CN115142085B - High-activity oxygen evolution electrode material with thermocatalytic effect and preparation method thereof - Google Patents

High-activity oxygen evolution electrode material with thermocatalytic effect and preparation method thereof Download PDF

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CN115142085B
CN115142085B CN202210834408.3A CN202210834408A CN115142085B CN 115142085 B CN115142085 B CN 115142085B CN 202210834408 A CN202210834408 A CN 202210834408A CN 115142085 B CN115142085 B CN 115142085B
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oxygen evolution
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metal sulfate
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CN115142085A (en
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王晓荣
刘中清
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Chengdu Wanrongda Technology Co ltd
Sichuan University
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Sichuan University
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Abstract

The invention discloses a high-activity oxygen evolution electrode material with a thermocatalytic effect and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) placing the metal substrate with the flat surface into a mixed aqueous solution of transition metal sulfate and alkali metal sulfate for self-assembly reaction, and heating the obtained substrate with the corroded surface in a reducing gas atmosphere at 400-600 ℃ for reduction reaction to obtain the electrode material. The electrode material has excellent electrocatalytic activity and stability, and has a thermocatalytic effect that the overpotential of oxygen evolution is obviously reduced along with the rise of the temperature of electrolyte.

Description

High-activity oxygen evolution electrode material with thermocatalytic effect and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts for hydrogen production by water electrolysis, and particularly relates to the technical field of catalysts for anodic oxygen evolution reaction.
Background
The electrolyzed water has the advantages of rich resources, renewable resources, effective utilization of clean energy sources such as wind power, photoelectricity, valley period water power and the like for electric hydrogen conversion, combination with fuel cells and the like, and is an important way for realizing hydrogen economy. The electrolyzed water comprises two half reactions of anodic oxygen evolution and cathodic hydrogen evolution, wherein the oxygen evolution reaction often becomes a dynamic limiting step due to the fact that four electrons are involved, and the two half reactions are main sources of high energy consumption and low efficiency in the electrolytic hydrogen production process.
Noble metals Ru and Ir-based compounds are considered as catalysts with optimal oxygen evolution performance, but large-scale industrialized application cannot be realized due to high price and scarce resources. Therefore, the development of non-noble metal catalysts with low oxygen evolution overpotential is an important research direction.
Among the non-noble metal oxygen evolution electrocatalysts, transition metals such as nickel and cobalt based catalysts exhibit high oxygen evolution electrocatalytic activity, but most of them reach 10mA cm -2 At current density, a high overpotential of 250-400 mV is still required, and the application effect is poor.
On the other hand, the anode surface modification method is one of the important methods for preparing oxygen evolution electrodes, and the method utilizes the oxide on the metal surface as an electrode active coating, wherein the electrochemical stability, thickness, morphology, magnetism, chemical bond structure, surface electronic structure, conductivity and the like of the oxide layer are main factors influencing the oxygen evolution performance. The current methods for preparing the anode active coating mainly comprise an electroplating method, a metal diffusion method, a thermal decomposition method and the like, and the active coating electrode prepared by the methods has the defects of short service life, complex preparation process and the like, and is difficult to meet industrial application.
In addition, in the actual process of producing hydrogen by electrolysis of water, there is a concern that the water electrolysis process is accompanied by a thermal effect which cannot be ignored even at a faraday efficiency of 100%, in the face of high current densities (500 to 1000mA cm -2 ) This effect is more pronounced when the temperature of the electrolysis system (including electrodes, separator, electrolyte, etc.) is increased to 50-90 ℃, which not only increases the power consumption of the hydrogen production by electrolysis, but also makes a serious test on the tolerance of the catalyst used. Most current research on water electrolysis electrocatalysts does not take into account their concomitant thermal effects or the effective use of other low-value thermal energy.
