CN114566394B - Preparation method and application of iodine ion doped modified Fe-MOF bulk electrode material - Google Patents
Preparation method and application of iodine ion doped modified Fe-MOF bulk electrode material Download PDFInfo
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- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 98
- 239000007772 electrode material Substances 0.000 title claims abstract description 90
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 13
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229940006461 iodide ion Drugs 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 62
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 30
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 12
- 229940038773 trisodium citrate Drugs 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 239000003990 capacitor Substances 0.000 abstract description 11
- 239000012621 metal-organic framework Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000009832 plasma treatment Methods 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- -1 iodide ions Chemical class 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- 239000007832 Na2SO4 Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
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- 239000006227 byproduct Substances 0.000 description 2
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- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a preparation method and application of an iodide ion doped modified Fe-MOF bulk electrode material, wherein a coprecipitation method is adopted, ferric salt and potassium ferrocyanide are respectively dissolved, Fe-based MOF is prepared by mixing at normal temperature, then plasma treatment is carried out for 5-20 min, the treated material is subjected to heat treatment in a potassium iodide solution for 12-48 h, and after the heat treatment, drying and centrifuging are carried out to prepare the MOF electrode material. The invention has the beneficial effects that: the preparation method is simple, low in cost and easy for batch production, and is energy-saving and environment-friendly. The prepared modified MOF material is applied to an iodide ion supercapacitor at 1A g‑1Over 400F g at current density‑1Has a fast reaction rate and has a high energy density. The number of cycles of 5000 maintains a coulombic efficiency of nearly 98%. Is expected to have wide application value in electrode materials of super capacitors and other energy storage devices.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a preparation method and application of a Fe-MOF bulk electrode material modified by doping iodide ions.
Background
With the diversified pursuit of energy structures in modern society, the limitation of traditional fossil fuels and the problems of greenhouse effect and environmental protection brought by the traditional fossil fuels, new clean energy becomes the hot research. The storage of clean energy (such as wind, solar and tidal energy) is of great importance for sustainable energy utilization and consumption. In this respect, electrochemical supercapacitors have become one of the most promising candidates, especially for large-scale energy storage infrastructure, which have the advantages of fast charge and discharge capability, high safety and long lifetime. Electrode materials are used for electrochemical super capacitors, but the conventional Electric Double Layer (EDL) electrode materials store charges through a surface-controlled ion adsorption/desorption mechanism, and the problem of low energy density cannot be overcome. For this reason, efforts have been made to explore strategies for combining pseudocapacitive materials with surface faradaic redox activity, such as Fe-MOF metal organic framework materials, with redox electrolytes. The traditional Fe-MOF material uses a coprecipitation method, has limited energy density in a redox electrolyte and slow reaction rate, and has low coulombic efficiency and capacitor damage caused by byproducts generated in the electrochemical reaction process, thereby influencing the application of the Fe-MOF material in an iodide ion supercapacitor.
Disclosure of Invention
The invention aims to solve the technical problems that the energy density of a Fe-MOF material prepared by a preparation method in the prior art in a redox electrolyte is limited, the reaction rate is slow, and coulombic efficiency is low due to byproducts generated in the electrochemical reaction process, and the like, and provides a preparation method of an iodine ion doped modified Fe-MOF bulk electrode material.
The invention also aims to provide the iodine ion doped modified Fe-MOF bulk electrode material prepared by the preparation method.
The invention also aims to provide the application of the iodine ion doped modified Fe-MOF bulk electrode material prepared by the preparation method in an iodine ion super capacitor.
