CN111302403A - Preparation method and application of ferroferric oxide @ iron disulfide nanocomposite - Google Patents
Preparation method and application of ferroferric oxide @ iron disulfide nanocomposite Download PDFInfo
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Abstract
The invention relates to the field of capacitor composite materials, in particular to a ferroferric oxide @ iron disulfide nano composite material and a preparation method thereof, wherein the ferroferric oxide @ iron disulfide nano composite material is prepared by the following steps: firstly, preparing ferrous sulfate monohydrate, then calcining the ferrous sulfate monohydrate at high temperature to prepare ferric oxide, annealing the ferric oxide to obtain ferroferric oxide, and then carrying out high-temperature gas-phase vulcanization reaction on the ferroferric oxide in sulfur powder to prepare the ferroferric oxide @ iron disulfide nano composite particles. The preparation process of the invention is easy to operate, the content of each component is controllable, the reproducibility is good, the electrode material used in the super capacitor shows very high capacitance characteristic, and the mass production is easy.
Description
Technical Field
The invention relates to the field of capacitor composite materials, in particular to a ferroferric oxide @ iron disulfide nano composite material and a preparation method thereof.
Background
In recent years, with rapid progress in the fields of electric vehicles, hybrid electric vehicles, portable electronic devices, and the like, development of mobile chemical power sources having both high specific energy and high power density has become a direction of major attention of workers. The super capacitor has higher power density, excellent cycle life and rapid charge and discharge capacity, and is a unique energy storage device; as the core of the super capacitor, the development of the electrode material becomes a hot spot of the current research, and the iron-based oxide electrode material is widely used for the electrode material of the super capacitor due to the advantages of low price, easy obtaining, environmental friendliness, high theoretical capacity and the like. However, the capacitance of the iron-based oxide electrode material is generally low due to the low conductivity and proton transport capability of the iron-based oxide.
At present, researches report that the construction of an iron-based oxide nanocomposite for an electrode material of a supercapacitor is one of effective ways for improving the capacity of the electrode material of the iron-based oxide, and an iron-sulfur bond is a chemical bond weaker than an iron-oxygen bond, so that the iron-based sulfide has better conductivity than the iron-based oxide; however, the preparation method of the iron-based composite material is complicated at present and is not beneficial to mass production, so that the application of the iron-based composite material is limited to a certain extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the ferroferric oxide @ iron disulfide nano composite material and the preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of ferroferric oxide @ iron disulfide nanocomposite comprises the following steps:
(1) preparation of ferric oxide: preparing ferrous sulfate monohydrate, placing the prepared ferrous sulfate monohydrate in a vacuum tubular furnace, raising the temperature from room temperature to 650-750 ℃ at the temperature raising rate of 5 ℃/min under the argon atmosphere of 30sccm, annealing for 2-4h, and cooling to room temperature to obtain ferric oxide;
(2) preparing ferroferric oxide: annealing the ferric oxide prepared in the step (1) under a vacuum condition to prepare ferroferric oxide;
(3) preparing ferroferric oxide @ iron disulfide nano composite particles: placing the ferroferric oxide prepared in the step (2) in a vacuum tubular furnace, placing sulfur powder in an air source port of the vacuum tubular furnace, raising the temperature from normal temperature to 350-plus-one 450 ℃ at a heating rate of 2 ℃/min under the argon atmosphere of 30sccm, preserving the heat for 4 hours after the highest temperature is reached, cooling to room temperature, washing with deionized water and ethanol in sequence, and drying to prepare the ferroferric oxide @ iron disulfide nano composite particles;
wherein the mass ratio of the sulfur powder to the ferroferric oxide is 3-7: 1.
Preferably, the preparation method of the ferrous sulfate monohydrate in the step (1) comprises the following steps: dissolving ferrous sulfate heptahydrate and thiourea in absolute ethanol, mixing uniformly, stirring for 30-50min, refluxing at 80-90 deg.C for 40min, naturally cooling to room temperature, centrifuging, purifying, and vacuum drying;
wherein the mass ratio of the ferrous sulfate heptahydrate to the thiourea is 1: 1.5-2.5.