Disclosure of Invention
In view of the drawbacks of the prior art, an object of the present invention is to propose a highly active oxygen evolution electrode material with a thermocatalytic effect and a method for preparing the same, which can effectively utilize the thermal effect of electrolyzed water to enhance catalytic activity, the electrode material comprising an inexpensive current collector material, and an oxygen vacancy-rich layered transition metal oxide or hydroxide (LDH) active catalytic layer obtained by in-situ treatment on the current collector, which has excellent electrocatalytic activity and stability, and a thermocatalytic effect with a significantly reduced oxygen evolution overpotential as the temperature of the electrolyte increases.
The technical scheme of the invention is as follows:
the preparation method of the high-activity oxygen evolution electrode material with the thermocatalytic effect comprises the following steps:
placing a metal substrate with a flat surface into a mixed aqueous solution of transition metal sulfate and alkali metal sulfate for self-assembly reaction, and then cleaning and drying to obtain a substrate with a corroded surface;
heating the substrate with the corroded surface in a reducing gas atmosphere at 400-600 ℃ to perform a reduction reaction, so as to obtain the high-activity oxygen evolution electrode material with the thermocatalytic effect.
The preparation method has the advantages of simple and easy operation of the required equipment, large scale and low cost, meanwhile, electrolyte used in the preparation process does not contain any organic component, the active component and the current collector are tightly combined, and the preparation method not only has excellent electrocatalytic activity and stability, but also has excellent thermocatalytic effect, namely under the condition that other conditions are unchanged, the oxygen evolution overpotential is obviously reduced along with the temperature rise of the electrolyte.
The technical proposal can grow interlayer anions into SO on the surface of a metal substrate such as an iron sheet in situ through chemical corrosive self-assembly reaction 4 2- Layered transition metal oxides or hydroxides (LDHs) and then heat treated in a reducing atmosphere to give SO 4 2- Conversion to-SO 3 Obtaining interlayer grafting-SO 3 Electrode material of the group. For the four-electron process of water and electricity oxygen analysis, because of the high O-H rupture energy barrier, the-OH group in the adsorption state is directly connected with OH in the solution - Oxygen atom M-O in an adsorbed state is formed by reaction ads Often a rate limiting step. Thus, H on OH or OOH in the adsorbed state can be detected by the above + Producing capture-SO 3 The grafting of the groups can promote the rupture of O-H bonds in the oxygen evolution reaction process, thereby obviously reducing the oxygen evolution overpotential, the capturing effect has obvious thermocatalytic effect, the capturing capability is obviously enhanced along with the temperature rise, and the capturing effect has positive promotion effect on reducing the hydropower oxygen evolution overpotential at higher temperature.
Furthermore, the preparation method can form a proper amount of oxygen vacancies on the grafted LDH surface through the coordination and synergy of the corrosion reaction and the reduction reaction, so that the electrode material containing the LDH active ingredient prepared by the preparation method has high oxygen evolution activity and thermocatalytic performance, oxygen evolution overpotential is further reduced, and the electric energy utilization efficiency is improved.
Among them, the inventors have unexpectedly found that the oxygen evolution electrode material prepared by selecting the transition metal sulfate and the alkali metal sulfate has better oxygen evolution catalytic activity and thermal catalytic effect, lower production cost and higher environmental protection and innocuity compared with other anionic metal salts, and the preparation process is simpler.
According to the preparation process, transition metal perchlorate and alkali metal perchlorate are used as corrosive liquid, layered transition metal hydroxide (LDH) with perchlorate as intercalation anion is prepared, then alkali metal sulfate is used as exchange liquid, ion exchange is carried out on interlayer perchlorate into sulfate ion in an ion exchange mode, the same heating reduction reaction is carried out, and the obtained electrode material is also interlayer grafting-SO 3 The final performance of the electrode material of the group is slightly worse than that of the electrode material obtained by the preparation method, but the preparation process of the electrode material of the group needs expensive perchlorate and simultaneously increases the ion exchange step, the process is complicated, the time consumption is long, the preparation cost is high, and the process is not friendly to the environment due to the need of treating the wastewater containing the perchlorate.
According to some preferred embodiments of the invention, the substrate is selected from iron sheets.
