CN113451593B - Preparation method and application of amorphous nitrogen-doped ferrocobalt phosphate micro-tablet - Google Patents
Preparation method and application of amorphous nitrogen-doped ferrocobalt phosphate micro-tablet Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a preparation method and application of an amorphous nitrogen-doped ferrocobalt phosphate microchip, and belongs to the technical field of new energy materials. Mixing a cobalt source, an iron source, a phosphorus source and water, uniformly mixing and stirring to form an initial mixed solution, then transferring the initial mixed solution into an autoclave for hydrothermal reaction, and treating the obtained material at 200-600 ℃ for 1-4 h to obtain the amorphous nitrogen-doped ferrocobalt phosphate microchip catalytic material. The invention adopts a hydrothermal method, and the preparation method has the advantages of simplicity, environmental protection, easy operation, low cost, no need of special equipment in the whole reaction process and the like, is beneficial to industrial production, and finally obtains a product with high yield, high purity and high quality. The material can realize the double functions of oxygen evolution reaction and oxygen reduction reaction in electrocatalysis, the performance of a zinc-air battery and the like.
Description
Technical Field
The invention relates to preparation of an electrochemical catalyst, in particular to a preparation method and application of an amorphous nitrogen-doped ferrocobalt phosphate microchip, and belongs to the technical field of new energy materials.
Background
With the global energy shortage and the corresponding climate change problem becoming more serious, the search for alternative green energy sources is urgent. Electrochemical Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) are two key half-reactions on the air cathode of rechargeable metal-air batteries and renewable fuel cells. However, both ORR and OER have slower natural kinetics and their counter electrode reactions are also more energy intensive. To date, 4e, which is delayed in response to two reactions, has been accelerated - The most widely known catalysts for the transfer process are noble metal-based metals or metal oxides, e.g. Pt/C for ORR and IrO for OER 2 . However, their high cost and unsustainable supply prevent large-scale practical applications, so an effective electrocatalyst must be needed to reduce overpotential and accelerate the catalytic rate.
Two-dimensional (2D) materials with abundant active sites, fast electron/mass transfer pathways, and unique electronic properties are of great interest for their wide application in energy and environmental fields. In particular, 2D transition metal-based materials are widely used for electrochemical energy conversion and storage reactions. For example, they may be reacted by typical reactions, via O in alkaline electrolytes 2 -H 2 The O reaction, providing a renewable carbon-free energy source and high energy density in water electrolysis and rechargeable metal-air cells, however, hydrogen-based fuel cells and metal-air cells are hampered by inefficient OERs and ORRs because the ORR or O-H bond in OERs has a strong dioxygen bond.
Therefore, it is essential to develop bifunctional transition metal-based catalysts for ORR and OER to meet the demand for these energy conversion systems.
Disclosure of Invention
The invention aims to synthesize an amorphous nitrogen-doped ferrocobalt phosphate microchip catalytic material with high yield, low cost and high activity, thereby solving the problems of high cost, large initial potential, high overpotential, low power density and the like of the existing catalyst. Therefore, the amorphous N-doped mesoporous cobalt iron-based phosphate is successfully obtained through an in-situ nitrogen strategy, the unique structure of the amorphous N-doped mesoporous cobalt iron-based phosphate can be beneficial to mass transfer and ion diffusion, and the electrocatalytic performance of the electrocatalyst is obviously improved through the coordination configuration of the transition metal center by the simple and environment-friendly method.
Specifically, the purpose of the invention is realized by the following technical scheme:
a preparation method of an amorphous nitrogen-doped cobalt iron phosphate microchip catalytic material comprises the steps of mixing a cobalt source, an iron source, a phosphorus source and water, uniformly mixing and stirring to form an initial mixed solution, transferring the initial mixed solution into a high-pressure kettle to perform hydrothermal reaction, and treating the obtained material at 200-600 ℃ for 1-4 hours to obtain the amorphous nitrogen-doped cobalt iron phosphate microchip catalytic material.