Preferably, the annealing conditions of step (2) are as follows: in an argon atmosphere, raising the temperature from normal temperature to 450-550 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 5h after reaching the highest temperature, then cooling to the room temperature, washing with deionized water and ethanol in sequence, and then drying in vacuum for 10-12 h.
Preferably, the method of the vacuum tube furnace in the step (1) and the step (3) comprises the following steps: the tube furnace is firstly vacuumized, and then argon is repeatedly filled for many times until the air in the tube furnace is exhausted.
The invention also provides the ferroferric oxide @ iron disulfide nanocomposite prepared by the preparation method of the ferroferric oxide @ iron disulfide nanocomposite.
The invention also protects the application of the ferroferric oxide @ iron disulfide nanocomposite material as an electrode material in a super capacitor.
Preferably, the supercapacitor is used in a device for providing power.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the iron-based composite material is relatively complicated at present, is not beneficial to mass production, and has certain limitation on application, the preparation process of the preparation method of the ferroferric oxide @ iron disulfide nano composite material is easy to operate, specifically, ferrous sulfate heptahydrate is dehydrated through thiourea to obtain ferrous sulfate monohydrate, and then, calcining ferrous sulfate monohydrate at high temperature to prepare ferric oxide, annealing the ferric oxide to obtain ferroferric oxide, and performing high-temperature gas-phase vulcanization reaction on the ferroferric oxide in sulfur powder to prepare the ferroferric oxide @ iron disulfide nano composite particles.
2. The method for preparing the iron-based nano material in the prior art has complicated steps, for example, the method for preparing FeS by Sun et al is complicated2The GNS material needs microwave-assisted high-temperature hydrothermal reaction (Z.Q.Sun, H.M.Lin, F.Zhang, X.Yang, H.Jiang, Q.Wang and F.Y.Qu, J.Mater.chem.A,2018,6, 14956-plus 14966), and the hydrothermal temperature reaches 180 ℃; wang et al preparation of FeS2The @ C nanomaterial requires a four-step reaction (F.B.Wang, G.D.Li, X.G.Meng, Y.X.Li, Q.F.Gao, Y.Q.xu and W.F.Cui, Inorg.chem.Front.,2018,5,2462-2471), and the hydrothermal reaction of the first step requires a reaction at 180 ℃ for 30 hours; liu et al prepared eggshell knotsFeS of structure2@ carbon nanomaterial (Z.M.Liu, T.C.Lu, T.Song, X. -Y.Yuand X.W.Lou, Energy environ.Sci.,2017,10,1576- > 1580), the first step in the process requires adding Fe (OH)3The gel was reacted at 100 ℃ for a period of 4 days; the above methods either require high reaction temperature, have severe requirements on reaction equipment, or require long time, and the reason is that it is difficult to realize large-scale production of materials by the above preparation methods, thereby limiting the application of materials. According to the method for preparing the ferroferric oxide @ iron disulfide nanocomposite, the ferrous sulfate monohydrate is refluxed for 40min at the temperature of 80-90 ℃, and then the target product can be obtained through the annealing process, the preparation process is relatively mild, the preparation is carried out in a tubular furnace, the requirement on reaction equipment is not high, and the large-scale production of the material is easily realized.
3. Compared with the performance of the prepared electrode material for the super capacitor in the prior art, the nano composite material prepared by the invention can still have very high capacitance capacity under higher current density when being used for the electrode material of the super capacitor, the current density is 5A/g, the charging and discharging times is 10000 cycles, and the electrode material has excellent cycling stability, so that the electrode material for the super capacitor with huge potential is prepared by the invention.
4. The ferroferric oxide @ iron disulfide nano composite material prepared by the invention can obtain composite materials with different compositions through the change of the ratio of sulfur powder to ferroferric oxide, and the research on the ferroferric oxide @ iron disulfide nano composite materials with different compositions is carried out, and the result shows that: in the vulcanization process, the nano composite material prepared when the amount of ferroferric oxide and sulfur powder is 1:5 has the best electrochemical performance and the best cycle performance, and ferric oxide can be generated only after the ferrous sulfate monohydrate is annealed.
