CN108199051B - Oxygen precipitation electrode and preparation and application thereof - Google Patents

Oxygen precipitation electrode and preparation and application thereof Download PDF

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CN108199051B
CN108199051B CN201611121217.3A CN201611121217A CN108199051B CN 108199051 B CN108199051 B CN 108199051B CN 201611121217 A CN201611121217 A CN 201611121217A CN 108199051 B CN108199051 B CN 108199051B
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孙公权
燕召
王二东
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to an oxygen evolution electrode, which comprises a foam metal and a double metal hydroxide or a metal hydroxide compound loaded on a foam metal framework. The foam metal is immersed in a solution containing metal ions and deposited on the foam metal through a hydrolytic precipitation reaction of the metal ions in an aqueous solution. The invention does not use organic precipitator, thus avoiding the pollution to the environment; a strong alkaline precipitator is not used, the metal salt is slowly and uniformly hydrolyzed and precipitated, and finally the obtained catalyst is uniformly dispersed; high-temperature and high-pressure equipment is not used, the safety and the low price are realized, and the amplification and the batch preparation are easy; the catalyst is loaded on the carrier in situ, has strong binding force, is not easy to fall off, and has small contact resistance. The oxygen precipitation electrode prepared by the invention has the advantages of high overactivity, low potential, small internal resistance, difficult falling of the catalyst, long service life of the electrode, low cost and easy industrial production.

Description

Oxygen precipitation electrode and preparation and application thereof
Technical Field
The invention relates to an oxygen evolution electrode material, and also relates to a preparation method and application of the oxygen evolution electrode.
Background
Oxygen Evolution Reaction (OER) plays an important role in water electrolysis, renewable fuel cells, and secondary metal/air cells, but since the kinetics of the Oxygen Evolution Reaction is slow and requires a high overpotential, researchers at home and abroad have conducted extensive studies on catalysts and electrodes for the Oxygen Evolution Reaction.
At present, the catalysts for oxygen evolution reaction with higher performance are Ir-based and Ru-based noble metals and oxides thereof, but due to low reserves and high price, the non-noble metal oxygen evolution catalysts are widely researched in recent years. Among various non-noble metal catalysts, Layered Double Hydroxides (LDHs) catalysts, especially NiFe-based LDH catalysts, have high catalytic performance and stability, and are non-noble metal oxygen precipitation catalysts with wide application prospects. However, the preparation process of the catalyst is complex, and the catalyst can be generally prepared by a coprecipitation method, a hydrothermal method, an electrodeposition method and the like, and the preparation process needs to finely control conditions such as experimental pH and the like, use a high-pressure reaction device or expensive instruments and the like, so that the wide application of the LDHs catalyst is limited.
Disclosure of Invention
Aiming at the defects that the preparation process of the layered double hydroxide catalyst is complex and difficult to apply in the prior art, the invention prepares the flower-shaped microsphere catalyst which is self-assembled by the composite of the metal hydroxide or the metal oxide and the metal hydroxide and has a nano sheet shape on the microcosmic scale by soaking foamed nickel in the solution of metal cations such as Ni, Fe, Co and the like and performing hydrolysis precipitation. The invention is realized by adopting the following scheme:
an oxygen evolving electrode characterized in that: the oxygen precipitation electrode takes foam metal as an electrode support body and a framework, flower-shaped microspheres self-assembled by a nano-sheet catalyst are uniformly loaded on the oxygen precipitation electrode, and the catalyst is a double metal hydroxide, or a compound of a first metal hydroxide and a second metal hydroxide, or a compound of the double metal hydroxide and one or two hydroxides of the same metal in double metals.
The thickness of the nano flaky catalyst is 10-100 nm; the diameter of the flower-shaped microspheres is 500nm-5 μm.
The thickness of the nano flaky catalyst is preferably 10-50 nm; the diameter of the flower-shaped microspheres is preferably 500nm-2 μm.
The loading capacity of the double metal hydroxide in the oxygen precipitation electrode is 0.1-10mg/cm 2; or the loading capacity of the first metal hydroxide in the oxygen evolution electrode is 0.01-5mg/cm 2; the loading of the second metal hydroxide is 0.01-5mg/cm 2.
The thickness of the foam metal support body is 0.5-5 mm; the double metal hydroxides are hydroxides of any two of Ni, Fe, Co, Al, Zn and Mn, and one metal is 1-99% of the total molar content of the double metals in terms of metal; the first and second metal hydroxides in the composite of the first metal hydroxide and the second metal hydroxide are respectively hydroxides of any one metal of Ni, Fe, Co, Al, Zn and Mn; and the first and second metals are different, the first metal hydroxide being 1-99% of the total molar content of the two metal hydroxides.
Soaking the foamed nickel support in a salt solution containing two cations of Ni, Fe, Co, Al, Zn and Mn for more than 1 hour.
The temperature range of the solution is 0-100 ℃, and the temperature range of the solution is preferably 30-90 ℃; the soaking time of the foamed nickel in the salt solution is preferably between 3 and 15 days.
The pH difference of the two metal cations starting hydrolysis precipitation is less than 2; the pH difference is preferably less than 0.2.
The concentration of the metal cations in the salt solution is 0.0001-1mol/L, and the total concentration of the two metal cations is 0.1-2 mol/L.
The pH range of the solution is 4-10; the pH range is preferably 6 to 8.
The oxygen evolving electrode may be used as electrolyzed water, photo-electrolyzed water, a renewable fuel cell, or a rechargeable metal air cell.
The key point of the invention is to control the concentration of the two metal cations so that the pH at which the hydrolysis precipitation starts (the pH at which the hydrolysis precipitation starts can be calculated from the solubility product of the corresponding hydroxide, such as Ni (OH)2The solubility product is K-5.48 × 10-16When being Ni2+At a concentration c of 0.1mol/L, Ni2+Beginning to precipitate
Figure BDA0001174296600000021
Approximately equal to each other (less than 0.2), and the two metal cations are simultaneously hydrolyzed and precipitated in the aqueous solution, namely, the two metals can be uniformly dispersed in the whole catalyst, so that the prepared catalyst has higher performance.
The present invention proposes that by immersing the foam metal in an aqueous solution of a metal salt, unlike conventional impregnation methods, which merely serve to adsorb metal ions onto a carrier, a subsequent step of calcination or the like is still required to convert the metal salt from an ionic state to a solid state. The key point of the invention is that the metal salt is hydrolyzed and precipitated in the water solution to generateThe precipitate is directly loaded in situ on the carrier foam metal without the need for a subsequent calcination step. In addition, because the hydrogen ions generated by hydrolysis prevent the continuous hydrolysis reaction, if no carriers such as foam nickel and the like are added, the continuous hydrolysis reaction can not obtain precipitates+Further promotes the hydrolytic precipitation of the metal salt. The foamed silver, the carbon fiber felt, the carbon cloth, the carbon paper and the like cannot be corroded in the aqueous solution, namely, H generated by hydrolysis reaction cannot be consumed+And thus cannot be used as a carrier in the present invention. In the conventional impregnation method, the carrier plays a role of adsorbing metal ions, so that the carrier can be used as long as the carrier has a high specific surface area, such as carbon felt, carbon paper, foamed nickel and the like.
The invention has longer time for soaking the foam metal in the reaction solution, because the hydrolysis reaction rate of the metal salt is slower, the slow hydrolysis precipitation needs to be carried out for a longer time, and the other two hydroxide precipitates are slowly aged in water and are transformed into the layered double hydroxide or hydroxide compound through crystal form. Whereas the conventional impregnation method requires only the adsorption of the metal salt onto the carrier for a short period of time, even though the related patent proposes a long impregnation time, the object is only to allow the metal salt to be sufficiently adsorbed onto the carrier, rather than to wait for the hydrolytic precipitation reaction of the metal salt.
The common preparation methods of the layered double hydroxide include a coprecipitation method, a hydrothermal method and the like, and all require a precipitator (such as alkali, urea and other compounds capable of releasing hydroxide) to precipitate metal salts to generate hydroxide, and promote crystal form transformation through high-temperature and high-pressure reaction. In the invention, the water becomes a green precipitator, so that the metal salt is slowly hydrolyzed and precipitated, and is aged at normal temperature and normal pressure to carry out crystal form transformation.
The invention has the advantages that no organic precipitator is used, thereby avoiding the pollution to the environment; a strong alkaline precipitator is not used, the metal salt is slowly and uniformly hydrolyzed and precipitated, and finally the obtained catalyst is uniformly dispersed; high-temperature and high-pressure equipment is not used, the safety and the low price are realized, and the amplification and the batch preparation are easy; the catalyst is loaded on the carrier in situ, has strong binding force, is not easy to fall off, and has small contact resistance. The oxygen precipitation electrode prepared by the invention has the advantages of high overactivity, low potential, small internal resistance, difficult falling of the catalyst, long service life of the electrode, low cost and easy industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the embodiments are briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a photograph of a nickel foam electrode used in the examples.
FIG. 2 shows the catalytic performance of the nickel foam electrode used in the examples.
FIG. 3 is a photograph of the oxygen evolution electrode prepared in example 1.
FIG. 4 is a microscopic morphology of the oxygen evolving electrode prepared in example 1.
FIG. 5 is an X-ray diffraction pattern of the oxygen-evolving electrode prepared in example 1.
FIG. 6 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 1.
FIG. 7 is a photograph of an oxygen evolution electrode prepared in example 2.
FIG. 8 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 2.
FIG. 9 is a photograph of an oxygen evolution electrode prepared in example 3.
FIG. 10 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 3.
FIG. 11 is a photograph of an oxygen evolution electrode prepared in example 4.
FIG. 12 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 4.
FIG. 13 is a photograph of an oxygen evolution electrode prepared in example 5.
FIG. 14 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 5.
FIG. 15 is a photograph of an oxygen evolution electrode prepared in example 6.
FIG. 16 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 6.
FIG. 17 is a photograph of an oxygen evolution electrode prepared in example 7.
FIG. 18 is a graph showing the catalytic performance of the oxygen evolving electrode prepared in example 7.
FIG. 19 shows oxygen evolution electrodes prepared in examples 1 to 7 at 10mA cm-2Overpotential contrast graph below.
Detailed Description
The following is a clear and complete description of the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1: preparing FeCl containing 0.01mol/L2With 0.1mol/LNiCl2A piece of foam nickel with the thickness of 1cm × 2cm is added into the water solution, the solution is soaked for 15 days, and the electrode is taken out, washed and dried for standby application, wherein, FIG. 1 is a photo of the prepared oxygen precipitation electrode, FIG. 2 is the micro-morphology of the prepared oxygen precipitation electrode, FIG. 3 is an X-ray diffraction spectrum of the prepared oxygen precipitation electrode, and FIG. 4 is the performance of the prepared oxygen precipitation electrode in catalyzing oxygen precipitation in 1mol/L KOH solution.
Example 2: preparing FeCl containing 0.01mol/L3With 0.1mol/L NiCl2A piece of foam nickel with the thickness of 1cm × 2cm is added into the water solution, the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen precipitation electrode is shown in figure 5, and the picture of the prepared oxygen precipitation electrode is shown in figure 6, and the performance of the prepared oxygen precipitation electrode in 1mol/L KOH solution for catalyzing oxygen precipitation is shown in figure 6.
Example 3: the preparation contains 0.1mol/L CoCl2With 0.001mol/L NiCl2A piece of foamed nickel with the thickness of 1cm × 2cm is added into the aqueous solution of (1 cm) of (8), the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen precipitation electrode is shown in figure 7, and the picture of the prepared oxygen precipitation electrode is shown in figure 8, and the performance of the prepared oxygen precipitation electrode in a 1mol/L KOH solution for catalyzing oxygen precipitation is shown in figure 8.
Example 4: the preparation of ZnCl containing 0.06mol/L2With 0.1mol/L FeCl2A piece of foamed nickel with the thickness of 1cm × 2cm is added into the aqueous solution of (1 cm) of (3), the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen precipitation electrode is shown in figure 9, and the picture of the prepared oxygen precipitation electrode is shown in figure 10, and the performance of the prepared oxygen precipitation electrode in a 1mol/L KOH solution for catalyzing oxygen precipitation is shown in figure 10.
Example 5: the preparation contains 0.0005mol/L ZnCl2With 0.1mol/L CoCl2A piece of foamed nickel with the thickness of 1cm × 2cm is added into the aqueous solution of (1 cm) of (2 cm), the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen evolution electrode is shown in figure 11, and the picture of the prepared oxygen evolution electrode is shown in figure 12, and the performance of the prepared oxygen evolution electrode in a 1mol/L KOH solution for catalyzing oxygen evolution is shown in figure 12.
Example 6: the preparation contains 0.0055mol/L ZnCl2With 0.1mol/L NiCl2A piece of foamed nickel with the thickness of 1cm × 2cm is added into the aqueous solution of (1 cm) of (3), the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen evolution electrode is shown in figure 13, and the picture of the prepared oxygen evolution electrode is shown in figure 14, and the performance of the prepared oxygen evolution electrode in a 1mol/L KOH solution for catalyzing oxygen evolution is shown in figure 14.
Example 7: preparing MnCl containing 0.1mol/L2With 0.0031mol/L CoCl2A piece of foamed nickel with the thickness of 1cm × 2cm is added into the aqueous solution of (1 cm) of (3), the solution is soaked for 15 days, the electrode is taken out and washed and dried for standby application, the picture of the prepared oxygen evolution electrode is shown in figure 15, and the picture of the prepared oxygen evolution electrode is shown in figure 16, and the performance of the prepared oxygen evolution electrode in a 1mol/L KOH solution for catalyzing oxygen evolution is shown in figure 16.

Claims (13)

1. An oxygen evolving electrode characterized in that: the oxygen precipitation electrode takes foam metal as an electrode support body and a framework, flower-shaped microspheres self-assembled by a nano-sheet catalyst are uniformly loaded on the oxygen precipitation electrode, the catalyst is a double-metal hydroxide, or a compound of a first metal hydroxide and a second metal hydroxide, or a compound of the double-metal hydroxide and a hydroxide of one or two metals in double metals, the double-metal hydroxide is a hydroxide of any two of Ni, Fe, Co, Al, Zn and Mn, and one metal is 1-99% of the total molar content of the double metals calculated by the metal; the first metal hydroxide and the second metal hydroxide in the compound of the first metal hydroxide and the second metal hydroxide are respectively hydroxides of any one metal of Ni, Fe, Co, Al, Zn and Mn, the first metal and the second metal are different, and the first metal hydroxide is 1-99% of the total molar content of the two metal hydroxides;
the preparation method comprises the following steps: soaking the foam metal support body in a salt solution containing any two cations of Ni, Fe, Co, Al, Zn and Mn for 3-15 days; the difference in pH at which the two metal cations begin to hydrolytically precipitate is less than 2.
2. The oxygen evolving electrode according to claim 1, wherein: the thickness of the nano flaky catalyst is 10-100 nm; the diameter of the flower-shaped microspheres is 500nm-5 μm.
3. The oxygen evolving electrode according to claim 1 or 2, wherein: the thickness of the nano flaky catalyst is 10-50 nm; the diameter of the flower-shaped microspheres is 500nm-2 μm.
4. The oxygen evolving electrode according to claim 1, wherein: the loading capacity of the bimetal hydroxide in the oxygen precipitation electrode is 0.1-10mg/cm2(ii) a Or the loading capacity of the first metal hydroxide in the oxygen evolution electrode is 0.01-5mg/cm2The loading of the second metal hydroxide is 0.01-5mg/cm2。
5. The oxygen evolving electrode according to claim 1, wherein: the foam metal is one of foam nickel, foam iron nickel and foam copper; the thickness of the foam metal support body is 0.5-5 mm.
6. A method for producing an oxygen evolving electrode according to any one of claims 1 to 5, characterized in that: soaking the foam metal support body in a salt solution containing any two cations of Ni, Fe, Co, Al, Zn and Mn for 3-15 days; the difference in pH at which the two metal cations begin to hydrolytically precipitate is less than 2.
7. The method of producing an oxygen evolving electrode according to claim 6, wherein: the temperature range of the solution is 0-100 ℃.
8. The method of producing an oxygen evolving electrode according to claim 7, wherein: the temperature range of the solution is 30-90 ℃.
9. The method of producing an oxygen evolving electrode according to claim 8, wherein: the pH difference is less than 0.2.
10. The method for producing an oxygen evolving electrode according to claim 6 or 8, wherein: the concentration of the metal cations in the salt solution is 0.0001-1mol/L, and the total concentration of the two metal cations is 0.1-2 mol/L.
11. The method of producing an oxygen evolving electrode according to claim 6, wherein: the pH of the solution is in the range of 4-10.
12. The method of producing an oxygen evolving electrode according to claim 6, wherein: the pH of the solution is in the range of 6-8.
13. Use of an oxygen evolving electrode according to any of claims 1 to 5, wherein: the oxygen evolving electrode is useful as electrolyzed water, photo-electrolyzed water, a renewable fuel cell, or a rechargeable metal air cell.
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