is completely dissolved to obtain a solution D;
step five, dripping the solution D in the step four into the suspension C in the step three while stirring, and then carrying out hydrothermal reaction for 11h at the temperature of 150 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate after the centrifugal separation, and performing freeze drying to obtain the brown black humic acid layer piece-based bimetal MOFs composite powder, namely HA-NiCo-MOF-2.
SEM tests show that the microscopic morphology of the humic acid layer piece-based bimetallic MOFs composite powder prepared in the embodiment is similar to that of the embodiment 1, and the microstructure is represented by that two-dimensional MOFs layer pieces are loaded on the humic acid layer pieces. Raman tests show that each characteristic peak of the humic acid layer piece-based bimetallic MOFs composite powder prepared in the embodiment is similar to that of embodiment 1, and the peak has almost no change.
Example 3
The preparation method of the humic acid layer chip-based bimetallic MOFs composite powder specifically comprises the following steps:
step one, dissolving 22mg of sodium humate in 26mL of deionized water, and filtering by using qualitative filter paper to remove large particles to obtain a suspension A;
step two, adding 19.3mg of nickel nitrate hexahydrate and 38.7mg of cobalt nitrate hexahydrate into 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 35min, then carrying out hydrothermal reaction for 10h at 170 ℃, and carrying out ultrasonic treatment for 15min after the material after the hydrothermal reaction is cooled to room temperature (25 ℃) to obtain a suspension C; wherein the frequency of ultrasonic treatment is 40KHz, and the power is 150W;
dispersing 12mg of 4,4 '-biphenyldicarboxylic acid in 30mL of deionized water, then dropwise adding 1mL of 0.2mol/L sodium hydroxide aqueous solution, and stirring until the 4, 4' -biphenyldicarboxylic acid is completely dissolved to obtain a solution D;
step five, dripping the solution D in the step four into the suspension C in the step three while stirring, and then carrying out hydrothermal reaction for 9 hours at the temperature of 170 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate obtained after the centrifugal separation, and performing freeze drying to obtain the brown black humic acid layer sheet-based bimetallic MOFs composite powder.
SEM tests show that the microscopic morphology of the humic acid layer piece-based bimetallic MOFs composite powder prepared in the embodiment is also similar to that of the embodiment 1, and the two-dimensional MOF layer pieces are loaded on the humic acid layer pieces and have uniform sizes; the composite powder has good dispersibility and uniformity. Raman tests show that each characteristic peak of the humic acid layer piece-based bimetallic MOFs composite powder prepared in the embodiment is similar to that of embodiment 1, and the peak has almost no change.
Comparative example 1
The preparation method of the humic acid layer chip base Ni-MOFs composite powder comprises the following steps:
step one, dissolving 22mg of sodium humate in 20mL of deionized water, and filtering by using qualitative filter paper to remove large particles to obtain a suspension A;
step two, adding 87mg of nickel nitrate hexahydrate into 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 40min, then carrying out hydrothermal reaction for 12h at 190 ℃, cooling to room temperature, and carrying out ultrasonic treatment for 20min to obtain a suspension C; wherein the frequency of the ultrasonic wave is 60KHz, and the power is 180W;
step four, dispersing 24mg of 4, 4' -biphenyldicarboxylic acid in 30mL of deionized water, and then dropwise adding 1mL of 0.2mol/L sodium hydroxide aqueous solution to obtain a solution D;
step five, dripping the solution D into the suspension C while stirring, and then carrying out hydrothermal reaction for 12h at 190 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate obtained after the centrifugal separation, and performing freeze drying to obtain the brown black humic acid layer sheet base single metal Ni-MOFs composite powder.
Comparative example 2
The preparation method of the humic acid layer chip base Co-MOFs composite powder comprises the following steps:
step one, dissolving 22mg of sodium humate in 20mL of deionized water, and filtering by using qualitative filter paper to remove large particles to obtain a suspension A;
step two, adding 87mg of cobalt nitrate hexahydrate into 10mL of deionized water, and uniformly stirring to obtain a solution B;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 40min, then carrying out hydrothermal reaction for 12h at 190 ℃, cooling to room temperature, and carrying out ultrasonic treatment for 20min to obtain a suspension C; wherein the frequency of the ultrasonic wave is 60KHz, and the power is 180W;
step four, dispersing 24mg of 4, 4' -biphenyldicarboxylic acid in 30mL of deionized water, and then dropwise adding 1mL of 0.2mol/L sodium hydroxide aqueous solution to obtain a solution D;
step five, dripping the solution D into the suspension C while stirring, and then carrying out hydrothermal reaction for 12h at 190 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate obtained after the centrifugal separation, and performing freeze drying to obtain the brown black humic acid layer piece base Co-MOFs composite powder.