Drawings
FIG. 1 is a scanning electron micrograph of NP3 prepared in example 1 of the present invention, and the scanning magnification is gradually increased from a low-magnification scan to a high-magnification scan with the graphs of a-c;
FIG. 2 is a scanning electron micrograph of NP5 prepared in example 4 of the present invention, and the scanning magnification is gradually increased from a low-magnification scan to a high-magnification scan with the graphs of a-c;
FIG. 3 is a scanning electron micrograph of NP7 prepared in example 5 of the present invention, gradually increasing from a low power scan to a high power scan with FIGS. a-c;
FIG. 4 shows the X-ray diffraction control patterns of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5;
FIG. 5 shows X-ray spectra of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, wherein a is a sample of NP3 prepared in example 1, b is a sample of NP5 prepared in example 4, and c is a sample of NP7 prepared in example 5;
FIG. 6 is a cyclic voltammogram of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, wherein a is a sample of NP3 prepared in example 1, b is a sample of NP5 prepared in example 4, and c is a sample of NP7 prepared in example 5;
FIG. 7 is a graph showing the charge and discharge curves of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, wherein a is a sample of NP3 prepared in example 1, b is a sample of NP5 prepared in example 4, and c is a sample of NP7 prepared in example 5;
FIG. 8 is a graph showing capacitance curves at different current densities for NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5;
FIG. 9 is a graph showing impedance comparison of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5;
FIG. 10 is a graph showing the stability of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5.
Detailed Description
The following description of the preferred embodiments of the present invention will be made in conjunction with the accompanying drawings of FIGS. 1-10. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a ferroferric oxide @ iron disulfide nanocomposite material comprises the following steps:
(1) preparation of ferric oxide: sequentially dissolving ferrous sulfate heptahydrate and thiourea in 50mL of absolute ethanol under stirring, wherein the mass ratio of the ferrous sulfate heptahydrate to the thiourea is 1:1.5, stirring for 40min, refluxing for 40min at 80 ℃, naturally cooling to room temperature, centrifuging for three times by using ethanol, and drying for 11h at 70 ℃ in vacuum to obtain ferrous sulfate monohydrate;
vacuumizing the tubular furnace, then filling argon, repeatedly exhausting air for 3 times to ensure that the inside of the tubular furnace is in a vacuum state, putting ferrous sulfate monohydrate into the vacuum tubular furnace, raising the temperature from room temperature to 700 ℃ at the heating rate of 5 ℃/min under the protection of 30sccm argon, annealing for 2h, and cooling to obtain a ferric oxide sample;
(2) preparing ferroferric oxide: placing the ferric oxide sample prepared in the step (1) in a vacuum tube furnace for annealing, raising the temperature from normal temperature to 500 ℃ at the heating rate of 2 ℃/min in the argon atmosphere, preserving the heat for 5 hours after the highest temperature is reached, then cooling to room temperature, washing the sample by deionized water and ethanol in turn, and drying for 11 hours in a vacuum drying oven at 70 ℃;
(3) preparing ferroferric oxide @ iron disulfide nano composite particles: and (3) placing the ferroferric oxide sample prepared in the step (2) in a vacuum tubular furnace, placing sulfur powder at an air source port of the vacuum tubular furnace, wherein the mass ratio of the sulfur powder to the ferroferric oxide is 3:1, carrying out high-temperature gas-phase vulcanization reaction under the argon atmosphere of 30sccm, raising the temperature from normal temperature to 400 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 4 hours after the temperature reaches the highest temperature, then cooling to room temperature, washing the sample with deionized water and ethanol in sequence, and drying in a vacuum drying oven at 70 ℃ for 11 hours to obtain the ferroferric oxide @ iron disulfide nano composite particles (NP 3).
