CN112164594A - Preparation method and application of double-MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material - Google Patents
Preparation method and application of double-MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material Download PDFInfo
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- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 78
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 60
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims abstract description 40
- 239000013118 MOF-74-type framework Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 96
- 239000007795 chemical reaction product Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims 2
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013299 conductive metal organic framework Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/84—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A preparation method and application of a double-MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material relate to a preparation method and application of a graphene oxide composite material. The invention aims to solve the problem that the MOF prepared by the existing method is poor in conductivity. The method comprises the following steps: firstly, preparing FeNi-MIL-88; secondly, preparing FeNi-MIL-88/NiCo-MOF-74; thirdly, preparing NiFe2O4/NiCo2O4: fourthly, carrying out hydrothermal reaction to obtain NiFe2O4/NiCo2O4and/GO. A double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material is used as a supercapacitor electrode material. The invention can obtain a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
Description
Technical Field
The invention relates to a preparation method and application of a graphene oxide composite material.
Background
In order to alleviate the crisis of fossil fuel combustion and environmental pollution, people are beginning to search for more green energy storage devices, such as solar cells, super capacitors, fuel cells, lithium batteries. The super capacitor has excellent electrochemical performance, such as: rapid charge/discharge rate, high power density, long cycle life, and environmental friendliness, and thus has received much attention.
Metal-organic frameworks (MOFs) are a new class of porous crystalline materials, also known as porous coordination polymers. It is formed by linking a metal ion or metal cluster to an organic linker. MOFs have well-defined pore structures and large specific surface areas. Moreover, most MOF materials can be synthesized in a simple, mild, and environmentally friendly manner. These characteristics have attracted great interest to researchers. However, MOFs themselves are not very conductive and in particular are non-conductive MOFs. This makes MOFs alone undesirable as supercapacitor electrode materials. To increase the conductivity of MOFs, many researchers have chosen to convert MOFs to metal oxides. The MOF is pyrolyzed into metal oxide with definite morphology under different conditions, so that the inherent characteristics of the MOF can be maintained, and the conductivity of the MOF can be improved, and the MOF has great potential in the application of the electrochemical field.
At present, the single and poor electrochemical performance of the substances obtained by using MOFs as precursors limits their application in the field of supercapacitors. Researchers have proposed combining metal oxides/carbides with other electrochemically active materials to form stable composites, which would be more desirable for electrochemical applications. Meanwhile, the MOF-derived metal oxide has larger internal surface area and high pore structure, which has obvious advantages compared with other synthetic methods. Therefore, the metal oxide composite material obtained by selecting a proper MOF material for compounding and then derivatizing is beneficial to improving the electrochemical performance. The double MOF derived materials have greater attraction, mainly for the following reasons: (1) the double MOF can combine the good characteristics of each component based on the advantages of MOF phase recombination; (2) the double MOFs can exhibit excellent synergistic effects by modulating the components; (3) the double MOF derivatives can provide more active sites to enable the material to have high stability and high conductivity. Therefore, the material can be used as a good energy storage material.
The interaction of MOF/MOF derived material structures and compositions and the synergistic mechanisms are less well understood for the improvement of supercapacitor electrode material performance.
