CN115512977B - FeP hollow nanorod for super capacitor and preparation method thereof - Google Patents
FeP hollow nanorod for super capacitor and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
A FeP hollow nano rod material for a super capacitor is prepared by stacking FeP nano particles to form a hollow nano rod by MoO 3 And (3) taking the nanofiber as a template, depositing FeOOH nano particles on the surface of the nanofiber, and phosphating after the template is eliminated. The FeP material prepared by the invention has unique hollow rod-shaped morphology and developed hierarchical void structure, and has large specific surface area, so that the FeP material is favorable for the diffusion and transmission of electrolyte ions in the charge and discharge process, further the charge storage capacity is enhanced, and the specific capacitance can reach 245.2F/g. The FeP hollow nanorod material prepared by the method is extremely excellent in multiplying power performance and cycle stability in the charge and discharge process, and has 86.2% capacitance after continuous charge and discharge for 10000 times at a higher current density (5A/g), and is also superior to many reported iron-based supercapacitor electrode materials.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a FeP hollow nanorod for a super capacitor and a preparation method thereof.
Background
The super capacitor has a simple structure, a fast charge and discharge speed, a long service life, a large working temperature range and good stability, so that the super capacitor has a wider prospect in the energy storage field. There are several factors affecting the energy storage properties of the supercapacitor, such as electrode materials, separators, electrolytes, current collectors, etc., but among them the most significant ones are electrode active materials. Currently, commercial supercapacitors on the market mostly adopt porous carbon based on an electric double layer energy storage mechanism as an active material, and have stable charge and discharge properties, but lower specific capacity and relatively limited charge storage capacity. In order to overcome this disadvantage, electrode active materials based on pseudocapacitive energy storage mechanisms, such as various oxides, sulfides, phosphides, and the like, have been greatly developed in recent years.
As a typical representation of phosphide, iron phosphide has many advantages such as high theoretical specific capacity, flat charge-discharge curve, low cost and abundant reserves when used as electrode material. However, when iron phosphide is used as an electrode material of a supercapacitor, the problems of other metal oxides and sulfides are also faced: poor conductivity, serious capacity attenuation in the circulation process, poor multiplying power performance and large volume expansion in the charge and discharge processes. Due to the technical problems, the electrochemical performance of the iron phosphide is poor, the cycling stability is not satisfactory, and therefore, the large-scale commercial application is difficult to realize.
In the prior art, the composite material is often compounded with other materials such as carbon, so that the negative effect caused by the problems is reduced to a certain extent, but the effect is not obvious, and the problems are rarely solved from the optimization class of the FeP material to improve the performance of the FeP material. The conventional preparation process of iron phosphide is carried out by using iron oxide and phosphine (pH 3 ) Or phosphine generated by thermal decomposition of phosphate is synthesized by reaction under the high temperature condition. However, the prepared iron phosphide has large particle size and poor uniformity, the phase and morphology of the product are difficult to regulate and control in the preparation process, the pore structure is not developed enough, the specific surface area is small, and the diffusion and transmission of electrolyte ions in the charge and discharge process are not facilitated, so that the charge storage capacity of the iron phosphide is poor. Therefore, optimization is needed from the process, and the morphology, the size and the structural pore of FeP are regulated and controlled, so that the electrochemical energy storage performance of the FeP is improved.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a FeP hollow nanorod material for a supercapacitor.
The invention aims to provide a preparation method of the FeP hollow nanorod material. The electrochemical performance of the FeP material with a specific structure is improved by preparing the FeP material.
The invention aims at realizing the following technical scheme:
a FeP hollow nano rod material for a super capacitor is characterized in that: the FeP nano rod is a hollow structure nano rod formed by stacking FeP nano particles, and MoO is adopted 3 And (3) taking the nanofiber as a template, depositing FeOOH nano particles on the surface of the nanofiber, and phosphating after the template is eliminated.
Further, the saidThe FeP hollow nano rod material is prepared by firstly synthesizing MoO 3 Dispersing the nanofiber in deionized water, and adding Na 2 SO 4 And FeCl 3 ∙6H 2 O, heating, and removing MoO with ammonia water 3 Template, finally adopt NaH 2 PO 2 And (5) phosphating to obtain the product.
