阅读说明：本技术 非晶氧化钌薄膜包覆泡沫镍复合电极及其制备方法和应用 (Amorphous ruthenium oxide film coated foam nickel composite electrode and preparation method and application thereof ) 是由 乔梁 贺靖轩 于 2019-11-15 设计创作，主要内容包括：本发明提供了一种非晶氧化钌薄膜包覆泡沫镍复合电极及其制备方法和应用，制备方法包括以下步骤：将泡沫镍基底超声清洗，干燥得清洗后泡沫镍基底；然后固定在脉冲激光沉积系统样品台上，以氧化钌为靶材，在氧分压和激光能量密度恒定条件下，预烧灼，然后取下挡板沉积，在氮气气氛下取出样品，得氧化钌薄膜包覆泡沫镍复合电极。本发明还包括非晶氧化钌薄膜包覆泡沫镍复合电极在空气电池中的应用。本发明通过激光脉冲在泡沫镍基底上沉积生长非晶氧化钌，所得电极材料结合力高，稳定性好，并将电极材料应用于金属?空气电池中，不易腐蚀脱落，有效解决了复合电极结合力低稳定性差、反应时易腐蚀脱落、活性位被包覆导致利用率降低的问题。(The invention provides an amorphous ruthenium oxide film coated foam nickel composite electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: ultrasonically cleaning the foamed nickel substrate, and drying to obtain a cleaned foamed nickel substrate; and then fixing the electrode on a sample table of a pulse laser deposition system, pre-burning and burning the electrode under the conditions of constant oxygen partial pressure and constant laser energy density by taking ruthenium oxide as a target, then taking down a baffle for deposition, and taking out a sample under the nitrogen atmosphere to obtain the ruthenium oxide film coated foamed nickel composite electrode. The invention also comprises the application of the amorphous ruthenium oxide film coated foam nickel composite electrode in the air battery. The amorphous ruthenium oxide is deposited and grown on the foamed nickel substrate through laser pulse, the obtained electrode material has high binding force and good stability, and the electrode material is applied to a metal-air battery and is not easy to corrode and fall off, so that the problems of low binding force and poor stability of a composite electrode, easy corrosion and fall off during reaction and reduced utilization rate caused by coating of active sites are effectively solved.)

1. The preparation method of the amorphous ruthenium oxide film coated foam nickel composite electrode is characterized by comprising the following steps:

(1) ultrasonically cleaning a foamed nickel substrate in acetone, absolute ethyl alcohol and 4-6 vt% dilute sulfuric acid for 20-40 min in sequence, washing with deionized water for 2-4 times, and vacuum-drying at 50-70 ℃ for 11-13 h to obtain a cleaned foamed nickel substrate;

(2) fixing the foamed nickel substrate cleaned in the step (1) on a sample table of a pulse laser deposition system, starting a pulse laser under the conditions of constant oxygen partial pressure and laser energy density by taking ruthenium oxide as a target material, pre-burning for 2-5 min, then taking down a baffle for deposition for 30-90 min, and taking out a sample under a nitrogen atmosphere to obtain the ruthenium oxide film coated foamed nickel composite electrode.

2. The method for preparing the amorphous ruthenium oxide film-coated foamed nickel composite electrode according to claim 1, wherein the distance between the foamed nickel substrate and the target material is 50-80 mm.

3. The method for preparing the amorphous ruthenium oxide film-coated foamed nickel composite electrode according to claim 1, wherein in the step (2), the oxygen partial pressure is 1 component10^-4100Pa, and the laser energy density is 0.5-2J/cm²。

4. The amorphous ruthenium oxide film-coated foamed nickel composite electrode prepared by the preparation method of the amorphous ruthenium oxide film-coated foamed nickel composite electrode according to any one of claims 1 to 3.

5. The use of the amorphous ruthenium oxide film-coated nickel foam composite electrode according to claim 4 in the preparation of an air battery.