Example 2
A preparation method of a ferroferric oxide @ iron disulfide nanocomposite material comprises the following steps:
(1) preparation of ferric oxide: sequentially dissolving ferrous sulfate heptahydrate and thiourea in 55mL of absolute ethanol under stirring, wherein the mass ratio of the ferrous sulfate heptahydrate to the thiourea is 1:2, stirring for 30min, refluxing for 40min at 85 ℃, naturally cooling to room temperature, centrifuging for three times by using ethanol, and vacuum drying for 12h at 60 ℃ to obtain ferrous sulfate monohydrate;
vacuumizing the tubular furnace, then filling argon, repeatedly exhausting air for 3 times to ensure that the inside of the tubular furnace is in a vacuum state, putting ferrous sulfate monohydrate into the vacuum tubular furnace, raising the temperature from room temperature to 650 ℃ at the heating rate of 5 ℃/min under the protection of 30sccm argon, annealing for 2h, and cooling to obtain a ferric oxide sample;
(2) preparing ferroferric oxide: placing the ferric oxide sample prepared in the step (1) in a vacuum tube furnace for annealing, raising the temperature from normal temperature to 450 ℃ at the heating rate of 2 ℃/min in the argon atmosphere, preserving the heat for 5 hours after the highest temperature is reached, then cooling to room temperature, washing the sample by deionized water and ethanol in turn, and drying in a vacuum drying oven at 60 ℃ for 12 hours;
(3) preparing ferroferric oxide @ iron disulfide nano composite particles: and (3) placing the ferroferric oxide sample prepared in the step (2) in a vacuum tubular furnace, placing sulfur powder at an air source port of the vacuum tubular furnace, wherein the mass ratio of the sulfur powder to the ferroferric oxide is 3:1, carrying out high-temperature gas-phase vulcanization reaction in an argon atmosphere of 30sccm, raising the temperature from the normal temperature to 350 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 4 hours after the temperature reaches the highest temperature, then cooling to the room temperature, washing the sample with deionized water and ethanol in sequence, and drying in a vacuum drying oven at 60 ℃ for 12 to obtain the ferroferric oxide @ iron disulfide nano composite particles.
Example 3
A preparation method of a ferroferric oxide @ iron disulfide nanocomposite material comprises the following steps:
(1) preparation of ferric oxide: sequentially dissolving ferrous sulfate heptahydrate and thiourea in 50mL of absolute ethanol under stirring, wherein the mass ratio of the ferrous sulfate heptahydrate to the thiourea is 1:2.5, stirring for 50min, refluxing for 40min at 90 ℃, naturally cooling to room temperature, centrifuging for three times by using ethanol, and vacuum drying for 10h at 80 ℃ to obtain ferrous sulfate monohydrate;
vacuumizing the tubular furnace, then filling argon, repeatedly exhausting air for 3 times to ensure that the inside of the tubular furnace is in a vacuum state, putting ferrous sulfate monohydrate into the vacuum tubular furnace, raising the temperature from room temperature to 750 ℃ at the heating rate of 5 ℃/min under the protection of 30sccm argon, annealing for 2h, and cooling to obtain a ferric oxide sample;
(2) preparing ferroferric oxide: placing the ferric oxide sample prepared in the step (1) in a vacuum tube furnace for annealing, raising the temperature from normal temperature to 550 ℃ at the heating rate of 2 ℃/min in the argon atmosphere, preserving the heat for 5 hours after the highest temperature is reached, then cooling to room temperature, washing the sample by deionized water and ethanol in turn, and drying in a vacuum drying oven at 80 ℃ for 10 hours;
(3) preparing ferroferric oxide @ iron disulfide nano composite particles: and (3) placing the ferroferric oxide sample prepared in the step (2) in a vacuum tubular furnace, placing sulfur powder at an air source port of the vacuum tubular furnace, wherein the mass ratio of the sulfur powder to the ferroferric oxide is 3:1, carrying out high-temperature gas-phase vulcanization reaction under the argon atmosphere of 30sccm, raising the temperature from normal temperature to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 4 hours after the temperature reaches the highest temperature, then cooling to room temperature, washing the sample with deionized water and ethanol in sequence, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the ferroferric oxide @ iron disulfide nano composite particles.