The technical scheme is as follows for solving the technical problem of the invention:
a preparation method of an iodine ion doped modified Fe-MOF bulk electrode material comprises the following steps:
(1) dissolving ferric salt in deionized water to generate 0.1mol/L solution A, dissolving potassium ferrocyanide in deionized water to generate 0.1mol/L solution B, adding polyvinylpyrrolidone PVP template, sulfuric acid and trisodium citrate into the solution B, and mixing with the solution A, wherein the molar ratio of the ferric salt in the solution A to the potassium ferrocyanide in the solution B is 0.75: 0.75-2; stirring at room temperature, adding the mixture into a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 60-120 ℃ for 12-48 h; collecting a product obtained by the reaction after the hydrothermal reaction is finished, and centrifugally cleaning the product by using a mixed solution of ethanol and deionized water to finally obtain a blue product Fe-MOF bulk electrode material;
(2) grinding the Fe-MOF electrode material in the step (1), putting the ground Fe-MOF electrode material into a plasma etching machine for treatment for 5-20 min, then carrying out heat treatment in a potassium iodide solution with the vacuum degree of 0.01-40 Pa and the hydrogen gas, wherein the molar ratio of potassium iodide to the Fe-MOF electrode material is 10:1, the heat treatment temperature is 60-120 ℃, the heat treatment time is 12-48 h, and cooling, separating and washing after the heat treatment to obtain the Fe-MOF bulk electrode material modified by doping iodine ions.
In the step (1), the ferric salt is selected from one of ferric sulfate, ferric chloride, ferric acetate and ferric nitrate.
The relative molecular mass of the polyvinylpyrrolidone PVP template in the step (1) is 10000-.
And (2) when the polyvinylpyrrolidone PVP template agent, the sulfuric acid and the trisodium citrate are added into the solution B in the step (1), wherein the sulfuric acid is added according to 1% of the volume of the solution B, the molar concentration of the trisodium citrate is 0.01mol/L, and the molar ratio of the polyvinylpyrrolidone PVP template agent to the trisodium citrate is 1: 1.
The room-temperature stirring time in the step (1) is 5-60 minutes.
The grinding time in the step (2) is 5-80 minutes.
The flow rate of hydrogen introduced in the step (2) is 0.1-10 sccm.
The preparation method obtains the iodine ion doped modified Fe-MOF bulk electrode material.
The iodine ion doped modified Fe-MOF bulk electrode material is applied to an iodine ion super capacitor. The specific method comprises the following steps: fully grinding the iodine ion doped modified Fe-MOF bulk electrode material, NMP and acetylene black according to the mass ratio of 8: 1, uniformly coating 1.5-2mg per 4 square centimeters on carbon cloth, and drying in an oven at the temperature of 60-80 ℃ for 12-48 h.
The electrochemical properties of the iodine ion doped modified Fe-MOF bulk electrode material prepared by the method and the original Fe-MOF material which is not doped and modified by iodine ions are tested, and the method specifically comprises the following steps: cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), galvanostatic charge-discharge (GCD) measurements were measured using CHI 660E. Electrochemical Impedance Spectroscopy (EIS) was performed at 100 kHz to 10 mHz using a Multi AUTOLAB M204.
As shown in FIG. 6, the two materials before and after modification were at 5mmol/L KI +0.1mol/L H2SO4+1mol/L Na2SO4CV plot in electrolyte showing that the area of iodine ion doped modified Fe-MOF bulk electrode material is twice that of the original Fe-MOF material modified without iodine ion doping.
As shown in FIG. 7, the two materials before and after modification were at 5mmol/L KI +0.1mol/L H2SO4+1mol/L Na2SO4GCD profile in electrolyte, the area of the iodine ion doped modified Fe-MOF bulk electrode material is twice that of the original Fe-MOF material modified without iodine ion doping.
As shown in FIG. 8, the two materials before and after modification are at 5mmol/L KI +0.1mol/L H2SO4+1mol/L Na2SO4Tafel slope diagram in electrolyte, the area of the iodine ion doped modified Fe-MOF bulk electrode material was four times that of the original Fe-MOF material modified without iodine ion doping.
As shown in FIG. 9, the two materials before and after modification are at 5mmol/L KI +0.1mol/L H2SO4+1mol/L Na2SO4According to a coulombic efficiency graph in the electrolyte, the coulombic efficiency of the iodine ion doped modified Fe-MOF bulk electrode material is close to 100% and stable, the iodine ion doped modified Fe-MOF bulk electrode material can be used for a long time without damaging the electrode, the coulombic efficiency of the original Fe-MOF material which is not doped and modified by the iodine ion is less than 80%, only a few of the coulombic efficiencies reach 100%, and the coulombic efficiency is not as stable as that of the doped and modified Fe-MOF.
