CN108597913B - Iron-containing composite oxide electrode and preparation method and application thereof - Google Patents
Iron-containing composite oxide electrode and preparation method and application thereof Download PDFInfo
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- CN108597913B CN108597913B CN201810347089.7A CN201810347089A CN108597913B CN 108597913 B CN108597913 B CN 108597913B CN 201810347089 A CN201810347089 A CN 201810347089A CN 108597913 B CN108597913 B CN 108597913B
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- 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
- H01G11/46—Metal oxides
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- 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
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- 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 invention discloses an iron-containing composite oxide electrode and a preparation method thereof, wherein the composite oxide electrode comprises a current collector and a composite oxide active substance layer which contains vanadium and iron and is attached to the current collector; the electrode is free of binder. The preparation method of the iron-containing composite oxide electrode comprises the following steps: preparing a soluble salt solution containing vanadium and iron; placing the current collector in a mixed aqueous solution containing vanadium and iron for hydro-thermal treatment, so that the surface of the current collector is covered with a composite oxide of vanadium and iron; and finally, carrying out heat treatment on the current collector with the surface covered with the vanadium and iron composite oxide to obtain the iron-containing composite oxide electrode. The iron-containing composite oxide electrode can be used for an electrochemical super capacitor.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an iron-containing composite oxide electrode and a preparation method and application thereof.
Background
Although supercapacitors have the advantages of good high power output performance and long cycle life, their energy density is significantly lower than that of rechargeable batteries. In order to improve the performance of the super capacitor, i.e. to improve the specific energy while maintaining the advantages of large specific power, the transition metal oxide electrode with electric double layer capacitance and faraday pseudocapacitance behavior has become one of the main research hotspots in this field at present. For the positive electrode material, though RuO2The mass ratio energy is also high, but because of the resource limitation, the raw material cost is high, so that the commercial popularization is difficult to obtain. In order to seek an inexpensive supercapacitor electrode material, NiO and Co are surrounded3O4、V2O5、MnO2Preparation of equal transition metal oxide or composite oxide material and electrochemical performance research phaseAnd then expanding. Among the oxides, nickel, cobalt or composite oxides thereof show higher specific capacitance in alkaline electrolyte, and can reach more than 2000F/g. However, in terms of preparing high specific energy devices, the cathode materials capable of being used with these high specific capacitance cathode materials are still relatively lacking, the capacity of the carbon materials widely used at present can only reach about 200F/g, and when the two materials are used for preparing asymmetric capacitors, the specific energy of the final device is necessarily limited due to the large usage amount of the cathode materials, and it is difficult to fully embody the high specific capacitance characteristics of the cathode materials.
In order to obtain a negative electrode material having high specific capacitance characteristics in an alkaline electrolyte environment, another transition metal oxide, Fe, has been targeted in recent years2O3Or FeOOH materials are of interest. Although the theoretical specific capacitance of the material is higher, the specific capacitance of the material prepared by various experimental methods is not high (generally 50-200F/g) due to the influence of the electron conductivity of the material. Therefore, a great deal of research work needs to be carried out on finding a supercapacitor negative electrode material matched with an oxide positive electrode material such as nickel cobalt and the like in an alkaline environment. From the condition of literature reference, at present, no report of using iron-containing and other transition metal composite oxides as the cathode of the supercapacitor exists.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an iron-containing composite oxide electrode and a preparation method and application thereof.
The invention relates to an iron-containing composite oxide electrode which comprises a current collector and a composite oxide layer of vanadium and iron attached to the current collector, wherein the composite oxide layer of the iron and the vanadium contains vanadium in a pentavalent state, iron in a trivalent state, and iron, vanadium and oxygen in a ternary compound form.
The invention relates to an iron-containing composite oxide electrode, wherein vanadium and iron in the iron-containing composite oxide are FexVyOzAnd 3x +5y ═ 2z, where V and O form an anion and Fe is present in the form of a cation.
The invention relates to a composite oxide containing ironAn electrode, preferably, the vanadium and iron composite oxide is FexVyOzAnd 3x +5y ═ 2z, where V and O form an anion and Fe is present in the form of a cation. As further preferred wherein the ratio of x to y is 1 to 3: 1. as a further preference, the FexVyOzSelected from FeVO4,Fe4V6O21,Fe2V4O13,FeV3O9At least one of (1).
The invention relates to an iron-containing composite oxide electrode, wherein the current collector is preferably carbon paper or porous foam nickel. Of course, any material having the function of a current collector is suitable for use in the present invention. And are not limited herein.
The invention relates to an iron-containing composite oxide electrode, which does not contain a binder.