Further, the MoO 3 The mass volume ratio of the nanofiber to the deionized water is 1.2mg:1mL.
Further, the volume ratio of the deionized water to the mixed aqueous solution is 5:1.
Further, in the above mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
Further, the phosphating treatment is carried out by subjecting NaH 2 PO 2 And FeOOH nanorods at N 2 And (3) preserving the temperature for 1.5-2h at 350-360 ℃ under the atmosphere.
Further, the NaH 2 PO 2 And FeOOH nano rod with mass ratio of 2-40:1.
further, the above synthetic MoO 3 The nanofiber is prepared by mixing (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 A nanofiber.
Further, the above (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
Further, the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
The preparation method of the FeP hollow nanorod material is characterized by comprising the following steps of: first synthesizing MoO 3 Dispersing the nanofiber in deionized water, and adding Na 2 SO 4 And FeCl 3 ∙6H 2 O, heating, and removing MoO 3 And (5) template and finally performing phosphating treatment.
In MoO 3 In the process of preparing FeP for template deposition, the prepared FeP precursor substance is found to not form uniform deposition, in the process, few nano particles are generated, the deposition is non-uniform, and MoO cannot be completely coated 3 After the template is etched, the nano material on the surface of the template is severely cracked, a complete hollow structure cannot be formed, and in addition, obvious aggregation and agglomeration occur during precursor substance deposition. Fe appears in the finished product prepared by phosphating the precursor substance 2 O 3 、Fe 2 P, and other impurities. The above problems greatly affect the final electrochemical energy storage properties of the product.
In the present invention by reacting FeCl 3 Na is added into the aqueous solution 2 SO 4 Under the action of it, feCl 3 Hydrolysis to form a large amount of FOOH nanoparticles having uniform morphology and particle size, and in addition, it was found in research that in MoO 3 In the system as the template, na 2 SO 4 Plays a role in promoting the FOOH nano particles to be on MoO 3 Surface deposition, thereby enhancing FOOH on MoO 3 After the template is removed, the hollow nano rod structure can still be maintained, nano rods formed by nano particle deposition form a graded gap structure among particles, and the specific surface area of the material is increased, so that the diffusion and transmission of electrolyte ions in the charge and discharge process are promoted, the charge storage capacity of the electrolyte ions is enhanced, in addition, the nano particles form the hollow nano rod with the graded gap structure, a porous conductive grid is formed, the conductivity of the electrode material is improved, and the volume expansion effect in the charge and discharge process is relieved.
Further, the MoO 3 The mass volume ratio of the nanofiber to the deionized water is 1.2mg:1mL.
Further, the volume ratio of the deionized water to the mixed aqueous solution is 5:1.
Further, in the above mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
Further, the phosphating treatment is carried out by subjecting NaH 2 PO 2 And FeOOH nanorods at N 2 And (3) preserving the temperature for 1.5-2h at 350-360 ℃ under the atmosphere.
Further, the NaH 2 PO 2 And FeOOH nano rod with mass ratio of 2-40:1.
further, the above synthetic MoO 3 The nanofiber is prepared by mixing (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 A nanofiber.
Further, the above (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
Further, the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
The preparation method of the FeP hollow nanorod for the supercapacitor is characterized by comprising the following steps of:
step (one) MoO preparation 3 Nanofiber
Will (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO with the mass concentration of 68% is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) MoO preparation 3 FeOOH composite nanofiber
120mg of MoO 3 The nanofibers were added to 100mL deionized water and dispersed ultrasonically, followed by the addition of 20mL of pre-dissolved 112mg Na 2 SO 4 And 54-648mg FeCl 3 ∙6H 2 O aqueous solution, heating the reaction solution to 90-100 under stirring o C, keeping for 2h to enable FeOOH nano particles to be uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nanofiber 3 FeOOH composite nanofiber;
step (III) preparing FeOOH hollow nano rod
MoO 3 filtering/FeOOH composite nanofiber, repeatedly washing with water, ultrasonic dispersing in 50mL of water, dropwise adding 5mL of ammonia water with mass fraction of 10% under rapid stirring, and reacting overnight to fully dissolve MoO 3 The inner core is used for obtaining the FeOOH hollow nano rod;
step (III) phosphating
Spreading the dried FeOOH hollow nano rod on one end of a porcelain boat, and then spreading NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat into an atmosphere tube furnace to enable NaH 2 PO 2 The powder is at the windward end and then at N 2 In atmosphere of 350-360 o C is kept for 2h, naH 2 PO 2 The mass ratio of the powder to the FeOOH hollow nano rod is 2-40:1.