The synthesis method is simple, low in cost, environment-friendly due to the fact that the used solvent is water, and suitable for large-scale production. Prepared by the inventionThe iodine ion doped modified Fe-MOF bulk electrode material can be applied to iodine ion supercapacitors, and the application is the first time in the field. The iodine ion doped modified Fe-MOF bulk electrode material increases reaction substances by pre-embedding iodine ions, so that the capacity is improved; as the outmost electrons of the iodine are subjected to p-d hybridization between a 5p orbital and a 3d orbital of Fe to play a role in catalyzing and reducing potential barrier, the reaction rate reaches 153 mV dec-1After the iodide ions are pre-embedded, the oxidation reduction peak potential difference is minimum, and the process is more reversible. Therefore, the iodide ion super capacitor using the iodide ion doped modified Fe-MOF bulk electrode material has high energy density which reaches 436F g-1And the method has a rapid reaction process, the coulombic efficiency is close to 100%, the coulombic efficiency of nearly 98% is kept for 5000 times of circulation times, the circulation stability is good, and the method can be used for a long time. Is expected to have wide application value in electrode materials of super capacitors and other energy storage devices.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of an iodine ion doped modified Fe-MOF bulk electrode material prepared in example 1 of the invention;
FIG. 2 is a scanning electron microscope image of an iodine ion doped modified Fe-MOF bulk electrode material prepared in example 1 of the present invention;
FIG. 3 is an element distribution diagram of an iodine ion doped modified Fe-MOF bulk electrode material prepared in example 1 of the present invention;
FIG. 4 shows the modified Fe-MOF material doped with no iodine ion at 1mol/L Na in example 1 of the present invention2SO4Middle CV diagram;
FIG. 5 shows that the iodine ion doped modified Fe-MOF bulk electrode material prepared in example 1 of the present invention is 1mol/L Na2SO4Middle CV diagram;
FIG. 6 is a CV diagram of Fe-MOF bulk electrode material before and after doping with iodide ions in example 1 of the present invention;
FIG. 7 is a GCD graph of Fe-MOF bulk electrode materials before and after doping with iodide ions in example 1 of the present invention;
FIG. 8 is a Tafel slope graph of Fe-MOF bulk electrode materials before and after doping with iodide ions in example 1 of the present invention;
FIG. 9 is a coulombic efficiency curve of Fe-MOF bulk electrode materials before and after doping with iodide ions in example 1 of the present invention;
FIG. 10 is a scanning electron micrograph of the modified Fe-MOF material doped with iodide ion in example 2.
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
A preparation method of an iodine ion doped modified Fe-MOF bulk electrode material comprises the following specific steps:
(1) weighing 1 mmol of ferric chloride to be dissolved in 10 mL of deionized water to generate A solution, weighing 1 mmol of potassium ferrocyanide to be dissolved in 10 mL of deionized water to generate B solution, and adding 0.5g of polyvinylpyrrolidone PVP template, 1 mL of sulfuric acid and 0.5g of trisodium citrate into the B solution, wherein the relative molecular mass of the polyvinylpyrrolidone PVP template is 10000. Stirring the solution A and the solution B at room temperature for 5 minutes, and then adding the solution A and the solution B into an inner container of a hydrothermal kettle to perform hydrothermal reaction, wherein the molar ratio of ferric salt in the solution A to potassium ferrocyanide in the solution B is 0.75: 0.75; the hydrothermal reaction temperature is 60 ℃, and the reaction time is 24 hours; collecting a product obtained by the reaction, and centrifugally cleaning the product for 3 times by using a mixed solution of ethanol and deionized water to finally obtain a blue product, namely the Fe-MOF bulk electrode material;
(2) grinding the Fe-MOF electrode material in the step (1) for 60 minutes, placing the material into a plasma etching machine for treatment for 5 minutes, then, carrying out heat treatment on the material for 24 hours in a potassium iodide solution with the concentration of 0.5 mol/L under the condition of introducing 1 sccm hydrogen under the vacuum degree of 20 Pa, wherein the molar ratio of potassium iodide to the Fe-MOF electrode material is 10:1, the heat treatment temperature is 120 ℃, and cooling, separating and washing the material to obtain the Fe-MOF bulk electrode material after iodine ion doping modification.
