CN107230558B - Fe3O4Preparation method of/graphene composite material - Google Patents
Fe3O4Preparation method of/graphene composite material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/46—Metal oxides
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
Fe3O4The preparation method of the graphene composite material comprises the steps of placing anhydrous sodium acetate, sodium citrate and ferric trichloride in ethylene glycol for magnetic stirring to obtain an iron precursor suspension; ultrasonically dispersing graphene oxide in ethylene glycol to prepare a graphene oxide ethylene glycol turbid liquid; placing the oxidized graphene ethylene glycol turbid liquid and the iron precursor turbid liquid in a reaction kettle for sealing, cooling to room temperature after reaction, separating by using a magnet to obtain a solid phase sample, washing by using deionized water, and drying in vacuum to obtain Fe3O4A graphene composite material. According to the method, energy is stored through the Faraday quasi-capacitor generated in the charging and discharging processes, the graphene is prevented from being stacked in the charging and discharging processes, and Fe is enabled to be generated3O4And a synergistic effect is generated between the graphene and the graphene, so that the capacitor cathode material with good capacitive performance and good cycling stability is obtained.
Description
Technical Field
The invention relates to Fe3O4Preparation method of graphene composite material, in particular to Fe of super capacitor electrode material for energy storage3O4A preparation method of a graphene composite material.
Background
With the continuous development of the energy storage industry, the electric energy storage technology plays an increasingly important role in industrial life, and various energy storage devices are more and more widely applied to the fields of electronic products such as new energy automobiles, military equipment, high-power starting power supplies and the like. The super capacitor is a hot point of application due to the advantages of large energy density, high power density, long cycle life and the like.
As the application of the super capacitor is more and more extensive, the requirement for the performance of the super capacitor is gradually increased. However, due to the limitation of the specific capacity of the electrode material, the improvement of the performance meets the bottleneck, wherein the electrode material is the key, and the quality of the performance directly influences the quality of the performance of the supercapacitor. Therefore, the development of the electrode material with excellent performance has important significance for improving the performance of the supercapacitor.
Fe3O4The method has the advantages of high theoretical specific capacity, rich raw material resources, no environmental pollution and the like, and has wide application prospect in the field of cathode materials for supercapacitors. However, it is easily structurally broken during charge and discharge and has poor cycle stability. Preparation of nanostructured Fe3O4And construction of Fe3O4The composite material can solve the above problems to some extent.
The graphene has high specific surface area and excellent conductivity, so that the graphene can be mixed with Fe3O4One of the most promising carbon materials for compounding. Researches indicate that the Fe can be obviously improved by compounding with graphene3O4The cycling stability of the graphene is high, however, the graphene is easy to agglomerate in the charging and discharging processes, and the stable composite material is difficult to prepare. The existing composite material preparation methods mainly comprise a coprecipitation method and a vapor deposition method. Wherein the coprecipitation method is used for preparing Fe3O4The composite material needs solution to maintain accurate pH value, and has small temperature fluctuation and harsh reaction conditions in the synthesis process. The vapor deposition method requires more precise equipment and has higher requirements on synthesis equipment, thereby greatly improving the production cost and being difficult to realize industrialization.
Disclosure of Invention
The invention aims to provide a method for making Fe3O4Fe which is stably dispersed on the surface of graphene, does not agglomerate in the charge-discharge process of graphene, can be used as an electrode material of a supercapacitor, and has good cycle stability3O4A preparation method of a graphene composite material.
The inventionFe for solving the above technical problems3O4The preparation method of the graphene composite material comprises the following steps:
fe3O4The preparation method of the/graphene composite material comprises the following steps:
1) placing anhydrous sodium acetate, anhydrous sodium citrate and 0.2800g of anhydrous ferric chloride in 30mL of ethylene glycol, and stirring for 2 hours under the magnetic force of 300 r/min to obtain an iron precursor suspension;
2) ultrasonically dispersing graphene oxide in 30mL of glycol to prepare a graphene oxide glycol turbid liquid;
3) placing the graphene oxide ethylene glycol suspension and the iron precursor suspension in a reaction kettle for sealing, reacting at 205 ℃ for 15-30 h, cooling to room temperature, separating by using a magnet to obtain a solid phase sample, washing by using deionized water, and drying in vacuum at 50 ℃ to obtain Fe3O4A graphene composite material.