The preferred embodiment has a selected substrate that is inexpensive and can be intimately combined with the active component formed thereon in situ to provide an electrode material having excellent electrocatalytic activity, stability and thermocatalytic effect.
According to some preferred embodiments of the invention, the self-assembly reaction is carried out at a temperature of 20 to 90 ℃ for a time of 0.5 to 6.0 hours.
According to some preferred embodiments of the invention, the concentration of the transition metal sulfate is 0.002 to 0.01mol/L and the concentration of the alkali metal sulfate is 0.01 to 0.1mol/L.
According to some preferred embodiments of the invention, the reducing gas is H 2 And Ar.
The inventors have unexpectedly found that when the reduction reaction is carried out under the reducing gas, relatively rich oxygen-containing vacancies can be formed on the surface of the electrode material, and the oxygen evolution reaction activity and the thermocatalytic effect can be enhanced.
According to some preferred embodiments of the invention, the H 2 And Ar is (10-50%) in volume ratio: (50-90%).
According to some preferred embodiments of the invention, the transition metal sulphate is selected from NiSO 4 And/or CoSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The alkali metal sulfate is selected from K 2 SO 4 And/or Na 2 SO 4 。
According to some preferred embodiments of the invention, the preparation method further comprises: pretreating the metal substrate, the pretreatment comprising: derusting and polishing the metal substrate by using an HCl solution, performing ultrasonic treatment by using ultrapure water for 5-30 minutes, and performing air cooling to obtain a pretreated substrate; and carrying out the self-assembly reaction on the pretreated substrate.
According to some preferred embodiments of the invention, the mixed aqueous solution comprises 0.002 to 0.01mol/L NiSO 4 、0.002～0.01mol/L CoSO 4 And 0.01 to 0.1mol/L K 2 SO 4 Or 0.01 to 0.1mol/LNa 2 SO 4 The temperature of the self-assembly reaction is 20-90 ℃ and the time is 0.5-6.0H, and the reducing gas comprises 10-50% of H by volume percent 2 And 50-90% Ar, wherein the temperature of the reduction reaction is 400-600 ℃ and the time is 0.5-3.0 hours.
More preferably, the mixed aqueous solution comprises 0.005mol/L NiSO 4 、0.005mol/L CoSO 4 And 0.05mol/L K 2 SO 4 The temperature of the self-assembly reaction is 75 ℃ and the time is 3 hours, and the reducing gas comprises 10 percent of H by volume 2 And 90% Ar, the temperature of the reduction reaction was 500℃for 1.5 hours.
In some embodiments, the electrode material obtained is at 40mA/cm 2 The overpotential of the current density decreases from 272mV to 235mV at 100mA/cm as the temperature increases from 25 ℃ to 75 DEG C 2 Density followingThe temperature was increased from 25 ℃ to 75 ℃ and the overpotential was reduced from 323mV to 270mV. 40mA/cm at 25 DEG C 2 The fluctuation of the electrode potential in the lower continuous operation for 48 hours is only 1.525+/-10 mV (relative to a standard hydrogen electrode), and the electrode has excellent thermocatalytic effect and stability.
The invention further provides the high-activity oxygen evolution electrode material prepared by the preparation method.
The electrode material contains tightly combined metal substrate current collector and self-assembled active ingredient generated on the current collector in situ, can obviously reduce the contact resistance between the active ingredient and the current collector, and can effectively ensure the stable performance of the electrode material in oxygen evolution reaction.
The invention has the following beneficial effects:
the metal substrate, especially iron sheet, prepared by the method of the invention is used as a current collector, and sulfonic acid-SO is grafted between layers 3 The oxygen-separating electrode with the functional group and oxygen vacancy-enriched double metal hydroxide as the active component can generate obvious thermocatalytic effect in alkaline electrolyte such as KOH, namely, the oxygen-separating overpotential of the oxygen-separating electrode is obviously reduced along with the increase of the electrolyte temperature under other conditions, so that the oxygen-separating electrode has lower oxygen-separating overpotential at higher electrolyte temperature compared with the LDH electrode of the same type.