The iodine ion doped modified Fe-MOF bulk electrode material is applied to an iodine ion super capacitor, and the specific method comprises the following steps: weighing 8 mg of doped modified Fe-MOF bulk electrode material, 1 mg of NMP and 1 mg of acetylene black, fully grinding in a mortar, uniformly scraping and coating 1.5mg of doped modified Fe-MOF bulk electrode material on carbon cloth according to 4 square centimeters, and drying in an oven at 80 ℃ for 12 hours.
As shown in figure 1, an XRD diffraction pattern of the Fe-MOF bulk electrode material after iodide ion doping modification is obtained, obvious three strong lines can be seen, and the material prepared on the surface is the Fe-MOF bulk electrode material and has a crystal structure. As shown in FIG. 2, a scanning electron microscope image of the iodine ion doped and modified Fe-MOF bulk electrode material is obtained, the microscopic size of the sample belongs to the nanometer level, and the appearance of the sample is granular. As shown in FIG. 3, the element distribution diagram of the Fe-MOF bulk electrode material modified by doping iodine ions is obtained. It can be seen that the elements of the iodide ions are uniformly distributed in the material, indicating successful doping with iodide ions. As shown in FIG. 4, the control modified virgin Fe-MOF without doping with iodide ions was at 1mol/L Na2SO4Medium CV, no peak of iodide ion; as shown in figure 5, the prepared iodine ion doped modified Fe-MOF bulk electrode material is 1mol/L Na2SO4The CV diagram shows that the specific capacity after doping is twice that before doping, and reaches 436F g-1。
Example 2
A preparation method of an iodine ion doped modified Fe-MOF bulk electrode material comprises the following specific steps:
(1) weighing 1 mmol of ferric sulfate to be dissolved in 10 mL of deionized water to generate solution A, weighing 1 mmol of potassium ferrocyanide to be dissolved in 10 mL of deionized water to generate solution B, stirring the solution A and the solution B at room temperature for 60 minutes, adding the solution A and the solution B into a liner of a hydrothermal kettle, and carrying out hydrothermal reaction for 24 hours at the temperature of 60 ℃. Wherein the molar ratio of the ferric salt in the solution A to the potassium ferrocyanide in the solution B is 0.75: 0.75; and collecting a product obtained by the reaction, and centrifugally cleaning the product for 4 times by using a mixed solution of ethanol and deionized water to finally obtain a blue product, namely the Fe-MOF bulk electrode material.
(2) And (2) grinding the Fe-MOF electrode material in the step (1) for 5 minutes, placing the material into a plasma etching machine for treatment for 10 minutes, introducing 1 sccm hydrogen gas for treatment under the vacuum degree of 20 Pa, performing heat treatment on the treated material in 0.5 mol/L potassium iodide solution for 24 hours, cooling, separating and washing to obtain the iodine ion doped and modified Fe-MOF bulk electrode material.
The method for applying the iodine ion doped modified Fe-MOF bulk electrode material to the iodine ion super capacitor specifically comprises the following steps: weighing 8 mg of doped modified Fe-MOF bulk electrode material, 1 mg of NMP and 1 mg of acetylene black, fully grinding in a mortar, blade-coating on carbon cloth, and drying in an oven at 60 ℃. As shown in fig. 10, a scanning electron microscope image of the modified Fe-MOF bulk electrode material doped with iodide ions was obtained, and compared with the sample in example 1, the microscopic size of the sample was in the order of micrometers, and the appearance of the sample appeared in a square. Therefore, the addition of the polyvinylpyrrolidone PVP template agent, the sulfuric acid and the trisodium citrate effectively keeps the particle size at a nanometer level, is beneficial to obtaining particles with small diameters, and lays a foundation for obtaining good plasma treatment results subsequently.