Preferably, in the initial mixed solution, the mass ratio of the cobalt source, the iron source, the phosphorus source and the water is 1-4: 0.2-0.8: 2-6: 50.
preferably, the temperature of the hydrothermal reaction is 160-220 ℃, and the reaction time is 8-20 h.
Preferably, the selected cobalt source is optionally at least one of cobalt nitrate, cobalt acetate, cobalt difluoride, cobalt chloride, cobalt bromide.
Preferably, the source of phosphorus is optionally at least one of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, hypophosphorous acid, phosphorous acid, phosphoric acid.
Preferably, the iron source is optionally at least one of ferric nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferric bromide.
Preferably, the autoclave is a stainless steel self-autoclave with a polytetrafluoroethylene lining.
Preferably, after the hydrothermal reaction, natural cooling, washing, solid-liquid separation and drying are further included.
Preferably, the washing is to wash the product with water and ethanol for at least 3 times, and the drying temperature is 50-80 ℃.
Preferably, the atmosphere for high-temperature treatment of the material is one or two of nitrogen and argon.
The second object of the present invention is to provide a catalytic material prepared by the above preparation method.
The third purpose of the invention is to provide the application of the preparation method or the obtained catalytic material in electrocatalytic reaction.
Preferably, the electrocatalytic reaction comprises an electrocatalytic oxygen evolution reaction.
Preferably, the application method of the electrocatalytic oxygen evolution reaction comprises the steps of dripping the material on the surface of the glassy carbon electrode, airing at 25-45 ℃, and then carrying out the oxygen evolution reaction.
It is a fourth object of the present invention to provide an electrode or electrocatalytic device comprising the catalytic material described above.
The invention can produce beneficial effects at least comprising:
(1) the invention provides a method for preparing a cobalt iron phosphate material by a hydrothermal reaction, and the prepared cobalt iron phosphate material has the advantages of moderate specific size, a micro-sheet structure and two-dimensional layering.
(2) The method can obtain the two-dimensional sheet micron-sized structure without adding any surfactant, and has the advantages of simple operation, low cost and mild reaction conditions.
(3) According to the method, simple high-temperature treatment is directly carried out after the hydrothermal reaction of the raw materials, and nitrogen doping can be realized under the condition that a nitrogen source is not additionally introduced so as to improve the catalytic activity.
(4) The amorphous nitrogen-doped ferrocobalt phosphate microchip material provided by the application has excellent catalytic electrochemical oxygen evolution reaction effect and oxygen reduction effect in an alkaline solution of potassium hydroxide, and can effectively improve the efficiency of electrochemical water splitting. In 1M KOH solution, at a sweep rate of 5mV/s, at a current density of 10mA/cm 2 Under the conditions of (1), the OER overpotential is 278mV, the ORR half-wave potential is 0.74V, and the power density of the zinc-air battery is 74.6mW/cm 2 。
(4) Compared with the noble metal catalyst containing ruthenium element, iridium element and platinum element, the invention has the advantages of cheap and easily obtained raw materials, abundant resources and stable catalytic performance, and is suitable for commercial production.
Drawings
FIG. 1 is NH 4 CoPO 4 ·H 2 An X-ray diffraction pattern of O; wherein (a) is NH 4 CoPO 4 ·H 2 Fitting the crystal structure of O obtained by a single crystal X-ray diffractometer to obtain an X-ray diffraction spectrum; (b) is synthesized sample No. 2 NH 4 CoPO 4 ·H 2 And (4) testing the obtained spectrum of the powder material by X-ray diffraction. (c) And (d) are respectively sample No. 1 NH 4 Co 0.8 Fe 0.2 PO 4 ·H 2 A graph obtained by an OX-ray diffraction test and a graph obtained by an X-ray diffraction test after calcination at 350 ℃ for two hours under a nitrogen atmosphere.
FIG. 2 is a thermogravimetric analysis of sample # 1.
FIG. 3 is a scanning electron micrograph of sample No. 1 after calcination at 350 ℃ for two hours under a nitrogen atmosphere.
FIG. 4 shows sample No. 1, sample No. 2, sample No. 1 calcined at 350 deg.C for two hours in a nitrogen atmosphere, and IrO, a commercial catalyst 2 Linear scanning voltammograms obtained in 1M KOH electrolyte.
