CN115512977A - FeP hollow nanorod for supercapacitor and preparation method thereof - Google Patents
FeP hollow nanorod for supercapacitor and preparation method thereof Download PDFInfo
- Publication number
- CN115512977A CN115512977A CN202211257234.5A CN202211257234A CN115512977A CN 115512977 A CN115512977 A CN 115512977A CN 202211257234 A CN202211257234 A CN 202211257234A CN 115512977 A CN115512977 A CN 115512977A
- Authority
- CN
- China
- Prior art keywords
- moo
- fep
- nano
- feooh
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The FeP nanorod material for the super capacitor is a nanorod with a hollow structure formed by stacking FeP nanoparticles and is formed by MoO 3 The nanofiber is used as a template, feOOH nano particles are deposited on the surface of the nanofiber, and the nanofiber is obtained by phosphorization after the template is eliminated. The FeP material prepared by the invention has a unique hollow rod-shaped appearance, a developed hierarchical void structure and a large specific surface area, so that the diffusion and the transmission of electrolyte ions in the charge and discharge process are facilitated, the charge storage capacity is further enhanced, and the specific capacitance can reach 245.2F/g. The FeP hollow nanorod material prepared by the invention is extremely excellent in rate expression and cycle stability in the charging and discharging processes, and can be continuously charged and discharged at a high current density (5A/g)86.2 percent of capacitance is still maintained after 10000 times of electricity, and the capacitance 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 supercapacitor and a preparation method thereof.
Background
The super capacitor has a wider prospect in the field of energy storage due to simple structure, faster charge and discharge speed, long service life, large working temperature range and good stability. There are many factors affecting the energy storage properties of the super capacitor, such as electrode materials, separators, electrolytes, current collectors, etc., but among them, the most significant is affecting the current electrode active material. At present, a commercial supercapacitor on the market mostly adopts porous carbon based on an electric double layer energy storage mechanism as an active material, and although the charge-discharge property of the commercial supercapacitor is stable, the specific capacity of the commercial supercapacitor is low, and the charge storage capacity of the commercial supercapacitor is relatively limited. To overcome this disadvantage, electrode active materials based on a pseudocapacitive energy storage mechanism, such as various oxides, sulfides, phosphides, etc., have been vigorously developed in recent years.
As a typical representative 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 an electrode material. However, when the iron phosphide is used as the electrode material of the super capacitor, the iron phosphide also faces the problems of other metal oxides and sulfides: the conductivity is poor, the capacity attenuation is severe in the circulating process, the multiplying power performance is poor, and large volume expansion is generated in the charging and discharging process. Due to the technical problems, the electrochemical performance of the iron phosphide is poor, the cycling stability is not satisfactory, and large-scale commercial application is difficult to realize.
In the prior art, the FeP material is often compounded with other materials such as carbon to reduce the negative effects caused by the problems to a certain extent, but the effect is not obvious, and the FeP material is rarely optimized to solve the problems so as to improve the performance of the FeP material. The conventional process for preparing iron phosphide is by using iron oxide and Phosphine (PH) 3 ) Or phosphine generated by thermal decomposition of phosphate is synthesized by reaction under the condition of high temperature. But the prepared iron phosphide has large particle size and poor uniformity, the phase and the morphology of the product are difficult to regulate in the preparation process, the pore structure is not developed enough, the specific surface area is small, and the diffusion and the transmission of electrolyte ions in the charge and discharge processes are not facilitated, so that the charge storage capacity of the iron phosphide is poor. Therefore, the morphology of FeP needs to be regulated and controlled through technological optimizationSize and structural porosity, thereby improving the electrochemical energy storage performance.
Disclosure of Invention
In view of 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 FeP material with a specific structure is prepared, so that the electrochemical performance of the FeP material is improved.
The purpose of the invention is realized by the following technical scheme:
a FeP hollow nanorod material for a supercapacitor is characterized in that: the FeP nanorod is a nanorod with a hollow structure formed by stacking FeP nanoparticles and is MoO 3 The nanofiber is used as a template, feOOH nano particles are deposited on the surface of the nanofiber, and the nanofiber is obtained by phosphorization after the template is eliminated.