Example 3
A preparation method of an iodine ion doped modified Fe-MOF bulk electrode material comprises the following specific steps:
(1) weighing 1 mmol of ferric nitrate and dissolving in 10 mL of deionized water to generate A solution, weighing 1 mmol of potassium ferrocyanide and dissolving in 10 mL of deionized water to generate B solution, and adding 0.5g of polyvinylpyrrolidone PVP template, 1 mL of sulfuric acid and 0.1g of trisodium citrate into the B solution, wherein the relative molecular mass of the polyvinylpyrrolidone PVP template is 1300000. Stirring the solution A and the solution B at room temperature for 5 minutes, and then adding the solution A and the solution B into an inner container of a hydrothermal kettle for hydrothermal reaction, wherein the molar ratio of ferric salt in the solution A to potassium ferrocyanide in the solution B is 0.75: 2; the hydrothermal reaction temperature is 120 ℃, and the reaction time is 12 hours; collecting a product obtained by the reaction, and centrifugally cleaning the product for 5 times by using a mixed solution of ethanol and deionized water to finally obtain a blue product, namely the Fe-MOF bulk electrode material;
(2) grinding the Fe-MOF electrode material in the step (1) for 60 minutes, placing the material into a plasma etching machine for treatment for 20 minutes, then carrying out heat treatment on the material for 48 hours in a potassium iodide solution with the concentration of 0.1mol/L under the condition of introducing 10 sccm hydrogen under the vacuum degree of 0.01 Pa, wherein the molar ratio of potassium iodide to the Fe-MOF electrode material is 10:1, the heat treatment temperature is 60 ℃, and cooling, separating and washing to obtain the iodine ion doped and modified Fe-MOF bulk electrode material.
The iodine ion doped modified Fe-MOF bulk electrode material is applied to an iodine ion super capacitor, and the specific method comprises the following steps: weighing 8 mg of doped modified Fe-MOF bulk electrode material, 1 mg of NMP and 1 mg of acetylene black, fully grinding in a mortar, uniformly scraping and coating 2.0mg of doped modified Fe-MOF bulk electrode material on carbon cloth according to 4 square centimeters, and drying in an oven at 60 ℃ for 48 hours.
Example 4
A preparation method of an iodine ion doped modified Fe-MOF bulk electrode material comprises the following specific steps:
(1) weighing 1 mmol of ferric acetate to be dissolved in 10 mL of deionized water to generate A solution, weighing 1 mmol of potassium ferrocyanide to be dissolved in 10 mL of deionized water to generate B solution, and adding 0.5g of polyvinylpyrrolidone PVP template, 1 mL of sulfuric acid and 0.5g of trisodium citrate into the B solution, wherein the relative molecular mass of the polyvinylpyrrolidone PVP template is 1000000. Stirring the solution A and the solution B at room temperature for 50 minutes, and then adding the solution A and the solution B into an inner container of a hydrothermal kettle for hydrothermal reaction, wherein the molar ratio of ferric salt in the solution A to potassium ferrocyanide in the solution B is 0.75: 1; the hydrothermal reaction temperature is 80 ℃, and the reaction time is 48 hours; collecting a product obtained by the reaction, and centrifugally cleaning the product for 5 times by using a mixed solution of ethanol and deionized water to finally obtain a blue product, namely the Fe-MOF bulk electrode material;
(2) grinding the Fe-MOF electrode material in the step (1) for 80 minutes, placing the material into a plasma etching machine for treatment for 5 minutes, then carrying out heat treatment for 30 hours in a potassium iodide solution with the concentration of 5 mol/L under the condition of introducing 0.1 sccm hydrogen under the vacuum degree of 40 Pa, wherein the molar ratio of potassium iodide to the Fe-MOF electrode material is 10:1, the heat treatment temperature is 80 ℃, and cooling, separating and washing to obtain the iodine ion doped and modified Fe-MOF bulk electrode material.
