CN114804045A - Preparation method and application of iron-nickel phosphide nanosheet forming capacitor material - Google Patents
Preparation method and application of iron-nickel phosphide nanosheet forming capacitor material Download PDFInfo
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002135 nanosheet Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- YTQVNYGLBGECJA-UHFFFAOYSA-L [Fe].[Ni](O)O Chemical compound [Fe].[Ni](O)O YTQVNYGLBGECJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 3
- 238000000840 electrochemical analysis Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 230000001413 cellular effect Effects 0.000 description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000004692 metal hydroxides Chemical class 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
-
- 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
- H01G11/84—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention belongs to the field of super capacitors, and particularly relates to a preparation method and application of iron-nickel phosphide nanosheets forming capacitor materials. The technical scheme is as follows: the preparation method comprises the steps of adopting a conductive support material as an electrode current collector and a support, adopting a solvothermal method to grow an iron-nickel bimetal hydroxide nanosheet precursor on the surface in situ, and then carrying out heat treatment and phosphorization to form the honeycomb-shaped iron-nickel phosphide nanosheet array structure supercapacitor electrode material. The method is simple to operate, low in cost, environment-friendly and green, and the size and the shape of the material are easy to regulate and control. The iron-nickel phosphide nanosheet is an excellent supercapacitor electrode material, and has high specific capacity and excellent long-term cycling capability.
Description
Technical Field
The invention belongs to the field of super capacitors, and particularly relates to a preparation method and application of iron-nickel phosphide nanosheets forming capacitor materials.
Background
Compared with the traditional storage battery of the electric energy storage system, the super capacitor as a green energy storage element has the advantages of high power density, high charging point speed, long cycle life and the like, and has wide development prospect in the field of energy storage. The super capacitor can be divided into a double electric layer super capacitor and a pseudo capacitor super capacitor according to the energy storage characteristics of the super capacitor. The surface of the transition metal phosphide has rich active sites and can undergo a rapid and reversible redox reaction, so that the transition metal phosphide has a strong pseudocapacitance characteristic. Therefore, the theoretical specific capacitance of the transition metal phosphide is far higher than that of the double-layer capacitor of the carbon material (about 10-100 times), and the transition metal phosphide becomes a promising super capacitor electrode material. However, studies on iron-based phosphides have shown that they exhibit high specific capacity, but poor rate capability and cycling performance due to volume deformation during testing. In contrast, nickel phosphide has good rate properties and excellent stability, but has a limited specific capacitance value compared to other transition metal oxides. Compared with single-metal transition phosphide, the double-metal transition phosphide relates to coexistence of multiple oxidation states of different metal ions, can remarkably increase the number of redox sites, greatly improves the conductivity and stability, and has wide application prospect. Different from the traditional powder material, the nano array electrode material does not need to be added with an insulating adhesive. In addition, the independent nano unit and the independent porous structure have the advantages of enriching active sites, shortening an ion/electron transmission path and relieving volume strain. Therefore, the preparation method of the nano-array material which is simple to operate, environment-friendly and green and controllable in shape is significant.
In summary, there is an urgent need to develop a novel bimetallic phosphide nano-array material as an electrode material of a high-performance pseudocapacitance supercapacitor, which has solved the defects of the existing materials and technologies.
Disclosure of Invention
Aiming at the defects of the performance of the prior transition metal phosphide as the electrode material of the super capacitor and the optimization of the preparation method, the invention provides a preparation method of a cellular iron nickel phosphide nano array material and the application of the cellular iron nickel phosphide nano array material as the electrode material of the super capacitor.
In order to achieve the purpose, the preparation method of the iron-nickel phosphide nanosheet forming the capacitor material comprises the following steps:
(1) growing ferrite bimetal hydroxide nanosheets in situ on the substrate through a hydrothermal reaction;
(2) and (3) placing a base with the iron-nickel bimetal hydroxide nanosheets at the downstream of a tubular furnace, placing a phosphorus source at the upstream of the tubular furnace, and preparing the iron-nickel phosphide nanosheets by a chemical vapor deposition method.