The invention relates to a preparation method of an iron-containing composite oxide electrode, which comprises the following steps:
step one
Preparing an aqueous solution containing iron and vanadium according to a set molar ratio of iron to vanadium; in the aqueous solution containing iron and vanadium, vanadium exists in a positive quadrivalent state and/or a positive pentavalent state, and iron exists in a positive trivalent state;
step two
Putting the current collector into the aqueous solution containing iron and vanadium obtained in the step one, and carrying out hydrothermal treatment; obtaining a current collector coated with iron and vanadium composite oxides
Step three
And (4) placing the current collector coated with the iron and vanadium composite oxide obtained in the step two in an oxygen-containing atmosphere, and carrying out heat treatment to obtain the metal composite oxide electrode.
The invention relates to a preparation method of a metal composite oxide electrode. The water-soluble vanadium salt is preferably more than one of ammonium vanadate, potassium vanadate, sodium vanadate, ammonium metavanadate, potassium metavanadate, sodium metavanadate, vanadyl sulfate, vanadyl chloride, vanadyl nitrate and vanadyl sulfate; the water-soluble ferric salt is preferably at least one of ferric nitrate, ferric trichloride and ferric sulfate; when the valence of vanadium in the selected water-soluble vanadium salt is positive quadrivalence, the water-soluble iron salt is preferably ferric nitrate.
The invention relates to a preparation method of a metal composite oxide electrode, which is characterized in that in an aqueous solution containing iron and vanadium prepared in the step one, the concentration of an iron element is 0.01-0.3 mol/L, preferably 0.05-0.3mol/L, and more preferably 0.05-0.2 mol/L.
The invention relates to a preparation method of a metal composite oxide electrode, wherein in an aqueous solution containing iron and vanadium prepared in the step one, the concentration of vanadium element is 0.01-1.5 mol/L, preferably 0.05-0.9mol/L, and more preferably 0.05-0.6 mol/L.
The invention relates to a preparation method of a metal composite oxide electrode, which is characterized in that in an aqueous solution containing iron and vanadium prepared in the step one, in order to prevent iron salt and vanadium salt from quickly generating precipitate, the pH value of the solution is adjusted to 1-2.
The invention relates to a preparation method of a metal composite oxide electrode, which is characterized in that in an aqueous solution containing iron and vanadium prepared in the step one, the molar ratio of vanadium to iron is 1-5: 1. Preferably, in the aqueous solution containing iron and vanadium prepared in the first step, the molar ratio of vanadium to iron is 1-3: 1.
The preparation method of the metal composite oxide electrode comprises the step two, wherein the temperature of hydrothermal treatment is 70-150 ℃, and the treatment time is 8-24 hours. Preferably, the heat treatment temperature is 75 to 100 ℃ and the treatment time is 10 to 15 hours. In industrial applications, the hydrothermal treatment is carried out in a closed reaction vessel.
The preparation method of the metal composite oxide electrode comprises the third step, wherein the heat treatment temperature is 300-400 ℃, and the treatment time is 2-8 hours. Preferably, the heat treatment temperature is 300-350 ℃, and the treatment time is 3-5 hours.
In the third step of the preparation method of the metal composite oxide electrode, the atmosphere of the heat treatment is preferably air atmosphere.
The invention relates to application of a metal composite oxide electrode, which comprises the step of using the metal composite oxide electrode as a negative electrode of an electrochemical super capacitor.
When the electrode is used as the cathode of an electrochemical super capacitor, vanadium and iron in an active material layer can participate in electrochemical reaction to show good electrochemical performance.
When the electrode is used as the cathode of an electrochemical super capacitor, 1mol/L potassium hydroxide aqueous solution is used as electrolyte, the metal composite oxide electrode designed and prepared by the invention is used as a working electrode, and the area is 4 multiplied by 4cm2The platinum electrode is a counter electrode assembled three-electrode system, cyclic voltammetry is carried out, the test potential range is 0-minus 1.2V (relative to a mercury oxide electrode), the scanning rate is 10mV/s, and the specific capacitance of the active substance in the working electrode is 343F/g-390F/g through calculation.
Advantageous effects
The invention firstly proposes that the metal composite oxide containing iron and vanadium is used as the cathode of the super capacitor, and under the working environment of the cathode of the super capacitor, the iron and the vanadium in the composite oxide can participate in electrochemical reaction, so that the phenomenon that the electrode capacitance is reduced due to the fact that the composite oxide contains non-electroactive metal elements is avoided.
In the preferred scheme of the invention, the iron and vanadium in the metal composite oxide exist in a form, and the electronic conductivity of the metal composite oxide as a semiconductor material is obviously higher than that of the iron oxide or vanadium oxide alone, so that the electronic conductivity of the electrode and the utilization rate of the electrode active substance are improved, and the specific capacitance of the electrode material is improved.