The invention has the following technical effects:
the FeP material prepared by the invention can be used as an active ingredient of a supercapacitor electrode, has unique hollow rod-shaped morphology and developed hierarchical void structure, and has large specific surface area, so that the FeP material is favorable for the diffusion and transmission of electrolyte ions in the charge-discharge process, further enhances the charge storage capacity, has specific capacitance as high as 245.2F/g, and is far superior to the specific capacitance of many other iron-based materials and commercial porous carbon materials. The FeP hollow nanorod material prepared by the method is extremely excellent in multiplying power performance and cycle stability in the charge and discharge process, and has 86.2% capacitance after continuous charge and discharge for 10000 times at a higher current density (5A/g), and is also superior to many reported iron-based supercapacitor electrode materials.
Drawings
Fig. 1: moO (MoO) 3 Scanning electron microscope pictures of the high and low power of the nanofiber.
Fig. 2: moO (MoO) 3 Scanning electron microscope pictures of FeOOH composite nano-fiber under high and low power.
Fig. 3: scanning electron microscope pictures of FeOOH hollow nanorods under high and low power.
Fig. 4: is a scanning electron microscope image of FeP hollow nanorods under high and low power.
Fig. 5: and (3) a transmission electron microscope image of the FeP hollow nanorods under high and low power.
Fig. 6: XRD spectra of FeOOH hollow nanorods and FeP hollow nanorods.
Fig. 7: nitrogen adsorption-desorption curves for FeP hollow nanorods.
Fig. 8: pore size distribution of FeP hollow nanorods.
Fig. 9: cyclic voltammograms of FeP hollow nanorod electrodes at different sweep rates.
Fig. 10: charge-discharge curves of FeP hollow nanorod electrodes at different current densities.
Fig. 11: and a capacitance holding condition diagram of the FeP hollow nano rod electrode in 10000 continuous charge and discharge processes.
Fig. 12: and a last 10 charge-discharge curves in 10000 continuous charge-discharge processes of the FeP hollow nanorod electrode.
Fig. 13: electrochemical impedance spectra before and after 10000 times of continuous charge and discharge of the FeP hollow nanorod electrode.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the FeP hollow nanorod for the super capacitor comprises the following steps:
step (one) MoO preparation 3 Nanofiber
Will (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO with the mass concentration of 68% is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL：60mL；
Step (II) MoO preparation 3 FeOOH composite nanofiber
120mg of MoO 3 The nanofibers were added to 100mL deionized water and dispersed ultrasonically, followed by the addition of 20mL of pre-dissolved 112mg Na 2 SO 4 And 216mg FeCl 3 ∙6H 2 O aqueous solution, heating the reaction solution to 90 ℃ under stirring o C, keeping for 2h to enable FeOOH nano particles to be uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nanofiber 3 FeOOH composite nanofiber;
step (III) preparing FeOOH hollow nano rod
MoO prepared in the step (II) is carried out 3 filtering/FeOOH composite nanofiber, repeatedly washing with water, ultrasonic dispersing in 50mL of water, dropwise adding 5mL of ammonia water with mass fraction of 10% under rapid stirring, and reacting overnight to fully dissolve MoO 3 The inner core is used for obtaining the FeOOH hollow nano rod;
step (III) phosphating
Spreading 50mg of dried FeOOH hollow nano rod on one end of a porcelain boat, and then spreading 500mg of NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat into an atmosphere tube furnace to enable NaH 2 PO 2 The powder is at the windward end and then at N 2 In atmosphere at 350 o C is held for 2h.