In the above technical solution, further technical features are as follows:
the molar ratio of the anhydrous sodium acetate to the anhydrous ferric chloride is 3.5-4.8; the molar ratio of the anhydrous sodium citrate to the anhydrous ferric chloride is 0.25-0.35; the mass ratio of the graphene oxide to the anhydrous ferric chloride is 1.4-1.8.
The graphene oxide is surface functionalized graphene oxide; the surface functionalization method comprises the steps of adopting a nitric acid solution with the concentration of 0.1-2.0 mol/L to perform surface functionalization treatment on graphene oxide for 1-5 h at the temperature of 30-60 ℃ under the condition that the corresponding relation between the mass of the graphene oxide and the volume of the nitric acid solution is that 1 g corresponds to 20-50mL, and performing vacuum drying on an obtained solid phase sample to obtain the graphene oxide.
The invention provides Fe3O4The preparation method of the graphene composite material comprises the step of adding Fe in a precursor solution3+The acting force between the Fe and the oxygen-containing functional group on the surface of the graphene oxide is used for realizing Fe3+The surface of the graphene oxide is tightly combined with the surface of the graphene oxide,in the suspension system formed, Fe having positive electric charge3+Assembling the graphene oxide with negative electricity on the surface through interaction to obtain the graphene oxide with Fe combined on the surface3+The graphene oxide material of (1). In a reaction kettle at 205 ℃ and Fe3O4Fe which will oxidize the surface of graphene3+As a starting point, the graphene oxide gradually and uniformly grows on the surface of the graphene oxide. Wherein the ethylene glycol plays the role of a solvent and a reducing agent, and on the one hand, it is Fe3O4The preparation of (2) provides a better liquid phase environment, and on the other hand, part of Fe can be mixed3 +Reduction to Fe2+Thereby making Fe3O4And growing, and reducing the graphene oxide into graphene. The preparation method of the invention skillfully utilizes glycol as a reducing agent to obtain Fe3O4Meanwhile, graphene oxide is reduced into graphene in situ in a reaction system, so that the subsequent reduction operation is omitted.
Fe prepared by the method3O4The/graphene composite material can be used as a cathode material of a super capacitor, wherein Fe3O4Energy storage is carried out through Faraday quasi-capacitor generated in the charging process, and Fe is improved through graphene3O4Is electrically conductive and provides a channel for electron transport, Fe3O4The formed lamellar space is favorable for the migration of anions and cations in the electrolyte, thereby being capable of exerting Fe3O4And the graphene to obtain the super capacitor cathode material with good capacitive performance.
Drawings
FIG. 1 is Fe of example 1 of the present invention3O4XRD pattern of the/graphene composite material.
FIG. 2 is Fe of example 1 of the present invention3O4SEM images of/graphene composites.
FIG. 3 is Fe of example 1 of the present invention3O4The/graphene composite material is used as a cycle curve of the cathode material of the super capacitor.
Detailed Description
In order to make the technical problems, technical solutions and advantages solved by the present invention easier to understand, embodiments of the present invention are further described below with reference to the accompanying drawings.
Example 1
Fe of the present example3O4The preparation method of the graphene composite material comprises the following steps:
1) weighing 0.4000g of graphene oxide, placing the graphene oxide in 15.0mL of nitric acid solution with the concentration of 1.0mol/L, performing surface functionalization treatment on the graphene oxide for 4.5 hours at 40 ℃, and performing vacuum drying on the obtained solid phase sample to obtain functionalized graphene oxide.
2) 0.2800g of anhydrous ferric chloride, 0.6360g of anhydrous sodium acetate and 0.1500g of anhydrous sodium citrate are weighed and dispersed in 30mL of ethylene glycol, and the mixture is magnetically stirred for 2 hours to obtain an iron precursor suspension.