Further, the FeP hollow nanorod material is prepared by firstly synthesizing MoO 3 Dispersing the nano-fiber in deionized water, and adding Na 2 SO 4 And FeCl 3 ∙6H 2 Heating the mixed aqueous solution of O, and removing MoO with ammonia water 3 Template, finally using NaH 2 PO 2 And (4) carrying out phosphating treatment.
Further, the above MoO 3 The mass-volume ratio of the nano-fibers to the deionized water is 1.2mg:1mL.
Further, the volume ratio of the deionized water to the mixed aqueous solution was 5.
Further, in the above mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass-to-volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
Further, the phosphating treatment is to add NaH 2 PO 2 And FeOOH nanorods in N 2 Keeping the temperature for 1.5-2h at 350-360 ℃ under the atmosphere.
Further, the NaH is mentioned above 2 PO 2 And the FeOOH nano rod has the mass ratio of 2-40:1.
further, the above synthetic MoO 3 The nanofiber is a fiber of cellulose (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 And (3) nano fibers.
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 2h.
The preparation method of the FeP hollow nanorod material is characterized by comprising the following steps of: synthesis of MoO 3 Dispersing the nano-fiber in deionized water, and adding Na 2 SO 4 And FeCl 3 ∙6H 2 Mixed aqueous solution of O, heat treatment, and MoO removal 3 Template and final phosphorizing treatment.
In the presence of MoO 3 In the process of preparing FeP by template deposition, the prepared FeP precursor substance is not uniformly deposited, and in the process, generated nanoparticles are few, the deposition is not uniform, and MoO cannot be completely coated 3 After the template is etched, the nano material on the surface of the template is seriously cracked, a complete hollow structure cannot be formed, and in addition, the precursor substances are obviously aggregated and clustered during deposition. Fe appears in the finished product prepared by phosphorizing the precursor substance 2 O 3 、Fe 2 P and the like. The above problems greatly affect the final electrochemical energy storage properties of the product.
In the invention, through FeCl 3 Adding Na into the aqueous solution 2 SO 4 Under the action of which FeCl 3 Hydrolysis generates a large amount of FOOH nano-particles with uniform shape and particle size, and in addition, research finds that the FOOH nano-particles are formed by MoO 3 In a templated system, na 2 SO 4 Plays a role in promoting the FOOH nano-particles in the MoO 3 The effect of surface deposition is enhanced, thereby enhancing the effect of FOOH on MoO 3 The hollow nano rod structure can be still maintained after the template is removed, and nano rods formed by the deposition of nano particles are formed among the particlesThe hierarchical void structure is improved, the specific surface area of the material is improved, so that the diffusion and the transmission of electrolyte ions in the charge and discharge process are promoted, the charge storage capacity of the material is enhanced, in addition, the hollow nano-rods formed by the nano-particles have the hierarchical void 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 above MoO 3 The mass volume ratio of the nano-fiber to the deionized water is 1.2mg:1mL.
Further, the volume ratio of the deionized water to the mixed aqueous solution was 5.
Further, in the above mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass-to-volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
Further, the phosphating treatment is to add NaH 2 PO 2 And FeOOH nanorods on N 2 Keeping the temperature for 1.5-2h at 350-360 ℃ in the atmosphere.
Further, the NaH is mentioned above 2 PO 2 The mass ratio of the FeOOH nano rod to the FeOOH nano rod is 2-40:1.
further, the above synthetic MoO 3 The nanofiber is a fiber of cellulose (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 And (3) nano fibers.
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 2h.