In the preferable preparation scheme of the invention, vanadium and iron elements are uniformly distributed in the obtained composite oxide through the hydrothermal reaction of the mixed solution of soluble salts containing vanadium and ferric iron, thereby ensuring that the mixed solution can be converted into homogeneous Fe in the subsequent hydrothermal and heat treatment processesxVyOz. The method can ensure the consistency of the electrode material no matter the method is used for preparing the binderless electrode or the powder electrode material.
Drawings
FIG. 1 is a cyclic voltammetry curve of a vanadium iron metal composite oxide capacitor electrode prepared in example 1 of the present invention, from which the specific capacitance of the electrode material can be calculated
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method. The specific embodiment of the invention is as follows:
example one
Respectively dissolving ammonium metavanadate and ferric nitrate in water, mixing to prepare a mixed solution containing 0.05mol/L of ammonium metavanadate and 0.05mol/L of ferric nitrate, and adjusting the pH value of the solution to 1.5 by using nitric acid.
The cut area is 4 multiplied by 1cm2And (2) taking carbon paper as a current collector, carrying out ultrasonic washing on the current collector by using acetone, finally, washing the current collector by using water, putting the current collector into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, injecting a mixed solution containing 0.05mol/L ammonium metavanadate and 0.05mol/L ferric nitrate, sealing, keeping the temperature at 75 ℃ for 12 hours, taking out the obtained electrode after the high-pressure autoclave is cooled to room temperature, washing the electrode by using deionized water, drying the electrode, and finally, carrying out heat treatment in a 350 ℃ muffle furnace for 3 hours to obtain the needed iron-containing composite oxide electrode.
Using 1mol/L potassium hydroxide aqueous solution as electrolyte, using the obtained metal oxide electrode as working electrode, and its area is 4X 4cm2The platinum electrode is a counter electrode assembled three-electrode system, cyclic voltammetry is carried out, the testing potential range is 0 to-1.2V (relative to a mercury oxide electrode), the scanning rate is 10mV/s, the obtained cyclic voltammetry curve is shown in figure 1, and the specific capacitance of the electrode active substance is calculated to be 363.8F/g according to the cyclic voltammetry curve.
Example two
The operation process is the same as that of the first example, except that vanadyl nitrate is used to replace ammonium metavanadate, the concentration of the vanadyl nitrate is 0.6mol/L, the concentration of ferric nitrate is 0.4mol/L, and the pH value of the solution is adjusted to 1 by nitric acid.
The hydrothermal treatment temperature is 100 ℃, the heat preservation time is 10 hours, the obtained electrode is taken out after the high-pressure kettle is cooled to the room temperature, washed by deionized water and dried, and then the electrode is subjected to heat treatment in a muffle furnace at the temperature of 400 ℃ for 5 hours to obtain the required composite oxide electrode. The specific capacitance of the electrode active material was calculated to be 342.7F/g from the cyclic voltammogram (the test conditions and methods were in full agreement with example one).
EXAMPLE III
The operation process is the same as that of the first example, except that sodium metavanadate is used to replace ammonium metavanadate, the concentration of sodium metavanadate is 0.6mol/L, the concentration of ferric nitrate is 0.2mol/L, and the pH value of the solution is adjusted to 1.8 by nitric acid.
The hydrothermal treatment temperature is 120 ℃, the heat preservation time is 15 hours, the obtained electrode is taken out after the high-pressure kettle is cooled to the room temperature, the electrode is washed by deionized water and dried, and the electrode is subjected to heat treatment in a muffle furnace at the temperature of 300 ℃ for 5 hours to obtain the required composite oxide electrode. The specific capacitance of the electrode active material was calculated to be 389.2F/g from the cyclic voltammogram (test conditions and methods were in full agreement with example one).
Example four
Only sodium metavanadate is used for replacing ammonium metavanadate, the concentration of the sodium metavanadate is 0.6mol/L, the concentration of ferric nitrate is 0.4mol/L, and the pH value of the solution is adjusted to be 2 by nitric acid.
The hydrothermal treatment temperature is 90 ℃, the heat preservation time is 15 hours, the obtained electrode is taken out after the high-pressure kettle is cooled to the room temperature, the electrode is washed by deionized water and dried, and the electrode is subjected to heat treatment in a muffle furnace at the temperature of 300 ℃ for 5 hours to obtain the required composite oxide electrode. The specific capacitance of the electrode active material was calculated to be 351.1F/g from the cyclic voltammogram (test conditions and methods were in full agreement with example one).