The composite powders prepared in examples 1, 2 and 3 and comparative examples 1 and 2 were used as active materials, respectively, and electrode materials were prepared according to the "method for preparing electrode materials" disclosed in "method for preparing bimetallic MOFs derivative electrode materials" of granted patent No. ZL201810178186.8, and the specific preparation method was:
step one, adding polyvinylidene fluoride, conductive carbon black and a composite powder active material into N, N-dimethylformamide, performing ultrasonic dispersion for 30min, and stirring for 4h to obtain a slurry mixture; the mass ratio of the polyvinylidene fluoride to the conductive carbon black to the powdery nickel-cobalt bimetallic MOFs material prepared in the first step is 10: 10: 80; the volume of the N, N-dimethylformamide is 2 times of the mass of the powdery nickel-cobalt bimetallic MOFs material, wherein the unit of the volume is mL, and the unit of the mass is g;
step two, the slurry mixture in the step one is mixed according to the ratio of 0.5mg/cm2Dropping the load quantity on cleaned 1cm multiplied by 4cm foam nickel, naturally airing, and then drying in vacuum to constant weight to obtain the nickel-cobalt bimetallic MOFs electrode material; the foamed nickel is ultrasonically cleaned by acetone, ethanol, 0.3mol/L dilute hydrochloric acid and deionized water in sequence; the temperature of the vacuum drying is 60 ℃;
and step three, placing the nickel-cobalt bimetallic MOFs electrode material in the step two in a potassium hydroxide aqueous solution with the concentration of 2mol/L, circulating 200 times at the scanning speed of 100mV/s by using a cyclic voltammetry method, and then circularly charging and discharging 50 times by using a constant current charging and discharging method under the current density of 5A/g to obtain the electrode material.
And carrying out electrochemical test according to an electrochemical test method disclosed in a preparation method of the bimetallic MOFs derivative electrode material with the granted patent number of ZL201810178186.8, wherein the specific test method comprises the following steps: a three-electrode system is adopted, the prepared electrode material is used as a working electrode, Ag/AgCl (saturated KCl solution) is used as a reference electrode, a Pt sheet is used as an auxiliary electrode, a 2mol/LKOH aqueous solution is used as an electrolyte, and cyclic volt-ampere and constant-current charge-discharge tests are performed on a Shanghai Hua CE660d electrochemical workstation. The results of the relevant tests are shown in table 1.
TABLE 1 capacitance Performance data for composite powders prepared in examples and comparative examples
As can be seen from Table 1, the specific capacitance of the humic acid layer piece-based bimetallic MOFs composite powder prepared by the invention is obviously higher than that of the two comparative examples. Compared with the specific capacitance of pure single metal MOFs in a comparative example disclosed in 'a preparation method of a bimetallic MOFs derivative electrode material' with the granted patent number of ZL201810178186.8, the specific capacitance of the humic acid layer piece base single metal MOFs composite powder is also obviously higher. This shows that MOFs and humic acid laminas are compounded, and a composite electrode material with higher specific capacitance can be obtained. The coordination effect of the humic acid and the transition metal ions and the regulation and control effect of the surface activity of the humic acid on the growth of the MOFs are mainly due to the fact that the humic acid and the bimetallic MOFs play a good synergistic effect.