3) Taking 0.3950g of functionalized graphene oxide, and ultrasonically dispersing in 30mL of glycol to obtain a graphene oxide glycol suspension;
4) placing the oxidized graphene ethylene glycol suspension and the iron precursor suspension together in a self-boosting reaction kettle with a polytetrafluoroethylene lining for sealing, reacting at 205 ℃ for 24 hours, cooling to room temperature, separating by using a magnet to obtain a solid phase sample, washing by using deionized water, and drying in vacuum at 50 ℃ to obtain Fe3O4A graphene composite material.
Comparative example is "Fe" published in volume III of 2017 "journal of Fuel chemistry3O4Preparation of/RGO composite material and electrochemical performance research thereof ".
The procedure in the comparative example was:
1) 30 mg of graphene oxide was added to 30mL of a solution containing 0.33 mmol of phenylphosphonic acid and Fe (NO)3)3·9H2And (4) dispersing the mixture in deionized water of O by ultrasonic uniformly.
2) 600 mg of urea was added, and the solution was transferred to a 75 mL hydrothermal kettle and reacted at 180 ℃ for 48 hours
3) Putting the sample into a quartz tube reactor, and placing the quartz tube reactor under the protection of Ar atmosphere at one atmospheric pressure for rapid heatingRapidly heating to 500 deg.C, maintaining for 1 h, cooling to room temperature under the protection of Ar, and collecting to obtain Fe3O4A graphene composite material.
The phenylphosphonic acid adopted in the comparative example is a toxic and corrosive organic chemical raw material, and the steps of raising the temperature to 500 ℃ in an Ar gas atmosphere and preserving the temperature for 1 h are adopted after hydrothermal treatment, so that the energy consumption is large.
Example 2
Fe of the present example3O4The preparation method of the graphene composite material comprises the following steps:
1) weighing 0.4600 g of graphene oxide, placing the graphene oxide in 20 mL of nitric acid solution with the concentration of 0.5 mol/L, performing surface functionalization treatment on the graphene oxide for 5 hours at 50 ℃, and performing vacuum drying on the obtained solid phase sample to obtain functionalized graphene oxide.
2) 0.2800g of anhydrous ferric chloride, 0.5381 g of anhydrous sodium acetate and 0.1200 g of anhydrous sodium citrate are weighed and dispersed in 30mL of ethylene glycol, and the mixture is magnetically stirred for 2 hours to obtain an iron precursor suspension.
3) 0.4500 g of functionalized graphene oxide is ultrasonically dispersed in 30mL of glycol to prepare a graphene oxide glycol suspension;
4) placing the oxidized graphene ethylene glycol suspension and the iron precursor suspension together in a self-boosting reaction kettle with a polytetrafluoroethylene lining for sealing, reacting for 28 h at 205 ℃, cooling to room temperature, separating by using a magnet to obtain a solid phase sample, washing by using deionized water, and drying in vacuum at 50 ℃ to obtain Fe3O4A graphene composite material.
Comparative example 2015 published inSynthetic MetalsVolume 209 "contamination of magnetic angular hexagonal-Fe3O4 sheets/reduced graphene oxide composite for supercapacitors”。
The procedure used in the comparative example was:
1) 8 g of ferric chloride was dissolved in 40 mL of deionized water.
2) Dropwise adding the iron salt solution into 200 mL of boiling water within 10 min, and reacting for 2 min
Comparative example Fe (OH)3The preparation method increases the reaction steps, and the specific capacitance of the prepared sample is only 193F/g.
Example 3
Fe of the present example3O4The preparation method of the graphene composite material comprises the following steps:
1) weighing 0.5500 g of graphene oxide, placing the graphene oxide in 15 mL of nitric acid solution with the concentration of 2.0 mol/L, performing surface functionalization treatment on the graphene oxide for 2 hours at 40 ℃, and performing vacuum drying on the obtained solid phase sample to obtain functionalized graphene oxide.