FIG. 5 is an ORR plot obtained by scanning a linear voltammogram in a 1M KOH electrolyte for samples 1# and 1# calcined at 350 deg.C for two hours under nitrogen.
Fig. 6 is a graph of the power density of the material for sample # 1 and sample # 1 calcined at 350 c for two hours under nitrogen.
Fig. 7 is a graph of the cell specific capacitance of the materials of sample No. 1 and sample No. 1 calcined at 350 c for two hours under a nitrogen atmosphere.
Fig. 8 is a graph of the charge and discharge cycle stability of the materials of sample No. 1 and sample No. 1 calcined at 350 c for two hours under a nitrogen atmosphere.
FIG. 9 is a line scan voltammogram obtained for sample # 1 calcined under nitrogen atmosphere at different temperatures in 1M KOH electrolyte.
Detailed Description
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
As a preferred embodiment for preparing amorphous nitrogen-doped ferrocobalt phosphate micro-tablets, a typical process is as follows: sealing raw materials including an iron source, a cobalt source, a phosphorus source and water in a hydrothermal reaction kettle for hydrothermal reaction at 160-220 ℃ for 8-20 h, naturally cooling to 30 ℃, filtering and cleaning to obtain a pink material, and treating at 200-600 ℃ for 1-4 h to obtain a blue amorphous nitrogen-doped cobalt iron phosphate microchip material.
The test is carried out by adopting a three-electrode system and using a linear sweep voltammetry method, and the electrolyte is 1M KOH. The electrocatalytic oxygen reduction reaction method is provided, the material is coated on a rotating disk electrode, a three-electrode system is adopted to carry out testing by using a linear sweep voltammetry method, and the electrolyte is 1M KOH. The method for providing the zinc-air battery comprises the steps of coating a material on carbon paper to serve as a positive electrode, and coating an electrolyte of 6M KOH +0.2M Zn (CH) 3 COO) 2 。
EXAMPLE 1 sample preparation
Mixing an iron source, a cobalt source, a phosphorus source and water, uniformly stirring to form an initial mixture solution, sealing the initial mixture solution in a 25mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the hydrothermal reaction kettle into a box-type resistance furnace, reacting for a period of time at a reaction temperature, filtering, cleaning and drying to obtain pink NH 4 Co 0.8 Fe 0.2 PO 4 ·H 2 And (3) O material. The relationship between the kind and ratio of raw materials in the initial mixed solution, the reaction temperature, the reaction time and the sample number is shown in Table 1.
TABLE 1 relationship between sample Synthesis conditions and sample number
Example 2 structural analysis of sample
The structure of samples 1# to 11# was analyzed by powder X-ray diffraction method.
Powder X-ray diffraction was carried out on an X-ray powder diffractometer of Miniflex II, RIGAKU, Japan, under the conditions of a fixed target monochromatic light source Cu-Ka, wavelength
The voltage and current are 30kV/15A, the slit DivSlit/RecSlit/SctSlit is 1.25deg/0.3mm/1.25deg, the scanning range is 5-50 deg, and the scanning step is 0.02 deg.
The results show that samples 1# to 2# and 5# to 11# have the same X-ray diffraction peak, but the peak intensities are different, indicating that the chemical structural formula is the same as the crystal structure. The number 3# to 4# have a plurality of peaks, which shows that the chemical structure is different. Typically represented by sample # 1, as shown in FIG. 1. In FIG. 1(a), (NH) 4 )CoPO 4 ·H 2 And O, fitting the obtained X-ray diffraction pattern with the pattern obtained by X-ray diffraction test of the sample No. 2 figure 1(b) and the sample No. 1 figure 1(c) through the crystal structure obtained by a single crystal X-ray diffractometer, wherein the peak positions are consistent, and the obtained samples have high purity. FIG. 1(d) shows the calcination of sample No. 1 at 350 ℃ in a nitrogen atmosphere. FIG. 2 is a thermogravimetric analysis of sample # 1.