TABLE 2 specific capacitance values of the composite powder of example 1 at different current densities
| Current Density (A. g)-1) | 0.5 | 1 | 2 | 5 | 10 | 20 | 25 | 50 | 75 | 100 |
| Specific capacitance (F.g)-1) | 860 | 840 | 812 | 762 | 713 | 637 | 634 | 549 | 477 | 410 |
Fig. 6 and 7 show CV curves and GCD curves of an electrode prepared by using the humic acid layer chip-based bimetallic MOFs composite powder prepared in example 1 of the present invention as an active material, and it can be seen from the graphs that the composite material combines the electric double layer capacitance characteristics of a carbon material and the pseudocapacitance characteristics of a metal oxide. FIG. 8 shows a hair dryerSpecific data of a rate curve of an electrode prepared by taking the humic acid layer chip-based bimetallic MOFs composite powder as an active material in the embodiment 1 are shown in Table 2. As can be seen from the figure, the specific capacitance of the composite material is high under different current densities, and the composite material shows excellent rate characteristics at 5 A.g-1The specific capacitance of the capacitor can reach 762 F.g under the current density-1Even at 100A · g-1Can still work under the current density of (1), and the specific capacitance is kept to be 410 F.g-1. Fig. 9 is a cycle stability curve of an electrode prepared by using the humic acid layer chip-based bimetal MOFs composite powder prepared in example 1 of the present invention as an active material, and an interpolated graph is a last 10 times charge-discharge curve. As can be seen from the figure, the electrode has good charge-discharge cycle stability at 5 A.g-1At a current density of (2), the initial specific capacitance is 760F g-1After 3000 times of charge-discharge circulation, the specific capacitance still reaches 457F g-1The retention ratio was 61%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of humic acid layer chip-based bimetal MOFs composite powder is characterized by comprising the following steps:
dissolving sodium humate in deionized water, and filtering to obtain a suspension A; the volume of the deionized water is 0.9-1.2 times of the mass of the sodium humate, wherein the volume is mL, and the mass is mg;
step two, adding nickel nitrate hexahydrate and cobalt nitrate hexahydrate into deionized water, and uniformly stirring to obtain a solution B; the sum of the mass of the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate is 2.6-4.0 times of the mass of the sodium humate in the step one; the volume of the deionized water is 0.11-0.17 times of the sum of the mass of the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate, wherein the unit of the volume is mL, and the unit of the mass is mg;
step three, mixing the suspension A in the step one with the solution B in the step two, firstly carrying out ultrasonic treatment for 35-45 min, then carrying out hydrothermal reaction for 10-12 h at the temperature of 150-190 ℃, and carrying out ultrasonic treatment for 15-25 min after the material after the hydrothermal reaction is cooled to room temperature to obtain a suspension C;
dispersing 4, 4' -biphenyldicarboxylic acid in deionized water, and then dropwise adding a sodium hydroxide aqueous solution to obtain a solution D; the mass of the 4, 4' -biphenyl dicarboxylic acid is 0.5-1.1 times of that of the sodium humate in the step one;
step five, dripping the solution D in the step four into the suspension C in the step three while stirring, and then carrying out hydrothermal reaction for 9-12 h at the temperature of 150-190 ℃;
and step six, cooling the product obtained after the hydrothermal reaction in the step five to room temperature, performing centrifugal separation, washing the solid precipitate obtained after the centrifugal separation, and drying to obtain the brown black humic acid layer sheet-based bimetallic MOFs composite powder.
2. The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder according to claim 1, wherein the mass ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate in the second step is (0.5-2): 1.
3. The method for preparing the humic acid layer chip-based bimetallic MOFs composite powder according to claim 1, wherein the ultrasonic treatment in the third step has the frequency of 40 KHz-60 KHz and the power of 150W-200W.
4. The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder, according to claim 1, is characterized in that in the fourth step, the concentration of the sodium hydroxide aqueous solution is 0.2mol/L, and the molar ratio of sodium hydroxide to 4, 4' -biphenyldicarboxylic acid is (2-4): 1.
5. The preparation method of the humic acid layer piece-based bimetallic MOFs composite powder according to claim 1, wherein the volume of the deionized water in the fourth step is 1.25-2.5 times of the mass of 4, 4' -biphenyldicarboxylic acid, wherein the unit of the volume is mL, and the unit of the mass is mg.
6. The method for preparing the humic acid layer slice-based bimetallic MOFs composite powder according to claim 1, wherein the drying in the sixth step is freeze drying.
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| CN111244481B (en) * | 2020-01-24 | 2020-10-09 | 西安科技大学 | Preparation method of fulvic acid lamella-based MOFs-derived electrocatalyst material |
| CN112978814B (en) * | 2021-02-11 | 2021-12-24 | 陕西省煤田地质集团有限公司 | Preparation method of fulvic acid layer sheet-based NiCo-LDH composite powder |
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