Disclosure of Invention
The invention aims to solve the problem of poor conductivity of MOF prepared by the existing method, and provides a preparation method and application of a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
A preparation method of a double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material is completed according to the following steps:
firstly, preparing FeNi-MIL-88;
adding ferric chloride, copper nitrate and terephthalic acid into N, N-dimethylformamide under the condition of stirring, continuously stirring, adding a sodium hydroxide solution, and continuously stirring to obtain a mixed solution;
secondly, transferring the mixed solution into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, firstly, cleaning the reaction product I by using N, N-dimethylformamide, then cleaning the reaction product I by using absolute ethyl alcohol, and finally drying the cleaned reaction product I to obtain FeNi-MIL-88;
secondly, preparing FeNi-MIL-88/NiCo-MOF-74;
firstly, sequentially adding cobalt nitrate, nickel nitrate, 2, 5-dihydroxyterephthalic acid and FeNi-MIL-88 into an N, N-dimethylformamide/deionized water mixed solution, and uniformly stirring to obtain a mixture I;
secondly, transferring the mixture I into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product II;
thirdly, cleaning the reaction product II by using N, N-dimethylformamide, cleaning the reaction product II by using absolute ethyl alcohol, and finally drying the cleaned reaction product II to obtain FeNi-MIL-88/NiCo-MOF-74;
thirdly, preparing NiFe2O4/NiCo2O4：
Annealing FeNi-MIL-88/NiCo-MOF-74 in nitrogen atmosphere to obtain NiFe2O4/NiCo2O4；
Fourthly, preparing NiFe2O4/NiCo2O4/GO：
Firstly, graphene oxide and NiFe oxide2O4/NiCo2O4Uniformly mixing the mixture with deionized water, and performing ultrasonic treatment to obtain a mixture II;
secondly, transferring the mixture II into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product III;
thirdly, using deionized water to carry out suction filtration washing on the reaction product III, and then drying to obtain the double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
A double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material is used as a supercapacitor electrode material.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared by the invention2O4/NiCo2O4the/GO) is used as a super capacitor electrode material, has higher specific capacitance of 1258F/g-1470F/g, and can be applied to a super capacitor with high energy density;
secondly, the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared by the invention2O4/NiCo2O4the/GO) integral structure has a hollow structure, which is beneficial to increasing active sites and improving the conductivity and stability of the material;
thirdly, the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared by the invention2O4/NiCo2O4GO) has the characteristics of simple process, easy operation and low requirement on equipment.
The invention can obtain a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
Drawings
FIG. 1 shows the preparation of FeNi-MIL-88/NiCo-MOF-74, NiFe in example 12O4/NiCo2O4、NiFe2O4/NiCo2O4X-ray diffraction patterns of/GO and GO;
FIG. 2 is a NiFe alloy prepared in example 12O4/NiCo2O4Cyclic voltammogram of/GO at different sweep rates;
FIG. 3 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 cyclic voltammogram at the same sweep rate;
FIG. 4 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 constant current charge discharge diagrams at the same current density;
FIG. 5 is a NiFe alloy prepared in example 12O4/NiCo2O4A constant current charge discharge diagram of GO at different current densities;
FIG. 6 is a NiFe prepared according to example 1 plotted in FIG. 52O4/NiCo2O4Capacitive curves for GO at different current densities;
FIG. 7 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 impedance contrast plots;
FIG. 8 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO with NiFe prepared in example 42O4/NiCo2O4In phase of GOConstant current charge discharge plot at the same current density.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material, which is completed according to the following steps:
firstly, preparing FeNi-MIL-88;
adding ferric chloride, copper nitrate and terephthalic acid into N, N-dimethylformamide under the condition of stirring, continuously stirring, adding a sodium hydroxide solution, and continuously stirring to obtain a mixed solution;
secondly, transferring the mixed solution into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, firstly, cleaning the reaction product I by using N, N-dimethylformamide, then cleaning the reaction product I by using absolute ethyl alcohol, and finally drying the cleaned reaction product I to obtain FeNi-MIL-88;
secondly, preparing FeNi-MIL-88/NiCo-MOF-74;
firstly, sequentially adding cobalt nitrate, nickel nitrate, 2, 5-dihydroxyterephthalic acid and FeNi-MIL-88 into an N, N-dimethylformamide/deionized water mixed solution, and uniformly stirring to obtain a mixture I;
secondly, transferring the mixture I into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product II;
thirdly, cleaning the reaction product II by using N, N-dimethylformamide, cleaning the reaction product II by using absolute ethyl alcohol, and finally drying the cleaned reaction product II to obtain FeNi-MIL-88/NiCo-MOF-74;
thirdly, preparing NiFe2O4/NiCo2O4：
Annealing FeNi-MIL-88/NiCo-MOF-74 in nitrogen atmosphere to obtain NiFe2O4/NiCo2O4；
Fourthly, preparing NiFe2O4/NiCo2O4/GO：
Firstly, graphene oxide and NiFe oxide2O4/NiCo2O4Uniformly mixing the mixture with deionized water, and performing ultrasonic treatment to obtain a mixture II;
secondly, transferring the mixture II into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product III;
thirdly, using deionized water to carry out suction filtration washing on the reaction product III, and then drying to obtain the double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
Compared with the prior art, the beneficial effects of this embodiment are:
first, the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared in this embodiment2O4/NiCo2O4the/GO) is used as a super capacitor electrode material, has higher specific capacitance of 1258F/g-1470F/g, and can be applied to a super capacitor with high energy density;
secondly, the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared by the embodiment2O4/NiCo2O4the/GO) integral structure has a hollow structure, which is beneficial to increasing active sites and improving the conductivity and stability of the material;
thirdly, the double-MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe) prepared by the embodiment2O4/NiCo2O4GO) has the characteristics of simple process, easy operation and low requirement on equipment.