Most specifically, the preparation method of the FeP hollow nanorod for the supercapacitor is characterized by comprising the following steps of:
step (one) preparation of MoO 3 Nano-fiber
Will be (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolution of OAdding concentrated HNO with the mass concentration of 68 percent into deionized water 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass-to-volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) preparation of MoO 3 /FeOOH composite nano-fiber
120mg of MoO 3 Adding the nano-fiber into 100mL of deionized water, performing ultrasonic dispersion, and adding 20mL of the deionized water dissolved with 112mg of Na in advance 2 SO 4 And 54-648mg FeCl 3 ∙6H 2 Heating the reaction solution to 90-100 deg.C under stirring o C, keeping for 2 hours to ensure that FeOOH nano particles are uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nano-fiber 3 a/FeOOH composite nanofiber;
step (three) preparing FeOOH hollow nano rod
MoO 3 Performing suction filtration and repeated water washing on the/FeOOH composite nano-fiber, ultrasonically dispersing the composite nano-fiber in 50mL of water, dropwise adding 5mL of ammonia water with the mass fraction of 10% while rapidly stirring, reacting overnight, and fully dissolving MoO in the ammonia water 3 The core is adopted, so that the FeOOH hollow nanorod is obtained;
phosphating treatment in step (III)
Spreading the dried FeOOH hollow nano rod on one end of a porcelain boat, and then adding NaH 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat in an atmosphere tube furnace to make NaH 2 PO 2 The powder is at the upwind end and then at N 2 In 350-360% of atmosphere o C is maintained for 2h and NaH 2 PO 2 The mass ratio of the powder to the FeOOH hollow nano rod is 2-40.
The invention has the following technical effects:
the FeP material prepared by the invention can be used as an active component of a super capacitor electrode, has a unique hollow rod-shaped appearance and a developed hierarchical void structure, and has a large specific surface area, so that the FeP material is beneficial to the diffusion and transmission of electrolyte ions in the charging and discharging processes, and further enhances the charge storage capacity, the specific capacitance of the FeP material can reach 245.2F/g, and is far beyond that of other iron-based materials and commercial porous carbon materials. The FeP hollow nanorod material prepared by the invention is extremely excellent in rate performance and cycle stability in the charging and discharging process, and still maintains 86.2% of capacitance after 10000 times of continuous charging and discharging under a high current density (5A/g), and is also superior to many reported iron-based supercapacitor electrode materials.
Drawings
FIG. 1: moO 3 Scanning electron microscope images of the nanofibers at high and low magnification.
FIG. 2 is a schematic diagram: moO 3 Scanning electron microscope images of the/FeOOH composite nanofiber under high and low power.
FIG. 3: scanning electron microscope images of FeOOH hollow nanorods at high and low times.
FIG. 4: is a scanning electron microscope image under high and low magnification of the FeP hollow nano rod.
FIG. 5 is a schematic view of: and (3) transmission electron microscope images of the FeP hollow nanorod at high and low magnification.
FIG. 6: XRD spectrograms of FeOOH hollow nanorods and FeP hollow nanorods.
FIG. 7: the nitrogen adsorption-desorption curve of the FeP hollow nano-rod.
FIG. 8: the pore diameter distribution of the FeP hollow nano rod.
FIG. 9: cyclic voltammetry curves of the FeP hollow nanorod electrode at different scanning speeds.
FIG. 10: and (3) a charge-discharge curve of the FeP hollow nanorod electrode under different current densities.
FIG. 11: and (3) a capacitance retention condition diagram of the FeP hollow nanorod electrode in 10000 times of continuous charging and discharging processes.
FIG. 12: and (3) a charge-discharge curve diagram of the last 10 times in the 10000-time continuous charge-discharge process of the FeP hollow nanorod electrode.
FIG. 13: and electrochemical impedance spectrograms before and after the FeP hollow nanorod electrode is continuously charged and discharged for 10000 times.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A preparation method of a FeP hollow nanorod for a supercapacitor comprises the following steps:
step (one) preparation of MoO 3 Nano-fiber
Will be (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO with mass concentration of 68% 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 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) preparation of MoO 3 /FeOOH composite nanofiber
120mg of MoO 3 Adding the nano-fiber into 100mL of deionized water, performing ultrasonic dispersion, and adding 20mL of the deionized water dissolved with 112mg of Na in advance 2 SO 4 And 216mg FeCl 3 ∙6H 2 O aqueous solution, heating the reaction solution to 90 ℃ under stirring o C, keeping for 2 hours to ensure that FeOOH nano particles are uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nano-fiber 3 a/FeOOH composite nanofiber;
step (three) preparing FeOOH hollow nano rod
The MoO prepared in the step (two) is added 3 Performing suction filtration and repeated water washing on the/FeOOH composite nanofiber, ultrasonically dispersing the FeOOH composite nanofiber in 50mL of water, dropwise adding 5mL of ammonia water with the mass fraction of 10% under rapid stirring, reacting overnight to fully dissolve MoO in the ammonia water 3 The core is adopted, so that the FeOOH hollow nanorod is obtained;
phosphating treatment of step (III)
50mg of dry FeOOH hollow nano-rod is spread on one end of a porcelain boat, and then 500mg of NaH is put in 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat in an atmosphere tube furnace to make NaH 2 PO 2 The powder is at the upwind end and then at N 2 In an atmosphere of 350 deg.C o C is kept for 2h.