6. An air battery comprising the amorphous ruthenium oxide thin film coated nickel foam composite electrode according to claim 4.

7. The air cell of claim 6, further comprising a counter electrode and a reference electrode.

8. The air battery of claim 7, wherein the counter electrode is a platinum electrode; the reference electrode is a calomel electrode, an Hg/HgO electrode or an Ag/AgCl electrode.

9. The method of manufacturing an air battery according to claim 6, comprising the steps of: and fixing the ruthenium oxide film coated foam nickel composite electrode on a stainless steel electrode to form a working electrode, assembling the working electrode, a counter electrode and a reference electrode into a battery, and injecting electrolyte to obtain the air battery.

10. The method of claim 9, wherein the electrolyte is a potassium hydroxide solution having a concentration of 0.1 to 1 mol/L.

Technical Field

The invention belongs to the technical field of composite electrodes, and particularly relates to an amorphous ruthenium oxide film-coated foam nickel composite electrode and a preparation method and application thereof.

Background

A rechargeable metal-air battery is a device that converts chemical energy into electrical energy. During discharge, the metal is oxidized at the anode to produce electrons and protons, which pass throughThe external circuit reaches the cathode where oxygen is reduced to form O^2-(oxygen reduction, ORR) to form an external current path to provide electrical energy. During charging, the metal ions are reduced and deposited on the anode, H₂O is oxidized at the cathode to form O₂(oxygen evolution, OER), thereby completing the charging process. The cathode in a rechargeable metal-air battery is generally formed by pressing three parts, namely a catalyst layer, a current collector and an air diffusion layer. The catalyst layer is composed of an active catalyst having a charging function or a discharging function, and is a core part for realizing charging and discharging. The current collector is composed of a metal substrate having excellent conductive properties, and is a member responsible for conducting electrons generated by a catalytic reaction to an external circuit. The air diffusion layer is made of a breathable and water-impermeable highly hydrophobic material and is a key component responsible for providing an oxygen passage and protecting the electrolyte.

Research shows that the nickel-based ruthenium oxide composite electrode has been subjected to preliminary research in the field of electrocatalysis, and is mainly applied to ethanol oxidation and Hydrogen Evolution Reaction (HER), while the research on the catalytic decomposition of water to Oxygen (OER) of the metal-air battery anode is less. In particular, the conventional reports and patents have focused on "crystalline ruthenium oxide composite nickel", and relatively few studies have been made on "amorphous ruthenium oxide composite nickel". The amorphous ruthenium oxide film coated foam nickel has better catalytic activity, adaptability and durability in an alkaline solution, can effectively catalyze and promote the OER reaction, and realizes quick charging.

At present, the air electrode catalyst is prepared by chemical preparation processes such as an impregnation method, a sol-gel method, chemical vapor deposition, electrodeposition and the like, and the composite material prepared by the processes cannot effectively realize the compounding between the catalyst layer and the current collector, so that the binding force between the catalyst and the current collector is low, and the stability is poor. Most of the catalysts currently used need to be supported on the surface of the current collector by a binder and conductive carbon. If the above-described technology is used as an OER catalyst in a metal-air battery, when an oxygen evolution reaction occurs, a large amount of oxygen is generated on the surface of the catalyst so that it is corroded, thereby causing a serious consequence of catalyst falling. Meanwhile, the introduction of organic components such as adhesives can lead to the coating of active sites on the surface of the catalyst, lead to the partial inactivation of the catalyst and reduce the utilization rate of the catalyst.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides an amorphous ruthenium oxide film-coated foamed nickel composite electrode and a preparation method and application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the amorphous ruthenium oxide film coated foam nickel composite electrode comprises the following steps:

(1) ultrasonically cleaning a foamed nickel substrate in acetone, absolute ethyl alcohol and 4-6 vt% dilute sulfuric acid for 20-40 min in sequence, washing with deionized water for 2-4 times, and vacuum-drying at 50-70 ℃ for 11-13 h to obtain a cleaned foamed nickel substrate;

(2) fixing the foamed nickel substrate cleaned in the step (1) on a sample table of a pulse laser deposition system, starting a pulse laser under the conditions of constant oxygen partial pressure and laser energy density by taking ruthenium oxide as a target material, pre-burning for 2-5 min, then taking down a baffle for deposition for 30-90 min, and taking out a sample under a nitrogen atmosphere to obtain the ruthenium oxide film coated foamed nickel composite electrode.