The preparation method of the iron-nickel phosphide nanosheet forming the capacitor material comprises the steps of (1) taking foamed nickel as a substrate, ultrasonically cleaning the foamed nickel in dilute hydrochloric acid, ultrasonically cleaning the foamed nickel in ethanol, ultrasonically cleaning the foamed nickel in deionized water and drying the ultrasonically cleaned foamed nickel at the temperature of 60-90 ℃ for 12 hours before hydrothermal reaction; the concentration of the dilute hydrochloric acid is 2mol L -1 The size of the foamed nickel is 3.8 multiplied by 5.2cm 2 。
According to the preparation method of the iron-nickel phosphide nanosheet forming the capacitor material, the molar ratio of the iron source to the sodium salt in the hydrothermal solution is 1: 1.
the preparation method of the iron-nickel phosphide nanosheet forming the capacitor material comprises the steps of (1) immersing a substrate material into a hydrothermal solution containing an iron source and a sodium salt, carrying out hydrothermal reaction at 120 ℃, and washing and drying to obtain iron-nickel hydroxide nanosheets growing on the substrate; the iron source is ferric chloride, the sodium salt is sodium chloride, and the hydrothermal reaction time is 10 hours.
The preparation method of the iron-nickel phosphide nanosheet forming the capacitor material comprises the step (2) of respectively placing the substrate growing the iron-nickel hydroxide nanosheet and the phosphorus source into a pair of quartz boats, placing the quartz boat placing the substrate growing the iron-nickel hydroxide nanosheet at the downstream of the tubular furnace, placing the quartz boat placing the phosphorus source at the upstream of the tubular furnace, and under the nitrogen atmosphere, at the room temperature for 1-3 ℃ for min -1 And raising the temperature to 300-350 ℃ at the speed, and carrying out the phosphorization reaction for 100-120 minutes to obtain the in-situ growth iron-nickel phosphide nanosheet loaded on the foamed nickel substrate.
According to the preparation method of the iron-nickel phosphide nanosheet forming the capacitor material, in the step (2), the phosphorus source in the phosphating process is sodium hypophosphite, and the addition amount of the phosphorus source is 0.06g cm of the surface area of the foamed nickel -2 。
The iron nickel phosphide nanosheet forming the capacitor material is applied, and the honeycomb-shaped iron nickel phosphide is used as a super capacitor electrode material.
The iron-nickel phosphide nanosheet forming the capacitor material is applied to a three-electrode electrochemical system, and electrochemical testing is carried out by taking the electrode material of the supercapacitor with the honeycomb iron-nickel phosphide nanosheet array structure as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as a counter electrode.
The invention has the advantages and positive effects that:
since phosphorus has a lower electronegativity and the bond ionicity decreases, iron and nickel create a series of different redox pairs (Fe) 2+ /Fe 3+ ，Ni 1+ /Ni 2+ ) And compared with metal carbide and metal nitride, the electrochemical performance is better.
Unlike the traditional bimetallic coprecipitation method, the substrate nickel foam is used as a current collector and a nickel source in hydrothermal reaction. The hydrothermal product firmly grows on the three-dimensional current collector foamed nickel to form an in-situ grown nanometer honeycomb iron nickel phosphide nanosheet array, a binder is not required, and the active substance is not easy to fall off after continuous testing work. The unique interconnected nanoplate arrays can provide a plurality of large contact areas and efficient electron paths for charge storage.
Drawings
FIG. 1 is an XRD pattern of iron nickel phosphide provided by an embodiment of the present invention;
FIG. 2 is an SEM image of an iron-nickel double hydroxide provided by an embodiment of the invention;
FIG. 3 is an SEM image of iron nickel phosphide provided by an embodiment of the invention;
FIG. 4 is a TEM image of iron nickel phosphide provided by an embodiment of the present invention;
FIG. 5 is a selected area diffraction pattern of iron nickel phosphide provided by an embodiment of the invention;
FIG. 6 is a schematic view of cyclic voltammetry curves of the iron-nickel double metal hydroxide and iron-nickel phosphide provided in the embodiment of the present invention;
FIG. 7 is a graph showing the comparison of the rate capability of the iron-nickel double metal hydroxide and the iron-nickel phosphide provided by the embodiment of the invention;
FIG. 8 is a schematic view of cyclic voltammetry curves of nickel iron phosphide provided by the embodiments of the present invention;
FIG. 9 is a schematic view of a charge-discharge curve of iron nickel phosphide provided in an embodiment of the present invention;
fig. 10 is a graph of the cycle performance of nickel iron phosphide provided by the embodiment of the invention, wherein the left and right insets in fig. 10 are respectively: the first ten cycles of charge-discharge cycle curve and the last ten cycles of charge-discharge cycle curve.