MoO synthesized by the hydrothermal process 3 The nanofiber is white, and the scanning electron microscope image of the nanofiber is shown in fig. 1, so that the surface is easily found to be smooth. In MoO 3 Nano fiber is used as a substrate, feCl is caused to react through liquid phase 3 At Na (Na) 2 SO 4 The FeOOH nano particles generated by hydrolysis under the action are successfully and uniformly deposited on the surface of the substrate to obtain the yellow-brown MoO 3 FeOOH composite nanofibers. FIG. 2 is MoO 3 The scanning electron microscope image of the FeOOH composite nanofiber is obvious in that the surface of the composite nanofiber is rough, and the composite nanofiber is formed by stacking a plurality of FeOOH nano particles, and a good pore structure is formed. MoO is carried out by using dilute ammonia water 3 After template etching, a yellowish-brown FeOOH hollow nanorod (FIG. 3) is obtained, but the length thereof is obviousLess than MoO 3 FeOOH composite nanofibers. By NaH 2 PO 2 And (3) taking the FeOOH hollow nano rod as a phosphorus source, and synthesizing the FeOOH hollow nano rod in the invention after phosphating in an atmosphere tube furnace. Compared with FeOOH, the morphology of FeP is not changed significantly (FIGS. 3 and 4), but the color is grey-black, and the transmission electron microscopy image shows a well-defined hollow rod-like structure (FIG. 5). FIG. 6 is XRD spectra of FeOOH hollow nanorods and FeP hollow nanorods prepared in this example, and it can be seen from the figure that XRD of the FeP hollow nanorods shows 8 characteristic peaks, and 2 theta angles are located at 30.8 degrees, 32.7 degrees, 35.6 degrees, 37.1 degrees, 46.9 degrees, 48.2 degrees, 55.8 degrees and 59.4 degrees, corresponding to (020), (011), (200), (111), (220), (211), (031) and (002) crystal planes of FeP, respectively; it is worth mentioning that the XRD pattern does not show other peaks, again indicating a complete removal of the template and the formation of a purer final product FeP. FIG. 7 is N of FeP hollow nanorods 2 The adsorption-desorption curve shows a distinct hysteresis in the range of 0.7-1.0 relative pressure, indicating the porous nature, and further confirming the mesoporous nature and pore size distribution range in fig. 8. Furthermore, it has a specific surface area of up to 280 m by correlation calculation 2 The large specific surface area, the hollow structure and the porous characteristic of the FeP hollow nano rod are beneficial to the transmission and diffusion of electrolyte ions in the charge and discharge process, and meanwhile, active sites can be increased, so that the charge storage capacity is improved.
Example 2
The FeP hollow nanorods of example 1 were prepared as active materials into supercapacitor electrodes and used for electrochemical testing:
40mg of the FeP hollow nanorod in example 1, 5mg of acetylene black and 5mg of polyvinylidene fluoride were weighed separately, transferred to a mortar, added with a small amount of methylpyrrolidone, sufficiently ground into a paste, uniformly coated on the surface of a nickel foam having a size of 1cm by 3cm by a small brush, and coated on only one side, and then pressed into a sheet on a sheet press, and then dried in a vacuum drying oven to obtain an electrode. The foam nickel electrode is used as a working electrode, the Hg/HgO electrode is used as a reference electrode, the platinum sheet is used as a counter electrode, 2M KOH is used as electrolyte, and a typical three-electrode device is built for testing the electrochemical energy storage behavior.
FIG. 9 is a cyclic voltammogram of a FeP hollow nanorod electrode at a series of scan rates, wherein the potential test window of each curve is-0.8V-0V, and each curve has a wide redox peak, which indicates the energy storage characteristic of the pseudocapacitance. FIG. 10 is a charge-discharge curve at a range of current densities (0.2-5A/g), calculated to have a maximum specific capacitance at 0.2A/g up to 245.2F/g, far exceeding the specific capacitance of many other iron-based materials (e.g., various iron oxides, iron sulfides, etc.) and commercial porous carbon materials. The electrode multiplying power property of the FeP hollow nano rod in the embodiment is quite excellent, for example, after the current density is increased by 25 times, namely, the current density is increased from 0.2A/g to 5A/g, the specific capacitance value still has 145.1F/g, which is equivalent to 59.2% of the maximum value. It is noted that the electrode can still maintain 86.7% of capacitance after being continuously charged and discharged 10000 times under the high current density of 5A/g (figure 11), the last 10 charge and discharge curves in the test process keep good shape (figure 12), and the electrochemical impedance spectrogram before and after repeated charge and discharge is only slightly changed (figure 13), which reflects the outstanding cycling stability and long service life, and the remarkable electrochemical behaviors are also superior to those of many reported iron-based supercapacitor electrode materials, and the excellent energy storage advantage and bright application prospect are shown.