Example 4
A preparation method of a ferroferric oxide @ iron disulfide nanocomposite material comprises the following steps:
the method is the same as the step (1) and the step (2) of the example 1, and only differs from the step (3) that the mass ratio of the sulfur powder to the ferroferric oxide is 5: 1, preparing ferroferric oxide @ iron disulfide nano composite particles (NP 5).
Example 5
A preparation method of a ferroferric oxide @ iron disulfide nanocomposite material comprises the following steps:
the method is the same as the step (1) and the step (2) of the example 1, and only differs from the method in that the mass ratio of the sulfur powder to the ferroferric oxide in the step (3) is 7:1, preparing ferroferric oxide @ iron disulfide nano composite particles (NP 7).
The ferroferric oxide @ iron disulfide nanocomposite prepared in the embodiments 1 to 5 of the invention has excellent capacitance characteristics, and the morphology, the X-ray diffraction, the cycle performance, the charge and discharge performance, the capacitance performance and the impedance performance are researched by taking the embodiment 1 and the embodiment 4 grade embodiment 5 as an example, and the specific research method and the research result are as follows:
(1) the research method comprises the following steps:
testing an instrument: CHI660E electrochemical workstation, CT3001A blue battery tester;
preparing an electrode: mixing the prepared ferroferric oxide @ iron disulfide nano composite material, acetylene black and polytetrafluoroethylene PTEF according to the mass ratio of 8:1:1, then coating the mixed material on foamed nickel, drying in vacuum at 110 ℃ for 8-12h, and tabletting under the pressure of 5MPa to obtain a working electrode;
the test method comprises the following steps: an Ag/AgCl electrode is used as a reference electrode, a graphite rod is used as a counter electrode, an electrolyte is a KOH solution of 1mol/L, a three-electrode system is formed by the working electrode, the reference electrode and the counter electrode, nitrogen is introduced into the electrolyte for 20min before a three-electrode device is built, oxygen in the electrolyte is removed, a cyclic voltammetry curve (sweep speed is 10-200 mV/s, voltage range is-1.15-0.1V), a charge-discharge curve (current density is 3.0-15.0A/g, voltage range is-1.15-0.1V) and an impedance curve (frequency is 0.01 Hz-100 kHz, amplitude is 5.0mV) of a material are tested by an electrochemical workstation, and the stability of the material is tested by a blue cell tester.
The research results are as follows:
as shown in fig. 1 to 3, which are scanning electron microscope photographs of the ferroferric oxide @ iron disulfide nanocomposite prepared in examples 1, 4 and 5 of the present invention, respectively, fig. 1 is a scanning electron microscope photograph of the ferroferric oxide @ iron disulfide nanocomposite prepared in example 1 of the present invention, fig. 2 is a scanning electron microscope photograph of the ferroferric oxide @ iron disulfide nanocomposite prepared in example 4 of the present invention, and fig. 3 is a scanning electron microscope photograph of the ferroferric oxide @ iron disulfide nanocomposite prepared in example 5 of the present invention; as can be seen from fig. 1 to 3, the ferroferric oxide @ iron disulfide nanocomposite is spherical particles, and the graph a, the graph b and the graph c in fig. 1 to 3 are respectively compared, so that the following can be seen visually: with the increase of the content of the iron disulfide in the composite material, the particle size of the particles gradually increases, the average particle size is increased from 30-200nm of the embodiment 1 to 100-300nm of the embodiment 5, and the surface becomes rough gradually, which indicates that the ferroferric oxide @ iron disulfide nano composite material prepared by the invention is obtained.
As shown in fig. 4, the X-ray diffraction patterns of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5 of the present invention are shown in XRD diffractogram: the ferroferric oxide @ iron disulfide nano composite materials of NP3, NP5 and NP7 samples are successfully prepared by the preparation method, and the amount of iron disulfide in the composite materials can be increased by increasing the content of sulfur powder in the vulcanization process.