EXAMPLE 3 topographical characterization of samples
And (3) performing morphology characterization on the sample 1# calcined at 350 ℃ for two hours in a nitrogen atmosphere by adopting a scanning electron microscope method. The result shows that as shown in the scanning electron microscope image of fig. 3, the sample 1# after high-temperature treatment has a good flaky morphology, and the material has uniform morphology, good dispersibility and a size of 5 μm.
Example 4 electrochemical testing
The electrochemical oxygen evolution reaction test of the sample 1# after the sample 1# and the sample 1# are calcined for two hours at 350 ℃ in a nitrogen atmosphere is carried out on an electrochemical workstation of CHI760E model of Chen Hua corporation in Shanghai, the polarization curve is tested by a three-electrode system linear scanning voltammetry, and the reference electrode and the counter electrode are respectively an Hg/HgO electrode and a Pt wire electrode. Respectively taking 5mg of sample No. 1 and calcined sample No. 1 (calcined at 350 ℃ for two hours under nitrogen atmosphere), mixing with 0.5mL of water, 0.5mL of ethanol and 10 mu L of an Afion solution, carrying out ultrasonic treatment for 12 hours to ensure that the catalyst forms a uniformly dispersed suspension, and then taking 6 mu L of mixed liquid drop with the diameter of 0.07cm 2 And the glassy carbon electrode is naturally dried to be used as a working electrode. The electrolyte was 1M KOH and the scan rate was 5 mV/s.
The test results are shown in FIG. 4, which shows that the current density is 10mA cm -2 The overpotentials at these temperatures were NCFPO-350(278mV, sample # 1 calcined at 350 ℃ for two hours under nitrogen atmosphere), which was superior to NCPO (379mV, sample # 2), NCFPO (307mV, sample # 1), NCPO-350(312mV, sample # 2 calcined at 350 ℃ for two hours under nitrogen atmosphere), and IrO2(320mV), respectively. The calcined N-doped amorphous material has the lowest OER overpotential and the maximum current density, and the performance is obviously superior to that of commercial IrO 2 And a cobalt iron phosphate material prior to calcination.
The oxygen reduction reaction is carried out on an RRDE-3A type rotating disk electrode, the polarization curve is tested by a three-electrode system linear sweep voltammetry, and a reference electrode and a counter electrode are respectively saturated calomel electrodes (Hg/HgCl) 2 ) And a Pt wire electrode, taking 5mg of sample No. 1 and a calcined sample thereof and Super P conductive carbon 1: 1 is dispersed in a mixed solution of 240 mu L of isopropanol and 720 mu L of deionized water after being mixed, 40 mu L of 5 wt% Nafion membrane solution is added to ensure the stable loading of the catalyst, and the catalyst ink is subjected to ultrasonic treatment for 30min to be uniformly dispersed. 5 mu L of catalyst ink is dripped on the surface of the glassy carbon electrode, the glassy carbon electrode is placed at normal temperature until the solvent is completely volatilized to be used as a working electrode, the electrolyte is 1M KOH, and the scanning speed is 5 mV/s.
The test results are shown in fig. 5, and it can be seen that the calcined N-doped amorphous material has a higher ORR half-wave potential and a good limiting current density.
The cell was run on a BTS novyi cell tester, taking 5mg of sample # 1 and its calcined sample, respectively, first according to the catalyst: super P: the mass ratio of graphene to graphene is 4:4:1, and the active material and 5 wt% of graphene slurry are stirred and mixed in a mortar for 0.5h to obtain uniformly dispersed catalyst slurry. The catalyst slurry was coated on one side of the carbon paper using a knife coating method and dried in a 60 ℃ oven for 8 h. Thereafter, the dried carbon paper was cut into circular pieces having a diameter of 15mm for use, and the catalyst supporting amount was about 2mg cm -2 . The electrolyte is 6M KOH +0.2MZn (Ac) 2 The scan rate was 50 mV/s.