MoO synthesized by the hydrothermal process 3 The nanofibers are white, and fig. 1 is a scanning electron microscope image of the nanofibers, so that the surface of the nanofibers is smooth. With MoO 3 The nano-fiber is used as a substrate to react with FeCl through a liquid phase 3 In Na 2 SO 4 FeOOH nano particles generated by hydrolysis under the action are successfully and uniformly deposited on the surface of the substrate to obtain yellow-brown MoO 3 the/FeOOH composite nanofiber. FIG. 2 shows MoO 3 The scanning electron microscope image of the/FeOOH composite nanofiber shows that the surface of the/FeOOH composite nanofiber is rough, a plurality of FeOOH nano particles are stacked, and a good pore structure is formed. In the presence of dilute ammonia water to remove MoO 3 After the template is etched, a yellow-brown FeOOH hollow nanorod (figure 3) is obtained, but the length of the nanorod is obviously smaller than that of MoO 3 the/FeOOH composite nanofiber. With NaH 2 PO 2 And the FeOOH hollow nanorod is used as a phosphorus source and is synthesized after being phosphorized in an atmosphere tube furnace to obtain the FeP hollow nanorod. Compared to FeOOH, the FeP morphology did not change significantly (fig. 3 and 4), but the color appeared dark gray, while the transmission electron microscopy images well confirmed the more perfect hollow rod-like structure (fig. 5). FIG. 6 is an XRD spectrum of the FeOOH hollow nanorod and the FeP hollow nanorod prepared in this example, from which it can be seen that XRD of the FeP hollow nanorod shows 8 characteristic peaks with 2 θ angles located at 30.8 °, 32.7 °, 35.6 °, 37.1 °, 46.9 °, 48.2 °, 55.8 ° and 59.4 °, corresponding to (020), (011), (200), (111), (220), (211), (031) and (002) crystal planes of FeP, respectively; it is worth mentioning that the XRD spectrum shows no other miscellaneous peaks, again indicating complete removal of the template and formation of a purer final product, feP. FIG. 7 is N of FeP hollow nanorod 2 According to an adsorption-desorption curve, an obvious hysteresis loop appears in the spectrogram when the relative pressure is within the range of 0.7-1.0, which indicates the porous characteristic, and the mesoporous attribute and the pore size distribution range are further confirmed in fig. 8. In addition, the specific surface area is up to 280 m through correlation calculation 2 /g, feP hollow nanorods having such a large specific surface area, hollow structure andthe porous characteristic is beneficial to the transmission and diffusion of electrolyte ions in the charging and discharging processes, and can increase active sites and improve the charge storage capacity.
Example 2
The FeP hollow nanorod in example 1 is used as an active material to prepare a supercapacitor electrode and is used for electrochemical testing:
40mg of the FeP hollow nanorods, 5mg of acetylene black and 5mg of polyvinylidene fluoride in example 1 were weighed, respectively, transferred to a mortar, added with a small amount of methyl pyrrolidone, sufficiently ground into a paste, uniformly coated with a small brush to a nickel foam surface of 1cm × 3cm in size, coated with an area of 1cm × 1cm and coated with only one side, then tabletted on a tabletting machine, and dried in a vacuum drying oven to obtain an electrode. A typical three-electrode device is built by taking the foamed nickel electrode as a working electrode, an Hg/HgO electrode as a reference electrode, a platinum sheet as a counter electrode and 2M KOH as electrolyte, and the electrochemical energy storage behavior is tested.