Comparative example 1
The operation process is the same as that of the first example, except that the solution does not contain any soluble vanadium, the concentration of ferric nitrate is 0.225mol/L (the volume of the solution is completely consistent with that of the first example), and the pH value of the solution is adjusted to 1.5 by nitric acid;
the hydrothermal treatment temperature is 150 ℃, the heat preservation time is 12 hours, the obtained electrode is taken out after the high-pressure kettle is cooled to the room temperature, washed by deionized water and dried, and then the electrode is thermally treated in a muffle furnace at 350 ℃ for 3 hours to obtain the ferric oxide electrode. The specific capacitance of the electrode active material was calculated to be 89.1F/g from the cyclic voltammogram (the test conditions and methods were completely in accordance with the first example).
Comparative example No. two
The operation process is the same as that of the second embodiment except that the solution does not contain ferric nitrate, the concentration of vanadyl nitrate is 0.6mol/L, the hydrothermal treatment temperature is 120 ℃, the heat preservation time is 12 hours, the obtained electrode is taken out after the autoclave is cooled to the room temperature, washed by deionized water and dried, and then the vanadium pentoxide electrode is obtained after heat treatment in a muffle furnace at 350 ℃ for 3 hours. The specific capacitance of the electrode active material was calculated to be 10.3F/g from the cyclic voltammogram (the test conditions and methods were completely in accordance with the first example).
Comparative example No. three
The operation process is the same as that of the first embodiment, only nitric acid is not added to adjust the pH value of the solution, precipitation is found to occur after the ammonium metavanadate and the ferric nitrate solution are mixed, few active substances are found to be covered on the current collector after hydrothermal and thermal treatment, cyclic voltammetry tests find that the capacity of the active substances cannot be calculated due to the fact that no obvious oxidation current exists when the potential is scanned in the positive direction, and the capacity of the whole electrode is very low.
Claims (4)
1. An iron-containing composite oxide electrode, characterized in that: the composite oxide electrode comprises a current collector and an iron and vanadium composite oxide layer directly attached to the current collector, the electrode does not contain a binder, vanadium exists in a pentavalent state, iron exists in a trivalent state, and iron, vanadium and oxygen exist in a ternary compound form; the iron-containing composite oxide contains vanadium and iron as FexVyOzAnd 3x +5y =2z, wherein V and O constitute an anion, Fe is present in the form of a cation, and the molar ratio of vanadium to iron element is greater than 1: 1 and less than or equal to 3: 1;
the iron-containing composite oxide electrode is prepared by the following steps:
step one
Preparing an aqueous solution containing iron and vanadium according to a set molar ratio of iron to vanadium, wherein in the aqueous solution containing iron and vanadium, vanadium exists in a positive quadrivalent state and/or a positive pentavalent state, iron exists in a positive trivalent state, the pH value is 1-2, the concentration of iron element is 0.01-0.3 mol/L, the concentration of V element is 0.01-1 mol/L, and the molar ratio of vanadium to iron is more than 1 and less than or equal to 3;
step two
Putting the current collector into the aqueous solution containing iron and vanadium obtained in the step one, and carrying out hydrothermal treatment; obtaining a current collector coated with iron and vanadium composite oxides; the temperature of the hydrothermal treatment is 70-150 ℃, and the treatment time is 12-24 hours;
step three
Placing the current collector coated with the iron and vanadium composite oxide obtained in the step two in an oxygen-containing atmosphere, and carrying out heat treatment to obtain a metal composite oxide electrode; the heat treatment temperature is 300-400 ℃, and the treatment time is 2-8 hours.
2. The iron-containing composite oxide electrode according to claim 1, wherein: in the first step, water-soluble iron salt and water-soluble vanadium salt are used for preparing an aqueous solution containing iron and vanadium.
3. The use of an iron-containing composite oxide electrode according to claim 1, wherein: comprising using it as the negative electrode of an electrochemical supercapacitor.
4. The use of an iron-containing composite oxide electrode according to claim 3, wherein: when the vanadium-iron composite material is used as a negative electrode of an electrochemical super capacitor, vanadium and iron in an active material layer participate in electrochemical reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101913651A (en) * | 2010-07-30 | 2010-12-15 | 北京工业大学 | Hydrothermal method for preparing triclinic-phase FeVO4 micro particles |
| CN105958068A (en) * | 2016-07-21 | 2016-09-21 | 中南大学 | Preparation method of nanorod negative electrode material ferric vanadate for lithium-ion battery |
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913651A (en) * | 2010-07-30 | 2010-12-15 | 北京工业大学 | Hydrothermal method for preparing triclinic-phase FeVO4 micro particles |
| CN105958068A (en) * | 2016-07-21 | 2016-09-21 | 中南大学 | Preparation method of nanorod negative electrode material ferric vanadate for lithium-ion battery |
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
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