The iodine ion doped modified Fe-MOF bulk electrode material is applied to an iodine ion super capacitor, and the specific method comprises the following steps: weighing 8 mg of doped modified Fe-MOF bulk electrode material, 1 mg of NMP and 1 mg of acetylene black, fully grinding in a mortar, uniformly scraping and coating 2.0mg of doped modified Fe-MOF bulk electrode material on carbon cloth according to 4 square centimeters, and drying in an oven at 60 ℃ for 48 hours.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of an iodine ion doped modified Fe-MOF bulk electrode material is characterized by comprising the following steps:
dissolving ferric salt in deionized water to generate 0.1mol/L solution A, dissolving potassium ferrocyanide in deionized water to generate 0.1mol/L solution B, adding polyvinylpyrrolidone (PVP) template, sulfuric acid and trisodium citrate into the solution B, and mixing the solution B with the solution A, wherein the molar ratio of the ferric salt in the solution A to the potassium ferrocyanide in the solution B is 0.75: 0.75-2; stirring at room temperature, adding into a hydrothermal kettle, and carrying out hydrothermal reaction at 60-120 ℃ for 12-48 h; collecting a product obtained by the reaction after the hydrothermal reaction is finished, and centrifugally cleaning the product by using a mixed solution of ethanol and deionized water to finally obtain a blue product Fe-MOF bulk electrode material;
and (2) grinding the Fe-MOF electrode material in the step (1), putting the ground Fe-MOF electrode material into a plasma etching machine for treatment for 5-20 min, then performing heat treatment in a potassium iodide solution of 0.1-5 mol/L under the condition of a vacuum degree of 0.01-40 Pa through hydrogen, wherein the molar ratio of potassium iodide to the Fe-MOF electrode material is 10:1, the heat treatment temperature is 60-120 ℃, the heat treatment time is 12-48 h, and after the heat treatment, cooling, separating and washing to obtain the iodine ion doped and modified Fe-MOF bulk electrode material.
2. The preparation method of the iodine ion doped modified Fe-MOF bulk electrode material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the ferric salt is selected from one of ferric sulfate, ferric chloride, ferric acetate and ferric nitrate.
3. The method for preparing the iodine ion doped modified Fe-MOF bulk electrode material according to claim 1 or 2, wherein the method comprises the following steps: the relative molecular mass of the polyvinylpyrrolidone PVP template in the step (1) is 10000-.
4. The method for preparing the iodine ion doped modified Fe-MOF bulk electrode material according to claim 1 or 2, wherein the method comprises the following steps: and (2) when the polyvinylpyrrolidone PVP template agent, the sulfuric acid and the trisodium citrate are added into the solution B in the step (1), wherein the sulfuric acid is added according to 1% of the volume of the solution B, the molar concentration of the trisodium citrate is 0.01mol/L, and the molar ratio of the polyvinylpyrrolidone PVP template agent to the trisodium citrate is 1: 1.
5. The preparation method of the iodine ion doped modified Fe-MOF bulk electrode material according to claim 4, wherein the preparation method comprises the following steps: the room-temperature stirring time in the step (1) is 5-60 minutes.
6. The method for preparing the iodine ion doped modified Fe-MOF bulk electrode material according to claim 1 or 5, wherein the method comprises the following steps: the grinding time in the step (2) is 5-80 minutes.
7. The method for preparing the iodine ion doped modified Fe-MOF bulk electrode material according to claim 1 or 5, wherein the method comprises the following steps: the flow rate of hydrogen introduced in the step (2) is 0.1-10 sccm.
8. The preparation method of any one of the preceding claims, so as to obtain the iodine ion doped modified Fe-MOF bulk electrode material.
9. The use of the iodide ion doped modified Fe-MOF bulk electrode material of claim 8 in an iodide supercapacitor.
10. The application of the iodine ion doped modified Fe-MOF bulk electrode material in the iodine ion supercapacitor is characterized in that the specific method is as follows: fully grinding the iodine ion doped modified Fe-MOF bulk electrode material, NMP and acetylene black according to the mass ratio of 8: 1, uniformly coating 1.5-2mg per 4 square centimeters on carbon cloth, and drying in an oven at the temperature of 60-80 ℃ for 12-48 h.
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