The embodiment can obtain the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: adding ferric chloride, copper nitrate and terephthalic acid into N, N-dimethylformamide under the condition of stirring speed of 200 r/min-400 r/min, continuously stirring for 20 min-40 min under the condition of stirring speed of 200 r/min-400 r/min, adding sodium hydroxide solution, and continuously stirring for 20 min-30 min under the condition of stirring speed of 200 r/min-400 r/min to obtain a mixed solution. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the reaction product I is firstly cleaned for 3 to 5 times by using N, N-dimethylformamide, then cleaned for 3 to 5 times by using absolute ethyl alcohol, and finally dried, wherein the drying temperature is 70 to 80 ℃, and the drying time is 10 to 12 hours, so that the FeNi-MIL-88 is obtained. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the concentration of the sodium hydroxide solution in the first step is 0.1 mol.L-1～0.4mol·L-1(ii) a The molar ratio of the ferric chloride to the copper nitrate to the terephthalic acid in the first step is (6-7): 3-4): 10; the volume ratio of the ferric chloride substance to the N, N-dimethylformamide in the first step (6 mmol-7 mmol) is 100 mL; the volume ratio of the ferric chloride substance to the sodium hydroxide solution in the first step (6 mmol-7 mmol) is 20 mL; the hydrothermal reaction temperature in the first step is 80-120 ℃, and the reaction time is 10-15 h. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the molar ratio of the cobalt nitrate to the nickel nitrate to the 2, 5-dihydroxy terephthalic acid in the second step is (1-2) to 1; the mass ratio of the amount of the cobalt nitrate substance to the FeNi-MIL-88 in the second step is (0.3 mmol-0.5 mmol) to 0.1 g; the volume ratio of the N, N-dimethylformamide to the deionized water in the N, N-dimethylformamide/deionized water mixed solution in the second step is 2: 1; the volume ratio of the cobalt nitrate substance in the second step to the N, N-dimethylformamide/deionized water mixed solution is (0.3 mmol-0.5 mmol):15 mL; the hydrothermal reaction temperature in the second step is 80-120 ℃, and the reaction time is 20-24 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and step two, firstly, cleaning the reaction product II by using N, N-dimethylformamide, then cleaning the reaction product II by using absolute ethyl alcohol, and finally drying the cleaned reaction product II at the drying temperature of 70-80 ℃ for 10-12 h to obtain the FeNi-MIL-88/NiCo-MOF-74. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the annealing temperature in the third step is 300-450 ℃, and the annealing time is 3-5 h; the NiFe in the fourth step2O4/NiCo2O4The mass ratio of the graphene oxide to the graphene oxide is (8-10) to 1; the volume ratio of the mass of the graphene oxide to the deionized water in the step IV is (8 mg-10 mg) to 10 mL; the hydrothermal reaction temperature in the fourth step is 80-100 ℃, and the reaction time is 6-9 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the ultrasonic power in the step IV is 50-70W, and the ultrasonic time is 20-40 min; the graphene oxide in the fourth step is prepared by adopting an improved hummers method, and the specific preparation method is as follows:
firstly, 1g K2S2O8、1g P2O52g of graphite and 30mL of 98% concentrated sulfuric acid are uniformly mixed to obtain a mixture A; stirring the mixture A at 80 ℃ for reacting for 6h, adding 500mL of deionized water, stirring uniformly, and filtering by using a 0.2-micron membrane to obtain a solid substance; washing the solid substance with deionized water until pH is 7, and drying at 60 deg.C for 12 hr to obtain a mixtureCompound B;
secondly, uniformly mixing 3g of potassium permanganate, 30mL of 98 mass percent concentrated sulfuric acid and 1g of mixture B under the stirring condition, then stirring for 1H at 20 ℃, stirring for 8H at 35 ℃, then adding 50mL of deionized water, stirring for 15min, and finally adding 300mL of deionized water and 5mL of 30 mass percent H2O2And finally filtering the solution to obtain a precipitate, washing the precipitate for 5 times by using HCl with the mass fraction of 37%, and then washing the precipitate to the pH value of 7 by using deionized water to obtain the graphene oxide. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and fourthly, performing suction filtration and washing on the reaction product III for 3 to 5 times by using deionized water, and drying at the drying temperature of between 70 and 80 ℃ for 10 to 12 hours to obtain the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material is used as a supercapacitor electrode material.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: a preparation method of a double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material is completed according to the following steps:
firstly, preparing FeNi-MIL-88;
adding 0.7mmol of ferric chloride, 0.3mmol of copper nitrate and 1mmol of terephthalic acid into 10mL of N, N-dimethylformamide under the condition of stirring speed of 400r/min, continuously stirring for 30min under the stirring speed of 400r/min, adding 2mL of sodium hydroxide solution, and continuously stirring for 30min under the stirring speed of 400r/min to obtain a mixed solution;
secondly, transferring the mixed solution into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction at 100 ℃ for 15 hours, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, cleaning the reaction product I for 3 times by using N, N-dimethylformamide, cleaning the reaction product I for 3 times by using absolute ethyl alcohol, and finally drying the cleaned reaction product I, wherein the drying temperature is 70 ℃, and the drying time is 12 hours, so that FeNi-MIL-88 is obtained;
the concentration of the sodium hydroxide solution in the first step is 0.2 mol.L-1；
Secondly, preparing FeNi-MIL-88/NiCo-MOF-74;
sequentially adding 0.4mmol of cobalt nitrate, 0.4mmol of nickel nitrate, 0.4mmol of 2, 5-dihydroxyterephthalic acid and 0.1g of FeNi-MIL-88 into 15mL of N, N-dimethylformamide/deionized water mixed solution, and uniformly stirring to obtain a mixture I;
the volume ratio of the N, N-dimethylformamide to the deionized water in the N, N-dimethylformamide/deionized water mixed solution in the second step is 2: 1;
secondly, transferring the mixture I into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product II;
the hydrothermal reaction temperature in the second step is 100 ℃, and the reaction time is 24 hours;
thirdly, cleaning the reaction product II by using N, N-dimethylformamide for 3 times, cleaning the reaction product II by using absolute ethyl alcohol for 3 times, and finally drying the cleaned reaction product II at the drying temperature of 70 ℃ for 12 hours to obtain FeNi-MIL-88/NiCo-MOF-74;
thirdly, preparing NiFe2O4/NiCo2O4：
Annealing FeNi-MIL-88/NiCo-MOF-74 in nitrogen atmosphere to obtain NiFe2O4/NiCo2O4；
The annealing temperature in the third step is 450 ℃, and the annealing time is 4 hours;
fourthly, preparing NiFe2O4/NiCo2O4/GO：
Firstly, 10mg of Graphene Oxide (GO) and 100mg of NiFe2O4/NiCo2O4Uniformly mixing with 10mL of deionized water, and performing ultrasonic treatment to obtain a mixture II;
the ultrasonic power in the fourth step is 70W, and the ultrasonic time is 40 min;
preparing the graphene oxide by adopting an improved hummers method;
secondly, transferring the mixture II into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product III;
the hydrothermal reaction temperature in the step IV is 90 ℃, and the reaction time is 8 hours;
thirdly, using deionized water to carry out suction filtration washing on the reaction product III for 3 times, and then drying, wherein the drying temperature is 70 ℃, and the drying time is 12 hours, so as to obtain the double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material (NiFe)2O4/NiCo2O4/GO)。
The graphene oxide in the fourth step is prepared by adopting an improved hummers method, and the specific preparation method is as follows:
firstly, 1g K2S2O8、1g P2O52g of graphite and 30mL of 98% concentrated sulfuric acid are uniformly mixed to obtain a mixture A; stirring the mixture A at 80 ℃ for reacting for 6h, adding 500mL of deionized water, stirring uniformly, and filtering by using a 0.2-micron membrane to obtain a solid substance; washing the solid matter with deionized water until the pH value is 7, and drying at 60 ℃ for 12h to obtain a mixture B;
secondly, uniformly mixing 3g of potassium permanganate, 30mL of 98 mass percent concentrated sulfuric acid and 1g of mixture B under the stirring condition, then stirring for 1H at 20 ℃, stirring for 8H at 35 ℃, then adding 50mL of deionized water, stirring for 15min, and finally adding 300mL of deionized water and 5mL of 30 mass percent H2O2And finally filtering the solution to obtain a precipitate, washing the precipitate for 5 times by using HCl with the mass fraction of 37%, and then washing the precipitate to the pH value of 7 by using deionized water to obtain the graphene oxide.