Example 3
The preparation method of the FeP hollow nanorod for the super capacitor comprises the following steps:
step (one) MoO preparation 3 Nanofiber
Will (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO with the mass concentration of 68% is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 O, deionized water and concentrated sulfuric acidThe mass volume ratio is 1.8g:300mL:60mL;
step (II) MoO preparation 3 FeOOH composite nanofiber
120mg of MoO 3 The nanofibers were added to 100mL deionized water and dispersed ultrasonically, followed by the addition of 20mL of pre-dissolved 112mg Na 2 SO 4 And 54mg FeCl 3 ∙6H 2 O aqueous solution, the reaction solution was heated to 100℃under stirring o C, keeping for 2h to enable FeOOH nano particles to be uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nanofiber 3 FeOOH composite nanofiber;
step (III) preparing FeOOH hollow nano rod
MoO prepared in the step (II) is carried out 3 filtering/FeOOH composite nanofiber, repeatedly washing with water, ultrasonic dispersing in 50mL of water, dropwise adding 5mL of ammonia water with mass fraction of 10% under rapid stirring, and reacting overnight to fully dissolve MoO 3 The inner core is used for obtaining the FeOOH hollow nano rod;
step (III) phosphating
Spreading 50mg of dried FeOOH hollow nano rod on one end of a porcelain boat, and then spreading 100mg of NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat into an atmosphere tube furnace to enable NaH 2 PO 2 The powder is at the windward end and then at N 2 In atmosphere at 355 o C is held for 2h.
The FeP hollow nanorod prepared by the embodiment has a rough surface, is formed by stacking a plurality of nano particles, forms a good pore structure, and has a specific surface area reaching 277 and 277 m 2 /g。
Performance was tested as in example 2, with maximum specific capacitance up to 241.7F/g at a current density of 0.2A/g; after 10000 times of continuous charge and discharge under the high current density of 5A/g, the capacitor can also keep 83.9 percent of capacitance.
Example 4
The preparation method of the FeP hollow nanorod for the super capacitor comprises the following steps:
step (one) MoO preparation 3 Nanofiber
Will (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO with the mass concentration of 68% is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) MoO preparation 3 FeOOH composite nanofiber
120mg of MoO 3 The nanofibers were added to 100mL deionized water and dispersed ultrasonically, followed by the addition of 20mL of pre-dissolved 112mg Na 2 SO 4 And 648mg FeCl 3 ∙6H 2 O aqueous solution, heating the reaction solution to 90-100 under stirring o C, keeping for 2h to enable FeOOH nano particles to be uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nanofiber 3 FeOOH composite nanofiber;
step (III) preparing FeOOH hollow nano rod
MoO prepared in the step (II) is carried out 3 filtering/FeOOH composite nanofiber, repeatedly washing with water, ultrasonic dispersing in 50mL of water, dropwise adding 5mL of ammonia water with mass fraction of 10% under rapid stirring, and reacting overnight to fully dissolve MoO 3 The inner core is used for obtaining the FeOOH hollow nano rod;
step (III) phosphating
Spreading 50mg of dried FeOOH hollow nano rod on one end of a porcelain boat, and then spreading 2000mg of NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat into an atmosphere tube furnace to enable NaH 2 PO 2 The powder is at the windward end and then at N 2 In atmosphere at 360 o C is held for 2h.
The FeP hollow nanorod prepared by the embodiment has a rough surface, is formed by stacking a plurality of nano particles, forms a good pore structure, and has a specific surface area of 281 and 281 m 2 /g。
Performance was tested as in example 2, with maximum specific capacitance up to 244.3F/g at a current density of 0.2A/g; after 10000 times of continuous charge and discharge under the high current density of 5A/g, the capacitor can also keep 85.2 percent of capacitance.