Further, the distance between the foamed nickel substrate and the target material is 50-80 mm.

Further, in the step (2), the oxygen partial pressure was 1X 10^-4100Pa, and the laser energy density is 0.5-2J/cm²。

Further, the specification of the foamed nickel substrate is 10mm × 10mm × 0.5 mm.

The amorphous ruthenium oxide film-coated foam nickel composite electrode prepared by the preparation method of the amorphous ruthenium oxide film-coated foam nickel composite electrode is provided.

The amorphous ruthenium oxide film coated foam nickel composite electrode is applied to the preparation of an air battery.

An air battery comprises the amorphous ruthenium oxide film coated foam nickel composite electrode.

Further, the device also comprises a counter electrode and a reference electrode.

Further, the counter electrode is a platinum electrode; the reference electrode is a calomel electrode, an Hg/HgO electrode or an Ag/AgCl electrode.

The preparation method of the air battery comprises the following steps: and fixing the ruthenium oxide film coated foam nickel composite electrode on a stainless steel electrode to form a working electrode, assembling the working electrode, a counter electrode and a reference electrode into a battery, and injecting electrolyte to obtain the air battery.

Further, the electrolyte is a potassium hydroxide solution with the concentration of 0.1-1 mol/L.

In summary, the invention has the following advantages:

1. according to the invention, the amorphous ruthenium oxide film is deposited and grown on the foamed nickel substrate through laser pulse, the obtained amorphous ruthenium oxide film coated foamed nickel composite electrode has high binding force and good stability, and the electrode material is applied to a metal-air battery to be used as an OER catalyst, when an oxygen precipitation reaction occurs, the electrode material cannot fall off due to corrosion, an active site on the surface cannot be coated in the reaction process, partial inactivation of the catalyst is prevented, the utilization rate of the catalyst is improved, and the problems of low binding force and poor stability of the composite electrode, easiness in corrosion and falling off and reduced utilization rate caused by coating of the active site are effectively solved.

2. During preparation, high-energy and high-frequency laser generated by the pulse laser is focused on the surface of the target through the lens group, the target is excited to generate directional plasma under the action of high temperature and corrosion on the surface of the target, and a thin film is formed on a substrate at a certain distance. The film grown by the method has the same height with the target material, the elements in the film are uniformly distributed, the surface of the film is smoother, the thickness of the film is uniform, the combination is tight, and the service performance of the film is better.

3. The preparation method provided by the invention is simple, the raw material source is rich, the foam nickel substrate can be directly purchased in the market, the ruthenium oxide target can be repeatedly used for many times, the obtained composite electrode has excellent conductivity, the catalyst is directly coated on the surface of the current collecting layer, the stability is good, more catalysts participating in oxygen precipitation reaction under the geometric area of the fixed electrode are available, the electrochemical active surface area is large, and the OER performance is excellent.

Drawings

FIG. 1 is a cyclic voltammetry curve of the catalytic activity of the ruthenium oxide film coated foam nickel composite electrode OER reaction;

FIG. 2 is a linear voltammetry curve of the catalytic activity of the ruthenium oxide film coated foam nickel composite electrode OER reaction;

FIG. 3 is a cyclic voltammetry curve of a double-layer capacitor of a ruthenium oxide film-coated foam nickel composite electrode;

FIG. 4 is a schematic diagram of the double layer capacitance of the ruthenium oxide film-coated nickel foam composite electrode.

Detailed Description