2) 0.2800g of anhydrous ferric chloride, 0.5947 g of anhydrous sodium acetate and 0.1336 g of anhydrous sodium citrate are weighed and dispersed in 30mL of ethylene glycol, and the mixture is magnetically stirred for 2 hours to obtain an iron precursor suspension.
3) Taking 0.5000 g of functionalized graphene oxide, and ultrasonically dispersing in 30mL of glycol to obtain a graphene oxide glycol suspension;
4) placing the oxidized graphene ethylene glycol suspension and the iron precursor suspension together in a self-boosting reaction kettle with a polytetrafluoroethylene lining for sealing, reacting for 17 hours at 205 ℃, cooling to room temperature, separating by using a magnet to obtain a solid phase sample, washing by using deionized water, and drying in vacuum at 50 ℃ to obtain Fe3O4A graphene composite material.
Comparative example is published in 2013NanotechnologyVolume 24, phase 2 "furniture and straight forward Synthesis of pretreated reduced graphene oxide-Fe3O4 hybrid composite by a solvothermal reaction”。
Wherein the iron source adopts ferric acetylacetonate, and the embodiment adopts ferric trichloride, and the price is low.
Test example 1
1) Phase testing
Fe obtained in example 13O4XRD detection is carried out on the/graphene composite material, and the result is shown in the attached figure 1.
As can be seen from FIG. 1, the sample obtained in example 1 has a sharp diffraction peak corresponding to Fe in the position of standard card (JCPDS No. 65-3107)3O4Of inverse spinel type, indicating that the sample obtained was Fe3O4。
2) Topography testing
Fe obtained in example 13O4SEM detection is carried out on the/graphene composite material, and the results are respectively shown in the attached figures 2 and 3.
As can be seen from FIG. 2, in Fe3O4In the graphene composite material, Fe3O4Uniformly dispersed on the surface of graphene, and Fe3O4The particles are flaky and grow on the surface of graphene vertically.
3) Electrochemical performance test
Fe obtained in example 13O4The/graphene composite material is used as a cathode material of a super capacitor, a platinum electrode is used as a counter electrode, mercury oxide is used as a reference electrode, 0.9 mol/L KOH is used as an electrolyte, charge and discharge are carried out under the condition that the current density is 1A/g, and a charge and discharge cycle test is carried out, wherein the test result is shown in figure 3. As can be seen from FIG. 3, Fe prepared in example 13O4The specific capacitance of the graphene composite material as the cathode material of the super capacitor can reach 330F/g under the current density of 1A/g, and still can reach 305.7F/g after 500 times of circulation, which shows that the graphene composite material has good circulation stability.
Fe prepared in example 2 and example 33O4The specific capacitance of the/graphene composite material as the cathode material of the super capacitor is 325F/g and 305F/g respectively under the current density of 1A/g by adopting the method, and the specific capacitance of the/graphene composite material after 500 times of circulation is 305.2F/g and 291.8F/g respectively.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, all equivalent variations within the scope of the present invention are also within the scope of the present invention.
Carrying out one of the above-mentioned processes3O4A key step of the preparation method is that ferric trichloride, sodium acetate and sodium citrate are placed in ethylene glycol and stirred to prepare iron precursor suspension. Wherein: ferric trichloride, sodium acetate and sodium citrate must be anhydrous ferric trichloride, anhydrous sodium acetate and anhydrous sodium citrate, otherwise, the presence of water in the system would result in the hydrolysis of ferric trichloride to Fe (OH)3Further generate Fe2O3It will be difficult to obtain Fe3O4A graphene composite material; the molar ratio of anhydrous sodium acetate to anhydrous ferric chloride is 3.5-4.8, the molar ratio of anhydrous sodium citrate to anhydrous ferric chloride is 0.25-0.35, if the content of anhydrous sodium acetate is too little or too much, Fe is difficult to ensure3O4Too little anhydrous sodium citrate will make Fe difficult to guarantee3O4Too much will form a composite material, which increases costs.
Carrying out one of the above-mentioned processes3O4The preparation method of the graphene/graphene composite material has the other key step that the mass ratio of the graphene oxide to the anhydrous ferric chloride is 1.4-1.8. If the mass ratio is less than 1.4, Fe is caused3O4Excess of Fe3O4Will not be composited with graphene oxide; if the mass ratio is greater than 1.8, the graphene oxide may be excessive, and Fe on the surface of the graphene may be generated3O4Less growth also increases cost.
Carrying out one of the above-mentioned processes3O4The last key step of the preparation method is that the graphene oxide is the graphene oxide with functionalized surface, and the conditions of the surface functionalization are as follows: under the condition that the corresponding relation between the mass of the graphene and the volume of the nitric acid solution is that 1 g corresponds to 20-50mL, the surface functionalization treatment is carried out on the graphene for 1-5 h at the temperature of 30-60 ℃ by adopting the nitric acid solution with the concentration of 0.1-2.0 mol/L, and the obtained solid phase sample is dried in vacuum. If the concentration of the nitric acid solution is less than 0.1 mol/L, the dosage of the nitric acid solution is too small, the functionalization temperature is lower than 30 ℃, the treatment time is less than 1 h, and the graphene surface is difficult to perform better functionsChemical treatments, all above, can lead to excessive oxidation of the graphene surface, and eventually lead to difficulty in obtaining Fe3O4The consequence of the/graphene composite.
Claims (1)
1. Fe3O4The preparation method of the/graphene composite material comprises the following steps:
1) weighing 0.4000g of graphene oxide, placing the graphene oxide in 15.0mL of nitric acid solution with the concentration of 1.0mol/L, performing surface functionalization treatment on the graphene oxide for 4.5 hours at 40 ℃, and performing vacuum drying on the obtained solid phase sample to obtain functionalized graphene oxide;
2) weighing 0.2800g of anhydrous ferric trichloride, 0.6360g of anhydrous sodium acetate and 0.1500g of anhydrous sodium citrate, dispersing the anhydrous ferric trichloride, 0.6360g of anhydrous sodium acetate and 0.1500g of anhydrous sodium citrate in 30mL of ethylene glycol, and magnetically stirring for 2 hours to obtain an iron precursor suspension;
3) taking 0.3950g of functionalized graphene oxide, and ultrasonically dispersing in 30mL of glycol to obtain a graphene oxide glycol suspension;
4) placing the oxidized graphene ethylene glycol suspension and the iron precursor suspension together in a self-boosting reaction kettle with a polytetrafluoroethylene lining for sealing, reacting at 205 ℃ for 24 hours, cooling to room temperature, separating by using a magnet to obtain a solid phase sample, then washing by using deionized water, drying in vacuum at 50 ℃, and drying in Fe3O4In the graphene composite material, Fe3O4Uniformly dispersed on the surface of graphene, and Fe3O4The particles are flaky and grow on the surface of graphene vertically.
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| CN107910192A (en) * | 2017-11-17 | 2018-04-13 | 常州大学 | A kind of electrode material for super capacitor Fe2O3The preparation method of/rGO |
| CN108854962A (en) * | 2018-07-09 | 2018-11-23 | 内蒙古科技大学 | Heavy-metal adsorption material and the preparation method and application thereof based on magnetic oxygenated graphene |
| CN109546128A (en) * | 2018-11-28 | 2019-03-29 | 北京科技大学 | A kind of nanometer of ferrous sulfide/grapheme composite positive electrode material preparation method |
| CN110182894B (en) * | 2019-05-20 | 2022-01-04 | 长江大学 | Preparation method and application of magnetic carbon nanotube demulsifier |
| CN110492079A (en) * | 2019-08-26 | 2019-11-22 | 东北大学 | A kind of preparation method and application of sheet ferroso-ferric oxide negative electrode material |
| CN114853107B (en) * | 2022-04-13 | 2023-08-22 | 锦洋高新材料股份有限公司 | Deep defluorination process for fluorine-containing wastewater and aluminum source defluorination agent |
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