Detailed Description
In the specific implementation process, the preparation method of the iron-nickel phosphide nanosheet forming the capacitor material comprises the following steps: (1) cutting to obtain 3.8 × 5.2cm 2 The foamed nickel is ultrasonically cleaned by dilute hydrochloric acid, alcohol and deionized water respectively; (2) dissolving ferric salt and sodium salt in deionized water according to a certain molar ratio to prepare a reaction precursor solution; (3) and carrying out hydrothermal reaction on the precursor solution and the substrate at a certain temperature and time. The ferric salt is ferric chloride, and the sodium salt is sodium chloride; (4) carrying out chemical vapor deposition reaction of the iron-nickel double metal hydroxide and the phosphorus source at a certain temperature and time. The phosphorus source is sodium hypophosphite. The method is simple and easy to control, low in cost, green and environment-friendly, and is easy to regulate and control the appearance of the prepared sample. Meanwhile, the obtained cellular iron nickel phosphide has high specific capacity and long-acting cycle performance as the electrode material of the super low-voltage capacitor.
The invention will be further described with reference to specific embodiments.
Example 1:
in this embodiment, the preparation method of the iron-nickel phosphide nanosheet constituting the capacitor material is as follows:
clipping 3.8 × 5.2cm in step (1) 2 The foamed nickel is ultrasonically cleaned by dilute hydrochloric acid, alcohol and deionized water for 15 minutes.
Step (2) adding ferric chloride and sodium chloride in a ratio of 1: 1 molar ratio into 60mL deionized water, and magnetically stirring for 30 minutes to dissolve.
And (3) transferring the nickel foam cleaned in the step (1) and the mixed solution prepared in the step (2) to a 100mL hydrothermal reaction kettle, and reacting at 120 ℃ for 10 hours.
And (4) after the reaction is finished, cooling to room temperature, taking out the foamed nickel loaded with the iron-nickel double metal hydroxide, and washing with deionized water in a shaking way. Drying at 80 deg.C for 10 h.
And (5) placing the dried foamed nickel loaded with the iron-nickel double-metal hydroxide in a quartz boat and placing the quartz boat at the downstream of the tube furnace. 1.2g of sodium hypophosphite was weighed into a quartz boat and placed upstream of the tube furnace. Under argon atmosphere at 2 deg.C for min -1 The temperature rising rate is increased from room temperature to 300 ℃, and the temperature is kept for 2 h. And after the reaction is finished and the temperature is cooled to room temperature, obtaining the product, namely the honeycomb iron nickel phosphide nanosheet array material.
As shown in an X-ray diffraction (abbreviated as XRD) pattern of fig. 1, XRD is a means of obtaining information such as a composition of a material, a structure or a form of an atom or a molecule in the material by analyzing a diffraction pattern of the material by X-ray diffraction. XRD test of the cellular iron nickel phosphide obtained in the above example revealed that it was iron phosphide Fe 2 P and nickel phosphide Ni 2 P in the polycrystalline structure. As shown in the Scanning Electron Microscope (SEM) images of fig. 2 and 3, fig. 2 shows the SEM image of the iron-nickel double hydroxide, and fig. 3 shows the SEM image of the iron-nickel phosphide, the morphology of the honeycomb-shaped iron-nickel phosphide obtained in the above examples is more distinct than that of the obtained iron-nickel double hydroxide in the form of regular hexagon. It can be seen that the appearance is more regular after the phosphating reaction. And the honeycomb porous structure with high specific surface area not only provides more reaction area with the electrolyte, but also provides fast channels for the transmission of ions/electrons. The cellular iron nickel phosphide obtained in the above example was scraped off from the base nickel foam and subjected to ultrasonic dispersion treatment, and observed under a Transmission Electron Microscope (TEM) (as shown in fig. 4). The honeycomb iron-nickel phosphide array structure material obtained in the embodiment is composed of iron-nickel phosphide nanosheets, and the length of each single piece is about 120-200 nm. An electron diffraction pattern, as shown in fig. 5, showing a typical diffraction ring, demonstrates that the cellular iron-nickel phosphide obtained in the above example is a polycrystalline structure, corresponding to the XRD result.