Referring to FIG. 5, which shows X-ray energy spectra of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, wherein a is NP3 sample prepared in example 1, b is NP5 sample prepared in example 4, and c is NP7 sample prepared in example 5, in which a shows that the content of oxygen is 41.8% and the content of sulfur is 16.1%, in b shows that the content of oxygen is 33.1% and the content of sulfur is 31.3%, in c shows that the content of oxygen is 23.2% and the content of sulfur is 39.0%, as the mass ratio of sulfur powder to ferroferric oxide increases, the content of oxygen in the product decreases from 41.8% to 23.2%, and the content of sulfur increases from 16.1% to 39.0%, again, it is demonstrated that the amount of iron disulfide in the composite material gradually increases with the increase in the amount of sulfur.
FIG. 6 shows cyclic voltammograms of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, wherein a shows a sample NP3 prepared in example 1, b shows a sample NP5 prepared in example 4, and c shows a sample NP7 prepared in example 5, and each of CV diagrams of NP3, NP5, and NP7 shows a pair of redox peaks, and it is understood that the nanocomposite shows pseudocapacitance characteristics when it is used as an electrode material for a supercapacitor.
The charge-discharge curves of the NP3 prepared in example 1, the NP5 prepared in example 4 and the NP7 prepared in example 5 are shown in the graph, wherein the graph a is the NP3 sample prepared in example 1, the graph b is the NP5 sample prepared in example 4, the graph c is the NP7 sample prepared in example 5, and a discharge platform appears on the discharge curve in the GCD graph of the nano composite material, so that the pseudo capacitance mechanism of the material is further verified.
FIG. 8 is a capacitance diagram of the NP3 prepared in example 1, the NP5 prepared in example 4, and the NP7 prepared in example 5 at different current densities, wherein the capacitance diagram of the materials at different current densities shows that: when the current density of the three samples is 3A/g, the capacitance of the three samples reaches 450F/g or above, which shows that the three nano-composite materials prepared by the invention have excellent electrochemical performance, and the capacitance of the NP5 sample is obviously higher than that of NP3 and NP7 samples, which shows that the electrochemical performance of the nano-composite materials obtained when the amount of ferroferric oxide and sulfur powder is 1:5 in the vulcanization process is the best.
FIG. 9 is an impedance diagram of NP3 prepared in example 1 of the present invention, NP5 prepared in example 4, and NP7 prepared in example 5, from which: the proton transfer resistance of NP3 was 0.95 Ω, that of NP5 was 0.12 Ω, and that of NP7 was 0.85 Ω, indicating that all three samples had good conductivity.
Fig. 10 is a stability graph of NP3 prepared in example 1, NP5 prepared in example 4, and NP7 prepared in example 5, in which the capacitance performance decreases first when the number of cycles increases to 10000 with increasing the number of cycles, and remains stable after 500 cycles, and the capacitance is still stable even under the conditions of current density of 5A/g and number of charge and discharge of 10000 cycles, so that the stability curve of the nanocomposite electrode material shows that all three samples have excellent stability performance, and in comparison, the stability of the NP5 sample is superior to that of the other two samples, further demonstrating that the NP5 sample has more excellent electrochemical performance.
The invention is also compared with the performances of the electrode material for the super capacitor, which are reported in the prior art, and the electrode material and the performances of the capacitor, which are reported in the prior art, are shown in the table 1:
TABLE 1 capacitor electrode materials and their Properties that have been reported in the prior art
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Compared with the iron-based nano electrode material reported in the prior art, the nano composite material prepared by the invention can still have very high capacitance capacity under higher current density when being used as a super capacitor electrode material, so that the nano composite material prepared by the invention is simple in preparation process and the capacitance capacity reaches 597.1F g-1The iron-based nano electrode material is the highest iron-based nano electrode material reported in the prior art, and the ferroferric oxide @ iron disulfide nano composite particles prepared by the method are super capacitor electrode materials with huge potential when the current density is 5A/g and the charging and discharging times are 10000 cycles.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A preparation method of ferroferric oxide @ iron disulfide nanocomposite is characterized by comprising the following steps:
(1) preparation of ferric oxide: preparing ferrous sulfate monohydrate, placing the prepared ferrous sulfate monohydrate in a vacuum tubular furnace, raising the temperature from room temperature to 650-750 ℃ at the temperature raising rate of 5 ℃/min under the argon atmosphere of 30sccm, annealing for 2-4h, and cooling to room temperature to obtain ferric oxide;
(2) preparing ferroferric oxide: annealing the ferric oxide prepared in the step (1) under a vacuum condition to prepare ferroferric oxide;
(3) preparing ferroferric oxide @ iron disulfide nano composite particles: placing the ferroferric oxide prepared in the step (2) in a vacuum tubular furnace, placing sulfur powder in an air source port of the vacuum tubular furnace, raising the temperature from normal temperature to 350-plus-one 450 ℃ at a heating rate of 2 ℃/min under the argon atmosphere of 30sccm, preserving the heat for 4 hours after the highest temperature is reached, cooling to room temperature, washing with deionized water and ethanol in sequence, and drying to prepare the ferroferric oxide @ iron disulfide nano composite particles;
wherein the mass ratio of the sulfur powder to the ferroferric oxide is 3-7: 1.
2. The preparation method of ferroferric oxide @ iron disulfide nanocomposite material according to claim 1, wherein the preparation method of ferrous sulfate monohydrate in the step (1) comprises the following steps: dissolving ferrous sulfate heptahydrate and thiourea in absolute ethanol, mixing uniformly, stirring for 30-50min, refluxing at 80-90 deg.C for 40min, naturally cooling to room temperature, centrifuging, purifying, and vacuum drying;
wherein the mass ratio of the ferrous sulfate heptahydrate to the thiourea is 1: 1.5-2.5.
3. The preparation method of ferroferric oxide @ iron disulfide nanocomposite material according to claim 1, wherein the annealing conditions in the step (2) are as follows: in an argon atmosphere, raising the temperature from normal temperature to 450-550 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 5h after reaching the highest temperature, then cooling to the room temperature, washing with deionized water and ethanol in sequence, and then drying in vacuum for 10-12 h.
4. The preparation method of ferroferric oxide @ iron disulfide nanocomposite material according to claim 1, wherein the method of the vacuum tube furnace in the steps (1) and (3) comprises the following steps: the tube furnace is firstly vacuumized, and then argon is repeatedly filled for many times until the air in the tube furnace is exhausted.
5. The ferroferric oxide @ iron disulfide nanocomposite prepared by the preparation method of the ferroferric oxide @ iron disulfide nanocomposite according to claim 1.
6. The application of the ferroferric oxide @ iron disulfide nanocomposite material as defined in claim 5 in a supercapacitor as an electrode material.
7. The application of the ferroferric oxide @ iron disulfide nanocomposite material as an electrode material in a supercapacitor is characterized in that the supercapacitor is used in a device for providing power.
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| CN112582616A (en) * | 2020-12-11 | 2021-03-30 | 电子科技大学 | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof |
| CN113930866A (en) * | 2021-10-13 | 2022-01-14 | 广州航海学院 | Supercapacitor electrode material with capsule structure and preparation method and application thereof |
| CN114870870A (en) * | 2022-04-29 | 2022-08-09 | 成都理工大学 | Magnetic environment purifying material for co-processing MO and Cr (VI) pollution and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112582616A (en) * | 2020-12-11 | 2021-03-30 | 电子科技大学 | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof |
| CN113930866A (en) * | 2021-10-13 | 2022-01-14 | 广州航海学院 | Supercapacitor electrode material with capsule structure and preparation method and application thereof |
| CN114870870A (en) * | 2022-04-29 | 2022-08-09 | 成都理工大学 | Magnetic environment purifying material for co-processing MO and Cr (VI) pollution and preparation method thereof |
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