FIG. 9 is a cyclic voltammogram of a FeP hollow nanorod electrode at a series of scanning speeds, the potential test window of each curve is-0.8V to-0V, and each curve has a wide redox peak, which shows the energy storage characteristic of the pseudocapacitance. FIG. 10 is a charge-discharge curve at a range of current densities (0.2 to 5A/g), and the maximum specific capacitance at 0.2A/g is calculated to be as high as 245.2F/g, which far exceeds the specific capacitance of many other iron-based materials (such as various iron oxides, iron sulfides, etc.) and commercial porous carbon materials. The multiplying power property of the FeP hollow nanorod electrode 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 of the FeP hollow nanorod electrode is still 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 10000 times of continuous charging and discharging under the high current density of 5A/g (figure 11), while the charging and discharging curve of the last 10 times in the test process keeps a good shape (figure 12), and the electrochemical impedance spectrum before and after repeated charging and discharging is only slightly changed (figure 13), reflecting the superior cycle stability and long service life thereof, and the remarkable electrochemical behaviors are also beyond many reported iron-based supercapacitor electrode materials, thereby showing excellent energy storage advantages and bright application prospects.
Example 3
A preparation method of a FeP hollow nanorod for a supercapacitor comprises the following steps:
step (one) preparation of MoO 3 Nano-fiber
Will be (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO with mass concentration of 68% 3 After being stirred uniformly, the mixture is stirred at 180 DEG o Carrying out hydrothermal reaction on the mixture C for 8 hours, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass-to-volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) preparation of MoO 3 /FeOOH composite nano-fiber
120mg of MoO 3 Adding the nano-fiber into 100mL of deionized water, performing ultrasonic dispersion, and adding 20mL of Na dissolved with 112mg in advance 2 SO 4 And 54mg FeCl 3 ∙6H 2 Heating the reaction solution to 100 deg.C under stirring o C, keeping for 2 hours to ensure that FeOOH nano particles are uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nano-fiber 3 a/FeOOH composite nanofiber;
step three, preparing FeOOH hollow nano rod
The MoO prepared in the step (II) is added 3 Performing suction filtration and repeated water washing on the/FeOOH composite nanofiber, ultrasonically dispersing the FeOOH composite nanofiber in 50mL of water, dropwise adding 5mL of ammonia water with the mass fraction of 10% under rapid stirring, reacting overnight to fully dissolve MoO in the ammonia water 3 The core is adopted, so that the FeOOH hollow nanorod is obtained;
phosphating treatment of step (III)
50mg of dry FeOOH hollow nano-rod is spread on one end of a porcelain boat, and then 100mg of NaH is put in 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat in an atmosphere tube furnace to make NaH 2 PO 2 The powder is at the upwind end and then at N 2 Atmosphere(s)Middle school in 355 o C is kept for 2h.
The FeP hollow nanorod prepared in the embodiment has a rough surface, is formed by stacking a plurality of nanoparticles, forms a good pore structure, and has a specific surface area of 277 m 2 /g。
The performance of the capacitor is tested by the method of example 2, and the maximum specific capacitance at the current density of 0.2A/g is up to 241.7F/g; after 10000 times of continuous charging and discharging under the high current density of 5A/g, 83.9 percent of capacitance can be still kept.
Example 4
A preparation method of FeP hollow nanorods for super capacitors comprises the following steps:
step (one) preparation of MoO 3 Nano-fiber
Will be (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO with mass concentration of 68% 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 Nanofibers, (NH) 4 ) 2 MoO 4 ∙4H 2 The mass-to-volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL;
step (II) preparation of MoO 3 /FeOOH composite nano-fiber
120mg of MoO 3 Adding the nano-fiber into 100mL of deionized water, performing ultrasonic dispersion, and adding 20mL of Na dissolved with 112mg in advance 2 SO 4 And 648mg FeCl 3 ∙6H 2 Heating the reaction solution to 90-100 deg.C under stirring o C, keeping for 2 hours to ensure that FeOOH nano particles are uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nano-fiber 3 a/FeOOH composite nanofiber;
step (three) preparing FeOOH hollow nano rod
The MoO prepared in the step (II) is added 3 Performing suction filtration and repeated water washing on the/FeOOH composite nanofiber, ultrasonically dispersing the FeOOH composite nanofiber in 50mL of water, dropwise adding 5mL of ammonia water with the mass fraction of 10% under rapid stirring, reacting overnight to fully dissolve MoO in the ammonia water 3 The core is adopted, so that the FeOOH hollow nanorod is obtained;
phosphating treatment of step (III)
50mg of dry FeOOH hollow nano-rods are spread at one end of a porcelain boat, and 2000mg of NaH is then put in 2 PO 2 Placing the powder at the other end of the magnetic boat, placing the porcelain boat in an atmosphere tube furnace to make NaH 2 PO 2 The powder is at the upwind end and then at N 2 In the atmosphere at 360 o C is kept for 2h.