Example 2:
in this embodiment, the iron-nickel phosphide nanosheets constituting the capacitor material are applied as follows:
in the step (1), the molar concentration is selected to be 3mol L -1 And testing the cyclic voltammetry curve of the electrode material of the iron-nickel double metal hydroxide supercapacitor by taking the potassium hydroxide aqueous solution as electrolyte, a platinum electrode as a counter electrode and Ag/AgCl as a reference electrode.
In the step (2), the molar concentration is selected to be 3mol L -1 The potassium hydroxide aqueous solution is used as electrolyte, the platinum electrode is used as a counter electrode, the Ag/AgCl is used as a reference electrode, and the cyclic voltammetry curve, the charging and discharging curve and the cyclic performance of the iron-nickel phosphide nanosheet forming the capacitor material are tested.
In the step (3), the voltage range of the cyclic voltammetry curve test in the steps (1) and (2) is 0-0.45V, and the scanning speed range is 1-100 mVs -1 (ii) a The voltage range of the charge and discharge test in the step (2) is 0-0.4V, and the current density is 6-48 mAcm -2 (ii) a The cycle performance test in the step (2) is to use a current density of 21mAcm -2 10000 times of charging and discharging tests.
As shown in FIG. 6, the prepared Fe-Ni bimetal hydroxide electrode and the prepared Fe-Ni phosphide electrode have a concentration of 20mV s -1 A comparison of cyclic voltammograms at the sweep rate of (c). Calculating a formula according to the specific capacity C: c a (— j | (v) dV)/2 vAV. It is known that ^ I (V) dV, the integral area of the cyclic voltammogram, is proportional to the specific capacity C. The closed area of the cyclic voltammetry curve of the prepared iron-nickel phosphide electrode is much larger than that of an iron-nickel bimetal phosphide electrode. Thus, it can be concluded that phosphating can improve the specific capacity of iron-nickel based electrodes. More intuitive data is presented in fig. 7, where the specific capacity of the prepared iron-nickel phosphide electrode was greater than that of the iron-nickel double metal hydroxide at any sweep rate.
As shown in FIG. 8, two redox peaks are clearly observed on the cyclic voltammetry curves of the prepared honeycomb iron nickel phosphide electrode material at different sweep rates. This may be Ni during testing + /Ni 2+ And Fe 2+ /Fe 3+ With OH in the electrolyte - The abundant and reversible oxidation-reduction reaction is carried out. Is rich inThe redox active sites bring high specific capacity to the honeycomb iron nickel phosphide electrode material. As shown in fig. 10, the prepared honeycomb iron nickel phosphide electrode material has an obvious platform in the charge-discharge curve under different current densities, which indicates that the redox behavior is consistent with the CV curve result. At 6mAcm -2 Has a current density of 9.4Fcm -2 High specific capacity of (2). As shown in FIG. 9, the prepared cellular iron nickel phosphide electrode material has a capacity retention rate of 70.4% after 10000 times of charge-discharge tests, and has excellent long-term cycle performance. The inset is a first/last ten-turn charge-discharge cycle test curve, and it can be seen that the curve before and after the cycle has no large deformation. The following table 1 shows the comparison result of the electrochemical performance of the electrode material of the supercapacitor with the honeycomb iron nickel phosphide nanosheet array structure of the invention and the currently published electrode material of the transition metal phosphide.