Example 2: the present embodiment is different from embodiment 1 in that: the annealing temperature in step three is 350 ℃. The other steps and parameters were the same as in example 1.
Example 3: the present embodiment is different from embodiment 1 in that: the annealing temperature in step three is 400 ℃. The other steps and parameters were the same as in example 1.
Example 4: the present embodiment is different from embodiment 1 in that: the time of the hydrothermal reaction in the step IV is 6 hours. The other steps and parameters were the same as in example 1.
Example 5: the present embodiment is different from embodiment 1 in that: the concentration of the sodium hydroxide solution in the first step is 0.4 mol.L-1. The other steps and parameters were the same as in example 1.
The invention is further described below with reference to the accompanying drawings and example 1:
as shown in FIG. 1, FeNi-MIL-88/NiCo-MOF-74, NiFe prepared in example 12O4/NiCo2O4、NiFe2O4/NiCo2O4Typical XRD patterns of/GO and GO at 5 ° -70 °, see FIG. 1;
FIG. 1 shows the preparation of FeNi-MIL-88/NiCo-MOF-74, NiFe in example 12O4/NiCo2O4、NiFe2O4/NiCo2O4X-ray diffraction patterns of/GO and GO;
as can be seen from FIG. 1, NiFe2O4/NiCo2O4The diffraction peaks of (A) appear at 31.19 DEG, 35.64 DEG, 44.28 DEG, 51.49 DEG and 62.94 DEG and standard NiFe2O4(JCPDS No.10-0325) and NiCo2O4(JCPDS No. 73-1702). The peak at 10.83 ° indicates successful synthesis of GO. At the same time, NiFe2O4/NiCo2O4XRD (X-ray diffraction) spectrum and NiFe (nickel-iron-manganese) of/GO composite electrode2O4/NiCo2O4Consistent with the XRD pattern of GO. This indicates that NiFe2O4，NiCo2O4And co-existence of GO in the structure. Thus, according to the XRD results, NiFe was confirmed2O4/NiO2O4the/GO recombination was successful.
As shown in FIG. 2, NiFe prepared in example 12O4/NiCo2O4the/GO serving as the electrode material of the super capacitor is 10-60 mV.s-1At a scanning speed of 6 mol. L-1KOH is the cyclic voltammetry curve of the electrolyte solution, and the potential window is-0.1-0.6V, as shown in figure 2;
FIG. 2 is a NiFe alloy prepared in example 12O4/NiCo2O4Cyclic voltammogram of/GO at different sweep rates;
as can be seen from fig. 2, there is a pair of redox peaks in the cycle plot, indicating that the material relies primarily on redox reactions to store energy.
As shown in FIG. 3, is NiFe2O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 at 50 mV. s-1At a scanning speed of 6 mol. L-1KOH is the cyclic voltammogram of the electrolyte solution, see fig. 3;
FIG. 3 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 cyclic voltammogram at the same sweep rate;
as can be seen from FIG. 3, NiFe2O4/NiCo2O4/GO、NiFe2O4/NiCo2O4The areas of FeNi-MIL-88/NiCo-MOF-74 decreased in sequence, demonstrating the corresponding capacitive decrease in sequence.
As shown in FIG. 4, is NiFe2O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 at a current density of 1A/g and at a current density of 6 mol. L-1KOH is a charge-discharge performance test curve of the electrolyte solution, and is shown in figure 4;
FIG. 4 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 constant current charge discharge diagrams at the same current density;
from FIG. 4, it is evident that the discharge time NiFe2O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 decreased in sequence, consistent with the cyclic voltammogram conclusions.
As shown in FIG. 5, is NiFe2O4/NiCo2O4/GO is between 1 and 20Ag-1At a current density of 6 mo.L-1KOH is a charge-discharge performance test curve of the electrolyte solution, and is shown in figure 5;
FIG. 5 is a NiFe alloy prepared in example 12O4/NiCo2O4A constant current charge discharge diagram of GO at different current densities;
as can be seen from FIG. 5, the specific capacitance at 1A/g is 1470F g as calculated from the curve-1。
As shown in fig. 6, the correspondence of the capacitance to the current density is plotted according to fig. 5, see fig. 6;
FIG. 6 is a NiFe prepared according to example 1 plotted in FIG. 52O4/NiCo2O4Capacitive curves for GO at different current densities;
as can be seen from fig. 6, the specific capacitance of the material decreases with increasing current density, but the falling potential is gentle, indicating that the electrode material has excellent rate characteristics.
As shown in FIG. 7, is NiFe2O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 in the frequency range of 0.01Hz to 100kHz for electrochemical impedance test, see FIG. 7;
FIG. 7 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO、NiFe2O4/NiCo2O4FeNi-MIL-88/NiCo-MOF-74 impedance contrast plots;
as seen in FIG. 7, NiFe2O4/NiCo2O4The internal resistance of the/GO electrode material is relatively low, and the electrode material has rapid ion and electron transfer and shows good electrochemical performance.
As shown in FIG. 8, NiFe prepared in example 12O4/NiCo2O4/GO and NiFe prepared in example 42O4/NiCo2O4At a current density of 1A/g, at 6 mol. L-1KOH is a charge-discharge performance test curve of the electrolyte solution, and is shown in figure 8;
FIG. 8 is a NiFe alloy prepared in example 12O4/NiCo2O4/GO with NiFe prepared in example 42O4/NiCo2O4Constant current charge discharge plot of/GO at the same current density.
As seen in FIG. 8, the NiFe prepared in example 12O4/NiCo2O4/GONiFe2O4/NiCo2O4The longer discharge time and better electrochemical performance of the/GO electrode material indicate that example 1 is superior to example 4.
In summary, the following steps: NiFe prepared in example 12O4/NiCo2O4the/GO composite material has higher capacitor performance and excellent stability, and can be used as an active material of a super capacitor.
Claims (10)
1. A preparation method of a double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material is characterized in that the preparation method of the double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material is completed according to the following steps:
firstly, preparing FeNi-MIL-88;
adding ferric chloride, copper nitrate and terephthalic acid into N, N-dimethylformamide under the condition of stirring, continuously stirring, adding a sodium hydroxide solution, and continuously stirring to obtain a mixed solution;
secondly, transferring the mixed solution into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, firstly, cleaning the reaction product I by using N, N-dimethylformamide, then cleaning the reaction product I by using absolute ethyl alcohol, and finally drying the cleaned reaction product I to obtain FeNi-MIL-88;
secondly, preparing FeNi-MIL-88/NiCo-MOF-74;
firstly, sequentially adding cobalt nitrate, nickel nitrate, 2, 5-dihydroxyterephthalic acid and FeNi-MIL-88 into an N, N-dimethylformamide/deionized water mixed solution, and uniformly stirring to obtain a mixture I;
secondly, transferring the mixture I into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product II;
thirdly, cleaning the reaction product II by using N, N-dimethylformamide, cleaning the reaction product II by using absolute ethyl alcohol, and finally drying the cleaned reaction product II to obtain FeNi-MIL-88/NiCo-MOF-74;
thirdly, preparing NiFe2O4/NiCo2O4：
Annealing FeNi-MIL-88/NiCo-MOF-74 in nitrogen atmosphere to obtain NiFe2O4/NiCo2O4；
Fourthly, preparing NiFe2O4/NiCo2O4/GO：
Firstly, graphene oxide and NiFe oxide2O4/NiCo2O4Uniformly mixing the mixture with deionized water, and performing ultrasonic treatment to obtain a mixture II;
secondly, transferring the mixture II into a polytetrafluoroethylene high-pressure kettle for hydrothermal reaction, and naturally cooling to room temperature to obtain a reaction product III;
thirdly, using deionized water to carry out suction filtration washing on the reaction product III, and then drying to obtain the double MOF derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
2. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, characterized in that in the first step, under the condition that the stirring speed is 200r/min to 400r/min, ferric chloride, copper nitrate and terephthalic acid are added into N, N-dimethylformamide, the mixture is continuously stirred for 20min to 40min under the condition that the stirring speed is 200r/min to 400r/min, then sodium hydroxide solution is added, and the mixture is continuously stirred for 20min to 30min under the condition that the stirring speed is 200r/min to 400r/min, so as to obtain a mixed solution.
3. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, characterized in that in the step one, the reaction product I is firstly cleaned for 3 to 5 times by using N, N-dimethylformamide, then cleaned for 3 to 5 times by using absolute ethyl alcohol, and finally dried, wherein the drying temperature is 70 to 80 ℃, and the drying time is 10 to 12 hours, so that FeNi-MIL-88 is obtained.
4. The method for preparing the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, wherein the concentration of the sodium hydroxide solution in the first step is 0.1 mol.L-1～0.4mol·L-1(ii) a The molar ratio of the ferric chloride to the copper nitrate to the terephthalic acid in the first step is (6-7): 3-4): 10; the volume ratio of the ferric chloride substance to the N, N-dimethylformamide in the first step (6 mmol-7 mmol) is 100 mL; the volume ratio of the ferric chloride substance to the sodium hydroxide solution in the first step (6 mmol-7 mmol) is 20 mL; the hydrothermal reaction temperature in the first step is 80-120 ℃, and the reaction time is 10-15 h.
5. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, wherein the molar ratio of the cobalt nitrate to the nickel nitrate to the 2, 5-dihydroxyterephthalic acid in the second step is (1-2): 1; the mass ratio of the amount of the cobalt nitrate substance to the FeNi-MIL-88 in the second step is (0.3 mmol-0.5 mmol) to 0.1 g; the volume ratio of the N, N-dimethylformamide to the deionized water in the N, N-dimethylformamide/deionized water mixed solution in the second step is 2: 1; the volume ratio of the cobalt nitrate substance in the second step to the N, N-dimethylformamide/deionized water mixed solution is (0.3 mmol-0.5 mmol):15 mL; the hydrothermal reaction temperature in the second step is 80-120 ℃, and the reaction time is 20-24 h.
6. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, characterized in that in the second step, the reaction product II is firstly cleaned by N, N-dimethylformamide, then cleaned by absolute ethyl alcohol, and finally dried, wherein the drying temperature is 70-80 ℃ and the drying time is 10-12 h, so that FeNi-MIL-88/NiCo-MOF-74 is obtained.
7. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, wherein the annealing temperature in the third step is 300-450 ℃, and the annealing time is 3-5 h; the NiFe in the fourth step2O4/NiCo2O4The mass ratio of the graphene oxide to the graphene oxide is (8-10) to 1; the volume ratio of the mass of the graphene oxide to the deionized water in the step IV is (8 mg-10 mg) to 10 mL; the hydrothermal reaction temperature in the fourth step is 80-100 ℃, and the reaction time is 6-9 h.
8. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, wherein the ultrasonic power in the fourth step is 50-70W, and the ultrasonic time is 20-40 min; the graphene oxide in the fourth step is prepared by adopting an improved hummers method, and the specific preparation method is as follows:
firstly, 1g K2S2O8、1g P2O52g of graphite and 30mL of 98 mass percent concentrated sulfuric acid are uniformly mixed to obtain a mixtureA; stirring the mixture A at 80 ℃ for reacting for 6h, adding 500mL of deionized water, stirring uniformly, and filtering by using a 0.2-micron membrane to obtain a solid substance; washing the solid matter with deionized water until the pH value is 7, and drying at 60 ℃ for 12h to obtain a mixture B;
secondly, uniformly mixing 3g of potassium permanganate, 30mL of 98 mass percent concentrated sulfuric acid and 1g of mixture B under the stirring condition, then stirring for 1H at 20 ℃, stirring for 8H at 35 ℃, then adding 50mL of deionized water, stirring for 15min, and finally adding 300mL of deionized water and 5mL of 30 mass percent H2O2And finally filtering the solution to obtain a precipitate, washing the precipitate for 5 times by using HCl with the mass fraction of 37%, and then washing the precipitate to the pH value of 7 by using deionized water to obtain the graphene oxide.
9. The preparation method of the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material according to claim 1, characterized in that deionized water is used for carrying out suction filtration washing on the reaction product III for 3 to 5 times in the fourth step, and then drying is carried out, wherein the drying temperature is 70 to 80 ℃, and the drying time is 10 to 12 hours, so as to obtain the double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material.
10. The use of a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material prepared by the preparation method of claim 1, wherein a double MOF-derived nickel ferrite/nickel cobaltate/graphene oxide composite material is used as a supercapacitor electrode material.
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