The FeP hollow nanorod prepared in the embodiment has a rough surface, is formed by stacking a plurality of nanoparticles, forms a good pore structure, and has a specific surface area of 281 m 2 /g。
The performance of the capacitor is tested by the method of example 2, and the maximum specific capacitance at the current density of 0.2A/g is up to 244.3F/g; after 10000 times of continuous charging and discharging under the high current density of 5A/g, 85.2 percent of capacitance can be kept.
In a number of experimental procedures, we have attempted to replace Na with a salt such as NaCl 2 SO 4 It was found for FeCl 3 The FOOH nano-particles generated by hydrolysis have no promoting effect, and the hydrolysis product (precursor) is mainly Fe (OH) with irregular shapes (nano-sheets, nano-particles and the like with different sizes) 3 And Fe 2 O 3 And in MoO 3 The deposition promotion effect is not achieved during the deposition on the surface of the template, the aggregation of the deposits still exists, and the precursor can not completely coat MoO 3 The template causes the structure to collapse after the template is removed, and the structure of the hollow nano tube cannot be maintained.
Claims (10)
1. A FeP hollow nanorod material for a supercapacitor is characterized in that: the FeP nanorod is a hollow nanorod formed by stacking FeP nanoparticles and is MoO 3 The nanofiber is used as a template, feOOH nano particles are deposited on the surface of the nanofiber, and the nanofiber is obtained by phosphorization after the template is eliminated.
2. A method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 1, wherein the method comprises the following steps: synthesis of MoO first 3 Nanofibers dispersed in a solventAdding Na into the seed water 2 SO 4 And FeCl 3 ∙6H 2 Mixed aqueous solution of O, heat treatment, and MoO removal 3 Template and final phosphorization.
3. The preparation method of the FeP hollow nanorod material for the supercapacitor, according to claim 2, is characterized in that: the MoO 3 The mass-volume ratio of the nano-fibers to the deionized water is 1.2mg:1mL.
4. The preparation method of the FeP hollow nanorod material for the supercapacitor, according to claim 2 or 3, is characterized in that: the volume ratio of the deionized water to the mixed aqueous solution is 5.
5. The method for preparing the FeP hollow nanorod material for the supercapacitor according to any one of claims 2 to 4, wherein the FeP hollow nanorod material comprises the following components in percentage by weight: in the mixed aqueous solution, na 2 SO 4 、FeCl 3 ∙6H 2 The mass-to-volume ratio of O to water is 5.6mg:2.7-32.4mg:1mL.
6. The method for preparing an FeP hollow nanorod material for a supercapacitor, as claimed in any one of claims 2 to 5, wherein the FeP hollow nanorod material comprises: the temperature of the heating treatment is 90-100 ℃, and the treatment time is 2h.
7. The preparation method of the FeP hollow nanorod material for the supercapacitor, according to claim 6, is characterized in that: the phosphating treatment is to add NaH 2 PO 2 And FeOOH nanorods on N 2 Keeping the temperature for 1.5-2h at 350-360 ℃ under the atmosphere.
8. The method for preparing the FeP hollow nanorod material for the supercapacitor according to claim 7, wherein the method comprises the following steps: the synthetic MoO 3 The nanofiber is a fiber of (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 3 And (3) nano fibers.