In a number of experiments, we tried to replace Na with a salt such as NaCl 2 SO 4 It was found to be for FeCl 3 Hydrolysis to form FOOH nanoparticles does not have any promoting effect, and the hydrolysate (precursor) is mainly Fe (OH) with irregular morphology (nano-sheets, nano-particles with different sizes, etc.) 3 And Fe (Fe) 2 O 3 And at MoO 3 The template surface is not used for promoting deposition, sediment agglomeration still exists, and the precursor cannot completely coat MoO 3 The template is removed, so that the structure of the template is collapsed, and the hollow nano tube structure cannot be maintained.
Claims (14)
1. A FeP hollow nano rod material for a super capacitor is characterized in that: the FeP nano rod is a hollow structure nano rod formed by stacking FeP nano particles, and MoO is adopted 3 And (3) taking the nanofiber as a template, depositing FeOOH nano particles on the surface of the nanofiber, and phosphating after the template is eliminated.
2. A method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 1, which is characterized in that: first synthesizing MoO 3 Dispersing the nanofiber in deionized water, and adding Na 2 SO 4 And FeCl 3 ∙6H 2 O, heating, and removing MoO 3 And (5) template and finally performing phosphating treatment.
3. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 2, which is characterized by comprising the following steps: the MoO 3 The mass volume ratio of the nanofiber to the deionized water is 1.2mg:1mL.
4. A method for preparing a FeP hollow nanorod material for a supercapacitor according to claim 2 or 3, wherein the method comprises the following steps: the volume ratio of the deionized water to the mixed aqueous solution is 5:1.
5. A method for preparing a FeP hollow nanorod material for a supercapacitor according to claim 2 or 3, wherein the method comprises the following steps: in the mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
6. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 4, which is characterized by comprising the following steps: in the mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
7. A method for preparing a FeP hollow nanorod material for a supercapacitor according to claim 2 or 3, wherein the method comprises the following steps: the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
8. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 4, which is characterized by comprising the following steps: the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
9. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 5, wherein the method comprises the following steps: the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
10. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 6, wherein the method comprises the following steps: the temperature of the heating treatment is 90-100 ℃ and the treatment time is 2 hours.
11. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 10, which is characterized by comprising the following steps: the phosphating treatment is to make NaH 2 PO 2 And FeOOH nanorods at N 2 And (3) preserving the temperature for 1.5-2h at 350-360 ℃ under the atmosphere.
12. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 11, wherein the method comprises the following steps: the synthesis of MoO 3 The nanofiber is prepared by mixing (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 A nanofiber.
13. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 12, wherein the method comprises the following steps: said (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
14. The preparation method of the FeP hollow nanorod for the super capacitor is characterized by comprising the following steps of:
step (one) MoO preparation 3 Nanofiber
Will (NH) 4 ) 2 MoO 4 ∙4H 2 O is dissolved in deionized water, and concentrated HNO with the mass concentration of 68% is added 3 Stirring uniformly and then at 180 o C, carrying out hydrothermal reaction for 8 hours, and obtaining MoO after filtering, washing and drying the product 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) MoO preparation 3 FeOOH composite nanofiber
120mg of MoO 3 The nanofibers were added to 100mL deionized water and dispersed ultrasonically, followed by the addition of 20mL of pre-dissolved 112mg Na 2 SO 4 And 54-648mg FeCl 3 ∙6H 2 O aqueous solution, heating the reaction solution to 90-100 under stirring o C, keeping for 2h to enable FeOOH nano particles to be uniformly deposited to MoO 3 The surface of the nano fiber is provided with a plurality of nano fibers,synthesizing MoO 3 FeOOH composite nanofiber;
step (III) preparing FeOOH hollow nano rod
MoO 3 filtering/FeOOH composite nanofiber, repeatedly washing with water, ultrasonic dispersing in 50mL of water, dropwise adding 5mL of ammonia water with mass fraction of 10% under rapid stirring, and reacting overnight to fully dissolve MoO 3 The inner core is used for obtaining the FeOOH hollow nano rod;
step (III) phosphating
Spreading FeOOH hollow nano rod on one end of porcelain boat, and then spreading NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat into an atmosphere tube furnace to enable NaH 2 PO 2 The powder is at the windward end and then at N 2 In atmosphere of 350-360 o C is held for 2h.
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