The test results are shown in FIGS. 6-8, which show that the calcined N-doped amorphous material has higher battery power density and the battery power density is 10mA cm -2 Has a specific capacitance of 772mAHg of the material before calcination at a current density of (2) -1 The specific capacitance of the calcined material is 783mAHg -1 Although the samples before and after calcination have similar specific capacitance, the battery charge-discharge cycle stability of the samples after simple heat treatment is about 30h, which is obviously better than 20h before heat treatment, and has higher cycle stability.
Example 5
Will yield a pink NH 4 Co 0.8 Fe 0.2 PO 4 ·H 2 The specific relationship between the O material (sample # 1) and the different calcination temperatures in the inert gas atmosphere is shown in Table 2.
Table 2 sample No. 1 was subjected to different high temperature treatment conditions
| Calcination temperature (. degree. C.) | Calcination time (h) | Atmosphere of |
| 200 | 2 | |
| 200 | 2 | |
| 250 | 2 | |
| 250 | 2 | |
| 300 | 2 | |
| 300 | 2 | |
| 350 | 2 | |
| 350 | 2 | |
| 400 | 2 | |
| 400 | 2 | Argon gas |
As can be seen from FIG. 9, when the material was calcined at different temperatures in an inert gas atmosphere such as nitrogen and argon, the material was heat-treated at 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C and 450 deg.C to 10mA cm -2 The overpotentials of the OERs are 324mV, 341mV, 280mV, 278mV, 289mV and 305mV respectively under the current density of (1), and the result shows that the OER catalytic performance of the material after heat treatment at 350 ℃ is the best.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. The preparation method of the amorphous nitrogen-doped cobalt iron phosphate microchip catalytic material is characterized by comprising the following steps of mixing a cobalt source, an iron source, a phosphorus source and water, wherein the phosphorus source is at least one of ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate; uniformly mixing and stirring to form an initial mixed solution, transferring the initial mixed solution into a high-pressure kettle for hydrothermal reaction to obtain pink NH 4 Co 0.8 Fe 0.2 PO 4 ·H 2 An O material; NH pink 4 Co 0.8 Fe 0.2 PO 4 ·H 2 And treating the O material for 2 hours at 350 ℃ in the inert gas atmosphere to obtain the amorphous nitrogen-doped ferrocobalt phosphate microchip catalytic material.
2. The preparation method according to claim 1, wherein the mass ratio of the cobalt source, the iron source, the phosphorus source and the water in the initial mixed solution is 1-4: 0.2-0.8: 2-6: 50.
3. the preparation method according to claim 1 or 2, wherein the hydrothermal reaction is carried out at a temperature of 160-220 ℃ for 8-20 hours.
4. The method according to claim 1 or 2, wherein the selected cobalt source is at least one of cobalt nitrate, cobalt acetate, cobalt difluoride, cobalt chloride and cobalt bromide.
5. The method of claim 1 or 2, wherein the iron source is at least one of ferric nitrate, ferric chloride, ferrous chloride, ferric sulfate, and ferric bromide.
6. The production method according to claim 1 or 2, wherein in the initial mixed solution, the cobalt source is CoCl 2 The iron source is FeCl 2 The phosphorus source is (NH) 4 ) 3 PO 4 ，CoCl 2 :FeCl 2 :(NH 4 ) 3 PO 4 :H 2 The mass ratio of O is 1.9:0.4:4.0: 50.
7. The method according to claim 1 or 2, wherein the inert gas is one or both of nitrogen and argon.
8. The catalytic material prepared by the preparation method of any one of claims 1 to 7, wherein the catalytic material is swept in a 1M KOH solution at a sweep rate of 5mV/s at a current density of 10mA/cm 2 Under the condition of (1), the overpotential of the OER is 278 mV; ORR half-wave potential is 0.74V; the power density of the zinc-air battery is 74.6mW/cm 2 At 10mA cm -2 The specific capacitance of 783mAHg at the current density of -1 And the charge-discharge cycle stability of the battery is 30 h.
9. An electrode comprising the catalytic material of claim 8.
10. An electrocatalytic device comprising the catalytic material of claim 8.
11. Use of the catalytic material of claim 8 in electrocatalytic oxygen evolution reactions and/or electrochemical oxygen reduction reactions.
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