9. The preparation method of the FeP hollow nanorod material for the supercapacitor, according to claim 8, is characterized in that: said (NH) 4 ) 2 MoO 4 ∙4H 2 The mass-to-volume ratio of O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
10. A preparation method of a FeP hollow nanorod for a supercapacitor is characterized by comprising the following steps:
step (one) preparation of MoO 3 Nano-fiber
Will be (NH) 4 ) 2 MoO 4 ∙4H 2 Dissolving O in deionized water, and adding concentrated HNO with mass concentration of 68% 3 Stirring uniformly at 180 DEG o Carrying out hydrothermal reaction for 8h under C, and carrying out suction filtration, washing and drying on the product to obtain MoO 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) preparation of MoO 3 /FeOOH composite nanofiber
120mg of MoO 3 Adding the nano-fiber into 100mL of deionized water, performing ultrasonic dispersion, and adding 20mL of the deionized water dissolved with 112mg of Na in advance 2 SO 4 And 54-648mg FeCl 3 ∙6H 2 Heating the reaction solution to 90-100 deg.C under stirring o C, keeping for 2 hours to ensure that FeOOH nano particles are uniformly deposited to MoO 3 Synthesizing MoO on the surface of the nano-fiber 3 a/FeOOH composite nanofiber;
step (three) preparing FeOOH hollow nano rod
MoO 3 Performing suction filtration and repeated water washing on the/FeOOH composite nano-fiber, ultrasonically dispersing the composite nano-fiber in 50mL of water, dropwise adding 5mL of ammonia water with the mass fraction of 10% while rapidly stirring, reacting overnight, and fully dissolving MoO in the ammonia water 3 The core is adopted, thus obtaining the FeOOH hollow nano rod；
Phosphating treatment of step (III)
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 in an atmosphere tube furnace to make NaH 2 PO 2 The powder is at the upwind end and then at N 2 In 350-360% of atmosphere o C is kept for 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211257234.5A CN115512977B (en) | 2022-10-14 | 2022-10-14 | FeP hollow nanorod for super capacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211257234.5A CN115512977B (en) | 2022-10-14 | 2022-10-14 | FeP hollow nanorod for super capacitor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115512977A true CN115512977A (en) | 2022-12-23 |
| CN115512977B CN115512977B (en) | 2023-06-02 |
Family
ID=84510859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211257234.5A Active CN115512977B (en) | 2022-10-14 | 2022-10-14 | FeP hollow nanorod for super capacitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115512977B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520945A (en) * | 2018-03-13 | 2018-09-11 | 华南理工大学 | Nano-tube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof |
| CN108767260A (en) * | 2018-06-05 | 2018-11-06 | 武汉理工大学 | A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application |
| CN109616329A (en) * | 2018-11-23 | 2019-04-12 | 中国工程物理研究院化工材料研究所 | A kind of flexible fiber shape self-powered supercapacitor and preparation method thereof |
| CN111060575A (en) * | 2019-12-25 | 2020-04-24 | 广州钰芯传感科技有限公司 | Porous Co-P composite electrode for glucose enzyme-free detection and preparation method and application thereof |
| CN111188126A (en) * | 2020-01-08 | 2020-05-22 | 嘉兴学院 | Flexible iron phosphide/carbon nanofiber membrane and preparation method and application thereof |
| CN112838214A (en) * | 2021-01-26 | 2021-05-25 | 重庆十九分科技有限公司 | Mesoporous carbon in-situ modified FeP lithium ion battery cathode material and preparation method thereof |
| CN114203989A (en) * | 2021-11-30 | 2022-03-18 | 五邑大学 | FeP/Fe2P/NC composite material and preparation method thereof |
| CN114583123A (en) * | 2022-02-17 | 2022-06-03 | 宜都兴发化工有限公司 | Phosphorus-doped carbon-coated ultrathin lithium iron phosphate lamellar material and preparation method thereof |
| CN114804045A (en) * | 2022-05-19 | 2022-07-29 | 武汉科技大学 | Preparation method and application of iron-nickel phosphide nanosheet forming capacitor material |
-
2022
- 2022-10-14 CN CN202211257234.5A patent/CN115512977B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520945A (en) * | 2018-03-13 | 2018-09-11 | 华南理工大学 | Nano-tube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof |
| CN108767260A (en) * | 2018-06-05 | 2018-11-06 | 武汉理工大学 | A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application |
| CN109616329A (en) * | 2018-11-23 | 2019-04-12 | 中国工程物理研究院化工材料研究所 | A kind of flexible fiber shape self-powered supercapacitor and preparation method thereof |