TABLE 1
The electrochemical performance of the prepared honeycomb iron nickel phosphide electrode material is compared with the currently published transition metal phosphide electrode material as given in table 1. It can be concluded that the prepared honeycomb iron nickel phosphide electrode material has higher specific capacity (3925F g) -1 ) And long-lasting cycling performance (70.4%, 10000 cycles).
While the preferred embodiment of the present invention has been illustrated and described, it will be appreciated by those skilled in the art that it is not intended to limit the invention to the details shown, but rather, the invention is to be accorded the widest scope possible and many equivalents are possible without departing from the spirit and scope of the appended claims. All falling within the scope of protection of the present invention.
Claims (8)
1. A preparation method of iron nickel phosphide nanosheets forming a capacitor material is characterized in that a layer of iron nickel phosphide nanosheets which are arranged in order is uniformly covered on the surface of a porous foamed nickel conductive support material, and specifically comprises the following steps:
growing ferrite bimetal hydroxide nanosheets in situ on the substrate through a hydrothermal reaction; wherein the substrate is foamed nickel;
and (3) placing a base with the iron-nickel bimetal hydroxide nanosheets at the downstream of a tubular furnace, placing a phosphorus source at the upstream of the tubular furnace, and preparing the iron-nickel phosphide nanosheets by a chemical vapor deposition method.
2. The method for preparing iron-nickel phosphide nanosheets constituting a capacitor material as claimed in claim 1, wherein the base is subjected to ultrasonic cleaning in dilute hydrochloric acid, ultrasonic cleaning in ethanol, ultrasonic cleaning in deionized water and then drying at 60-90 ℃ for 12 hours before the hydrothermal reaction; the concentration of the dilute hydrochloric acid is 2mol L -1 The size of the foamed nickel is 3.8 multiplied by 5.2cm 2 。
3. The method for producing iron-nickel phosphide nanosheets constituting a capacitor material as set forth in claim 2, wherein the molar ratio of the iron source to the sodium salt in the mixed solution is 1: 1.
4. the method for preparing iron-nickel phosphide nanosheets constituting a capacitor material as claimed in claim 3, wherein the base material is immersed in a mixed solution containing an iron source and a sodium salt, subjected to hydrothermal reaction at 120 ℃, washed and dried to obtain iron-nickel hydroxide nanosheets growing on the base;
wherein the iron source is ferric chloride, the sodium salt is sodium chloride, and the hydrothermal reaction time is about 10 hours.
5. The method for preparing iron nickel phosphide nanosheets constituting a capacitor material as set forth in claim 1, wherein the base having iron nickel bimetal hydroxide nanosheets is placed downstream of a tube furnace, a phosphorus source is placed upstream of the tube furnace, and the iron nickel phosphide nanosheets are prepared by a chemical vapor deposition method, specifically comprising:
respectively placing the substrate with the iron-nickel hydroxide nanosheets and the phosphorus source into a pair of quartz boats, placing the quartz boat with the substrate with the iron-nickel hydroxide nanosheets at the downstream of the tube furnace, placing the quartz boat with the phosphorus source at the upstream of the tube furnace, and performing nitrogen atmosphere treatment at room temperature for 1-3 ℃ for min -1 And raising the temperature to 300-350 ℃ at the speed, and carrying out the phosphorization reaction for 100-120 minutes to obtain the in-situ growth iron-nickel phosphide nanosheet loaded on the foamed nickel substrate.
6. The method for preparing iron-nickel phosphide nanosheets constituting a capacitor material as claimed in claim 5, wherein the phosphorus source in the phosphating process is sodium hypophosphite, and the added mass of the phosphorus source is 1.0-1.2 g.
7. An application method of iron nickel phosphide nanosheets forming capacitor materials is characterized in that corresponding batteries are manufactured by using the honeycomb-shaped iron nickel phosphide prepared by the preparation method of any one of claims 1-6 as a supercapacitor electrode material.
8. Use according to claim 7, characterized in that in a three-electrode electrochemical system, electrochemical tests are carried out with the electrode material according to claim 7 as the working electrode, with an Ag/AgCl electrode as the reference electrode and with a platinum electrode as the counter electrode.
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