In some embodiments of the invention, the electrode uses an iron sheet as a current collector, and compared with other substrates in the prior art, such as foam nickel, carbon paper, glassy carbon electrode and the like, the electrode has the advantages of higher mechanical strength, better conductivity and low price, and the preparation cost of the electrode per unit area is only 1/6-1/5 of that of the electrode in the prior art.
The preparation method adopts a chemical corrosion method for in-situ growth and reduction heat treatment, does not introduce any organic reagent into the electrolyte, has the advantages of mild reaction conditions, simple equipment and environmental friendliness, and has strong binding force between the active component and the substrate, low contact resistance, high electrocatalytic activity, difficult falling off under the cavitation effect of oxygen evolution and stable performance.
The preparation method disclosed by the invention is simple and feasible in process, low in equipment requirement, easy to realize large-scale preparation, and capable of obtaining the oxygen-evolving electrode which is high in cost performance, environment-friendly and obvious in thermal catalytic oxygen evolution effect.
The oxygen evolution electrode prepared by the invention has excellent performance, such as in some specific embodiments, the obtained electrode material takes 1M KOH as electrolyte, and the current density is 100mA/cm at 75 DEG C 2 The overpotential of (a) was only 271mV (85% solution resistance compensation), which was reduced by 53mV from 324mV at 25 ℃; at the time of stability test, it had a current density of 40mAcm at 25 DEG C -2 The continuous operation is carried out for 48 hours, the potential is maintained at-1.525V, the fluctuation range is within 10mV, and the high-stability high-voltage power supply has good stability.
Drawings
FIG. 1 is a graph showing the linear voltammograms of the electrode material obtained in example 1 at 25 ℃, 55 ℃ and 75 ℃.
FIG. 2 is a graph showing the linear voltammograms of the electrode material obtained in example 2 at 25 ℃, 55 ℃ and 75 ℃.
FIG. 3 shows the electrode material obtained in example 2 at 25℃and 40mA/cm 2 Electrode potential fluctuation graph for 48 hours of continuous operation.
FIG. 4 is a graph showing the linear voltammograms of the electrode material obtained in example 3 at 25 ℃, 55 ℃ and 75 ℃.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
According to the technical scheme of the invention, some specific embodiments of the preparation method of the high-activity oxygen evolution electrode material with the thermocatalytic effect comprise the following steps:
(1) Pretreatment of the substrate, such as acid washing, polishing, water washing, drying and the like of the substrate; the substrate is preferably a relatively low cost sheet metal material, such as iron;
(2) The pretreated base material is subjected to chemical corrosion self-assembly treatment, which comprises the steps of placing the pretreated base material in a mixed water solution of transition metal sulfate and alkali metal sulfate, corroding for 0.5 to 6.0 hours at the temperature of 20 to 90 ℃, and then cleaning and drying to obtain the corroded base material;
(3) Subjecting the post-etch substrate to a reduction heat treatment comprising: and heating the corroded substrate in a reducing gas atmosphere to perform a reduction reaction, thereby obtaining the high-activity oxygen evolution electrode.
Some more specific embodiments are as follows:
the pretreatment of the step (1) comprises: the substrate is subjected to rust removal and polishing for 10 to 30 seconds by using an HCl solution, then subjected to ultrasonic treatment by using ultrapure water for 5 to 30 minutes, and then subjected to air cooling, so that the pretreated substrate is obtained. The concentration of the HCl solution is preferably 2.5 to 3.5mol/L.
In step (2), the transition metal sulfate is selected from nickel sulfate and/or cobalt sulfate.
In step (2), the alkali metal sulfate is selected from potassium sulfate and/or sodium sulfate.
In the step (2), the concentration of the transition metal sulfate is preferably 0.002 to 0.01mol/L.
In the step (2), the concentration of the alkali metal sulfate is preferably 0.01 to 0.1mol/L.
In the step (3), the volume ratio of the reducing gas is (10-50%): (50-90%) H 2 And Ar.
In the step (3), the temperature of the reduction reaction is 400-600 ℃ and the time is 0.5-3 hours.
The oxygen-evolving electrode produced in the above manner is suitable as an electrolytic water oxygen-evolving anode in an alkaline electrolyte such as KOH or NaOH aqueous solution.
The technical scheme of the invention is further shown by examples below.
Example 1
The electrode material is prepared by the steps of:
step one: rust removal and polishing pretreatment of iron sheets:
polishing an iron sheet with the thickness of 0.3mm in 3mol/L HCl for 15s, taking out, repeatedly washing with ultrapure water, washing in the ultrapure water for 10 minutes again, taking out, drying with cold air, and reserving;
step two: chemical corrosion:
preparation of 0.005mol/LNiSO 4 And 0.05mol/L K 2 SO 4 Suspending the polished iron sheet in the corrosive liquid, controlling the temperature of the corrosive liquid to be 25 ℃ and the time to be 6 hours, taking out the sample, repeatedly washing the sample with ultrapure water, and drying the sample with cold air for later use;
step three: reduction heat treatment:
placing the iron sheet after chemical corrosion in a tube furnace, and adding H with the volume ratio of 20% 2 And 80% Ar, heat treating for 2 hours at 450 ℃, naturally cooling and taking out to obtain the electrode material.
The obtained electrode material is used as a working electrode, a graphite sheet is used as a counter electrode, a saturated Hg/HgO is used as a reference electrode to form a three-electrode system, and 1mol/L KOH aqueous solution is used as electrolyte, and linear volt-ampere tests are respectively carried out at 25 ℃, 55 ℃ and 75 ℃. The results are shown in FIG. 1 (85% solution resistance compensation). As can be seen, the electrode material was at 10mA/cm 2 Overpotential at current density was 269mV, 227mV and 208mV, respectively, at 100mA/cm 2 The overpotential at current density was 375mV, 342mV and 274mV, respectively.
Example 2
The electrode material is prepared by the steps of:
step one: rust removal and polishing pretreatment of iron sheets:
polishing an iron sheet with the thickness of 0.3mm in 3mol/L HCl for 25s, taking out, repeatedly washing with ultrapure water, washing in the ultrapure water for 25 minutes again, taking out, drying with cold air, and reserving;
step two: chemical corrosion:
preparation of 0.005mol/LNiSO 4 And 0.005mol/L CoSO 4 And 0.05mol/L K 2 SO 4 The aqueous solution of (2) is etching solution, the iron sheet after polishing pretreatment is suspended in the etching solution, and the etching is controlledThe temperature of the liquid is 75 ℃ and the time is 3 hours, and after taking out the sample, the sample is repeatedly washed by ultrapure water and dried by cold air for standby;
step three: reduction heat treatment:
placing the chemically corroded iron sheet into a tube furnace, wherein the volume ratio of the iron sheet to the tube furnace is 10% H 2 And 90% Ar, and carrying out heat treatment for 1.5 hours at 500 ℃, and taking out after naturally cooling to obtain the electrode material.
The obtained electrode material is used as a working electrode, a graphite sheet is used as a counter electrode, a saturated Hg/HgO is used as a reference electrode to form a three-electrode system, and 1mol/L KOH aqueous solution is used as electrolyte, and linear volt-ampere tests are respectively carried out at 25 ℃, 55 ℃ and 75 ℃. The results are shown in FIG. 2 (85% solution resistance compensation), and it can be seen that the electrode material was at 40mA/cm 2 The overpotential at the current density was 272mV, 252mV and 235mV, respectively, at 100mA/cm 2 The overpotential at the current density was 323mV, 296mV and 270mV, respectively. It was 40mA/cm at 25 ℃ 2 The electrode potential fluctuation for the next 48 hours of continuous operation was 1.525.+ -. 10mV (relative to the standard hydrogen electrode), as shown in FIG. 3.
Example 3
The electrode material is prepared by the steps of:
step one: rust removal and polishing pretreatment of iron sheets:
polishing an iron sheet with the thickness of 0.3mm in 3mol/L HCl for 20s, taking out, repeatedly washing with ultrapure water, washing in the ultrapure water for 20 minutes again, taking out, drying with cold air, and reserving;
step two: chemical corrosion:
preparation of 0.01mol/L CoSO 4 And 0.1mol/L Na 2 SO 4 Suspending the polished iron sheet in the corrosive liquid, controlling the temperature of the corrosive liquid to be 55 ℃ and the time to be 5 hours, taking out the sample, repeatedly washing the sample with ultrapure water, and drying the sample with cold air for later use;
step three: reduction heat treatment:
placing the chemically corroded iron sheet into a tube furnace, wherein the volume ratio of the iron sheet to the tube furnace is 10% H 2 And 90% Ar, heat treating at 500 deg.C for 1.5 hr, naturallyAnd cooling and taking out to obtain the electrode material.
The obtained electrode material is used as a working electrode, a graphite sheet is used as a counter electrode, a saturated Hg/HgO is used as a reference electrode to form a three-electrode system, and 1mol/L KOH aqueous solution is used as electrolyte, and linear volt-ampere tests are respectively carried out at 25 ℃, 55 ℃ and 75 ℃. The results are shown in FIG. 4 (85% solution resistance compensation), which can be seen at 40mA/cm 2 The overpotential at the current density was 308mV, 269mV and 249mV, respectively, at 100mA/cm 2 The overpotential at the current density was 368mV, 332mV and 274mV, respectively.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims (8)

1. The preparation method of the high-activity oxygen evolution electrode material with the thermocatalytic effect is characterized by comprising the following steps of:
placing a metal substrate with a flat surface into a mixed aqueous solution of transition metal sulfate and alkali metal sulfate for self-assembly reaction, wherein the temperature of the self-assembly reaction is 20-90 ℃ and the time is 0.5-6.0 hours, and then cleaning and drying the metal substrate to obtain a substrate with a corroded surface;
heating the substrate with the corroded surface in a reducing gas atmosphere at 400-600 ℃ to perform a reduction reaction to obtain the high-activity oxygen evolution electrode material with the thermocatalytic effect;
wherein the transition metal sulfate is selected from NiSO 4 And/or CoSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The alkali metal sulfate is selected from K 2 SO 4 And/or Na 2 SO 4 。
2. The method of claim 1, wherein the substrate is selected from the group consisting of iron sheets.
3. The method according to claim 1, wherein the concentration of the transition metal sulfate is 0.002 to 0.01mol/L, and the concentration of the alkali metal sulfate is 0.01 to 0.1mol/L.
4. The method according to claim 1, wherein the reducing gas is H 2 And Ar.
5. The method according to claim 4, wherein H is 2 And Ar is (10-50%) in volume ratio: (50-90%).
6. The method of manufacturing according to claim 1, further comprising: pretreating the metal substrate, the pretreatment comprising: derusting and polishing the metal substrate by using an HCl solution, performing ultrasonic treatment by using ultrapure water for 5-30 minutes, and performing air cooling to obtain a pretreated substrate; and carrying out the self-assembly reaction on the pretreated substrate.
7. The method according to claim 1, wherein the mixed aqueous solution comprises 0.002-0.01 mol/L NiSO 4 、0.002~0.01 mol/L CoSO 4 And 0.01 to 0.1mol/L K 2 SO 4 Or 0.01 to 0.1mol/L Na 2 SO 4 The temperature of the self-assembly reaction is 20-90 ℃ and the time is 0.5-6.0H, and the reducing gas comprises 10-50% of H by volume percent 2 And 50-90% Ar, wherein the temperature of the reduction reaction is 400-600 ℃ and the time is 0.5-3.0 hours.
8. The high-activity oxygen evolution electrode material with the thermocatalytic effect prepared by the preparation method according to any one of claims 1-7.
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