| CN111060575A (en) * | 2019-12-25 | 2020-04-24 | 广州钰芯传感科技有限公司 | Porous Co-P composite electrode for glucose enzyme-free detection and preparation method and application thereof |
| CN111188126A (en) * | 2020-01-08 | 2020-05-22 | 嘉兴学院 | Flexible iron phosphide/carbon nanofiber membrane and preparation method and application thereof |
| CN112838214A (en) * | 2021-01-26 | 2021-05-25 | 重庆十九分科技有限公司 | Mesoporous carbon in-situ modified FeP lithium ion battery cathode material and preparation method thereof |
| CN114203989A (en) * | 2021-11-30 | 2022-03-18 | 五邑大学 | FeP/Fe2P/NC composite material and preparation method thereof |
| CN114583123A (en) * | 2022-02-17 | 2022-06-03 | 宜都兴发化工有限公司 | Phosphorus-doped carbon-coated ultrathin lithium iron phosphate lamellar material and preparation method thereof |
| CN114804045A (en) * | 2022-05-19 | 2022-07-29 | 武汉科技大学 | Preparation method and application of iron-nickel phosphide nanosheet forming capacitor material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115512977B (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107359054B (en) | Composite electrode material, preparation method and application thereof | |
| Liu et al. | Hierarchical CuO@ ZnCo–OH core-shell heterostructure on copper foam as three-dimensional binder-free electrodes for high performance asymmetric supercapacitors | |
| Fu et al. | Origami and layered-shaped ZnNiFe-LDH synthesized on Cu (OH) 2 nanorods array to enhance the energy storage capability | |
| Wang et al. | A new nano lead-doped mesoporous carbon composite as negative electrode additives for ultralong-cyclability lead-carbon batteries | |
| CN110061215B (en) | Composite structure for lithium ion battery cathode and preparation method thereof | |
| Song et al. | ZIF-67-derived NiCo 2 O 4@ Co 2 P/Ni 2 P honeycomb nanosheets on carbon cloth for high-performance asymmetric supercapacitors | |
| Chen et al. | Wood-derived scaffolds decorating with nickel cobalt phosphate nanosheets and carbon nanotubes used as monolithic electrodes for assembling high-performance asymmetric supercapacitor | |
| CN111564610B (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
| Evariste et al. | Hierarchical mesoporous Zn–Ni–Co–S microspheres grown on reduced graphene oxide/nickel foam for asymmetric supercapacitors | |
| Yuan et al. | Promising carbon nanosheets decorated by self-assembled MoO2 nanoparticles: Controllable synthesis, boosting performance and application in symmetric coin cell supercapacitors | |
| Li et al. | Construction of a novel three-dimensional porous lead-carbon network for improving the reversibility of deep discharge lead-carbon batteries | |
| Lu et al. | Novel bouquet-like cobalt phosphate as an ultrahigh-rate and durable battery-type cathode material for hybrid supercapacitors | |
| Luo et al. | Graphene-controlled FeSe nanoparticles embedded in carbon nanofibers for high-performance potassium-ion batteries | |
| Zhang et al. | Morphology and electrochemical properties of NiCo2O4 powders prepared by a facile hydrothermal method | |
| CN113594427B (en) | MoS 2 Negative electrode material of-MoP quantum dot @ carbon composite sodium ion battery and preparation method of negative electrode material | |
| Yu et al. | Electrospinning preparation and electrochemical supercapacitor performance of dendrite-like 3D MgCo2O4/C nanofibers | |
| Su et al. | Synthesis of CoNi@ ZIF-LDH with hierarchical porous structure based on structural design and site-directed transformation strategy assisted hybrid supercapacitor with high energy density | |
| Chen et al. | Self-grown nickel hydroxide nanosheets on 3D hierarchical porous turtle shell-derived activated carbon for high-performance supercapacitors | |
| CN111063549B (en) | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor | |
| CN110957145A (en) | Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof | |
| CN115512977B (en) | FeP hollow nanorod for super capacitor and preparation method thereof | |
| Wang et al. | A novel three-dimensional hierarchical porous lead-carbon composite prepared from corn stover for high-performance lead-carbon batteries | |
| Shi et al. | Construction of binder-free 3-D porous NiMn LDH electrode materials for high performance asymmetric supercapacitors using dynamic hydrogen bubbles as template | |
| CN111470494A (en) | Preparation method and application of three-dimensional graphene | |
| CN111341567A (en) | 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |