CN109030587B - Application of antimony-lead anodic oxidation composite reference electrode in high-concentration sulfuric acid system - Google Patents
Application of antimony-lead anodic oxidation composite reference electrode in high-concentration sulfuric acid system Download PDFInfo
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- CN109030587B CN109030587B CN201810416483.1A CN201810416483A CN109030587B CN 109030587 B CN109030587 B CN 109030587B CN 201810416483 A CN201810416483 A CN 201810416483A CN 109030587 B CN109030587 B CN 109030587B
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Abstract
The invention discloses an application of an antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system, which comprises an electrode body consisting of metal antimony and metal lead and an oxide film formed on the electrode body, wherein metal antimony powder and metal lead powder are mixed, heated and melted, and are placed into a mold for cooling and forming, and then an anodic oxidation method is adopted to generate a layer of compact oxide film on the surface of the electrode. Compared with an antimony electrode, the composite electrode has the advantages that the potential of the battery can be stably indicated in strong acid, the stability of the electrode can be guaranteed not to be affected by the fact that the electrode does not react with other substances in a system, and the stability of the electrode can be further improved due to the generated compact oxide film.
Description
The invention relates to a divisional application of a parent application 'antimony-lead anodic oxidation composite reference electrode and a preparation method and application thereof', wherein the parent application has an application number of 2015102877031 and an application number of 2015, 5 and 29.
Technical Field
The invention belongs to the field of battery material science, and particularly relates to an antimony-lead anodic oxidation composite reference electrode applicable to a concentrated sulfuric acid system and a preparation method thereof.
Background
With the rapid development of new power supplies such as electronic and communication equipment, electric automobiles, wind power generation and the like, people have higher and higher requirements on batteries of matched power supplies, and the development of power batteries and energy storage batteries is urgently needed.
The all-vanadium redox flow battery has the characteristics of mutual independence of power output and energy storage, quick response, high power output, safe, stable and easily maintained system and environmental friendliness, and draws the attention of scholars at home and abroad. At present, all-vanadium flow batteries have been successfully applied in wind energy, solar energy utilization and power grid peak shaving, the application market is worldwide, and the assembly of all-vanadium battery stacks is going to the megawatt marching. At present, reference electrodes for detecting the charge state of the all-vanadium redox flow battery are mainly silver/silver chloride electrodes, however, electrolyte of positive and negative electrodes in the all-vanadium redox flow battery contains concentrated sulfuric acid with high concentration (more than 3 mol/L), which can cause the potential of the silver/silver chloride reference electrode to be unstable, and therefore, the preparation of the reference electrode with stable potential in a concentrated sulfuric acid system is especially important.
When the metal antimony is contacted with the solution, reversible redox reaction is generated on a contact surface, and the ion migration on an interface forms a potential difference, wherein the difference is related to the concentration of hydrogen ions in the solution. The chemical property of antimony determines that when the antimony is in an aqueous solution, the surface can react with water in a trace amount, so that the surface is quickly covered with a layer of antimony trioxide (Sb) 2O3) The potential of the antimony electrode is generated between the metallic antimony and the antimony oxide, and the potential is determined by the concentration of antimony trioxide, which is in turn determined by the activity (pH value) of hydrogen ions in the solution to be measured, so that the antimony electrode can be practically used as a pH electrode.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and design a composite reference electrode which can be stably applied to a concentrated sulfuric acid system. Compared with an antimony electrode, the composite electrode has the advantages that the potential of the battery can be stably indicated in strong acid, and the electrode can be prevented from reacting with other substances in a system to influence the stability of the electrode. An anodic oxidation method can be adopted to generate a layer of compact oxide film on the surface of the electrode, thereby improving the stability of the electrode.
The technical purpose of the invention is realized by the following technical scheme:
antimony-lead anodic oxidation composite reference electrode, comprising an electrode body consisting of metal antimony and metal lead, and an oxide film formed on the electrode body, wherein:
the electrode body is prepared according to the following method: uniformly mixing metal antimony powder and metal lead powder, heating to 650-750 ℃, and keeping the temperature for 20-40 min to melt a mixture of the two kinds of powder; transferring the molten powder mixture into a mold for cooling; the mass portion ratio of the metal antimony powder to the metal lead powder is (85-95): (5-15);
The oxide thin film is prepared according to the following method: preparing a sulfuric acid aqueous solution as an electrolyte, taking an electrode body as a working electrode, taking a mercurous sulfate electrode as a reference electrode and taking a platinum electrode as a counter electrode, carrying out anodic oxidation to form an oxide film on the electrode body, wherein the applied potential is 500-700mV, and the applied time is 5-24 h.
In the technical scheme, the mass parts of the metal antimony powder and the metal lead powder are (90-95): (5-10).
In the technical scheme, in the preparation of the electrode body, the heating is selected to be 680-700 ℃, and the heat preservation time is 25-35 min.
In the technical scheme, in the preparation of the oxide film, the applied potential is 550-680mV, and the applied time is 10-20 h.
In the technical scheme, in the preparation of the oxide film, the concentration of sulfuric acid in the sulfuric acid aqueous solution used as the electrolyte is 3-5 mol/L.
In the technical scheme, an acid-resistant coating material, such as a cross-linked PE compound, or a PE film, a PP film and a PVC film, is selectively arranged on the surface of the electrode body.
The preparation method of the antimony-lead anodic oxidation composite reference electrode comprises the following steps:
step 1, uniformly mixing metal antimony powder and metal lead powder, heating to 650-750 ℃, and keeping the temperature for 20-40 min to melt a mixture of the two kinds of powder; transferring the melted powder mixture into a mould to be cooled to form an electrode body; the mass portion ratio of the metal antimony powder to the metal lead powder is (85-95): (5-15);
And 2, preparing a sulfuric acid aqueous solution as an electrolyte, taking an electrode body as a working electrode, taking a mercurous sulfate electrode as a reference electrode and taking a platinum electrode as a counter electrode, carrying out anodic oxidation to form an oxide film on the electrode body, wherein the applied potential is 500-700mV, and the application time is 5-24 h.
In the technical scheme, the mass parts of the metal antimony powder and the metal lead powder are (90-95): (5-10).
In the technical scheme, in the preparation of the electrode body, the heating is selected to be 680-700 ℃, and the heat preservation time is 25-35 min.
In the technical scheme, in the preparation of the oxide film, the applied potential is 550-680mV, and the applied time is 10-20 h.
In the technical scheme, in the preparation of the oxide film, the concentration of sulfuric acid in the sulfuric acid aqueous solution used as the electrolyte is 3-5 mol/L.
In the technical scheme, an acid-resistant coating material, such as a cross-linked PE compound, or a PE film, a PP film and a PVC film, is selectively arranged on the surface of the electrode body.
The application of the antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system.
The concentration of the sulfuric acid in the high-concentration sulfuric acid system is 3-5 mol/L.
The high-concentration sulfuric acid system is an electrolyte system of the all-vanadium redox flow battery.
As shown in the attached figure 1, the potential time curve of the test under the system of using the lead-antimony anodic oxidation composite electrode of the invention as a working electrode, using the mercurous sulfate electrode as a reference electrode and using the test solution as a 3M sulfuric acid solution is tested by using a PARSTAT2273 electrochemical workstation of American atlas Limited company, the potential is stable at-0.508 +/-0.02 volt (relative to the mercurous sulfate reference electrode) after 2500s, which shows that the potential of the electrode of the invention can be stable in a pure 3M sulfuric acid solution.
As shown in the attached figure 2, the test is carried out by utilizing a PARSTAT2273 electrochemical workstation of America, Inc., taking the electrode as a working electrode, a platinum electrode as a reference electrode, a test solution as a cathode electrolyte of an all-vanadium flow battery and a component of V2+(divalent vanadium ion) V3+(vanadium triion), 3M sulfuric acid, V thereof2+、V3+The components of (a) change with the change of the battery capacity, and the potential time curve of the electrode of the invention is tested in the system, so that the potential of the electrode is kept stable after 1700s of testThe voltage is set to be 0.1 +/-0.02 volt, which shows that the electrode not only can be used as a stable reference electrode in a pure 3M sulfuric acid solution, but also can be used as a reference electrode in a vanadium battery cathode electrolyte.
As shown in the attached figure 3, the test is carried out by utilizing a PARSTAT2273 electrochemical workstation of America, Inc., the electrode of the invention is taken as a working electrode, a platinum electrode is taken as a reference electrode, a test solution is an all-vanadium redox flow battery negative electrolyte, and a single-motor charge-discharge curve is measured in the system, wherein as can be seen in the figure, V is measured during the charging process3+To obtain an electron reaction of V2+The battery voltage decreases linearly with the increase of the charging time, during the discharge, V2+Electron-losing reaction of V3+The cell voltage increases linearly with the discharge time.
As can be seen from the above description, the composite electrode of the present invention has advantages over an antimony electrode in that it can both stabilize the potential of the indicating cell in a strong acid and ensure that the electrode itself does not react with other substances in the system to affect the stability of the electrode. An anodic oxidation method can be adopted to generate a layer of compact oxide film on the surface of the electrode, thereby improving the stability of the electrode.
Drawings
FIG. 1 is a time potential curve of the antimony-lead anodic oxidation composite electrode of the present invention in 3M concentrated sulfuric acid (the reference electrode is a mercurous sulfate electrode);
FIG. 2 is a potential time curve of the antimony-lead anodic oxidation composite electrode in the electrolyte of the all vanadium flow battery (the reference electrode is a platinum electrode);
FIG. 3 is a charge-discharge curve of the lead-antimony anodic oxidation composite electrode in the electrolyte of the all-vanadium redox flow battery.
Detailed Description
The technical scheme of the invention is further explained by combining the specific embodiment; the cross-linked PE was purchased from Kaishuan digital private store (online shopping) created in Beijing.
Example 1
Weighing 95:5 antimony powder and lead powder in a container, grinding for 30 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 750 ℃, and the heat preservation time is 20 min;
taking a 15cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
And preparing a 3M sulfuric acid solution as an electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 500mV, and the applied time is 5 hours.
Example 2
Weighing 85:15 antimony powder and lead powder in a container, grinding for 45 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 650 ℃, and the heat preservation time is 40 min;
taking a conductive wire with the length of 20cm, coating off a paint coat, clamping the conductive wire in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 5M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 700mmV, and the application time is 24 hours.
Example 3
Weighing 90:10 antimony powder and lead powder in a container, grinding for 35 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 700 ℃, and the heat preservation time is 25 min;
taking a 15cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 4M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 550mV, and the applied time is 10 h.
Example 4
Weighing 95:5 antimony powder and lead powder in a container, grinding for 40 minutes, pouring the ground sample into a crucible, moving into an electric furnace to heat, wherein the heating temperature is 680 ℃, and the heat preservation time is 35 min;
taking a 18cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
And preparing a 3M sulfuric acid solution as an electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 500mV, and the applied time is 5 hours.
Example 5
Weighing 85:15 antimony powder and lead powder in a container, grinding for 30 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 650 ℃, and the heat preservation time is 20 min;
taking a conductive wire with the length of 20cm, coating off a paint coat, clamping the conductive wire in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 5M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 700mV, and the applied time is 20 hours.
Example 6
Weighing 90:10 antimony powder and lead powder in a container, grinding for 40 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 750 ℃, and the heat preservation time is 25 min;
taking a 15cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 4M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 600mV, and the applied time is 15 h.
Example 7
Weighing 95:5 antimony powder and lead powder in a container, grinding for 35 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 700 ℃, and the heat preservation time is 30 min;
taking a 18cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 5M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode and taking a platinum electrode as a counter electrode, and carrying out anodic oxidation with the applied potential of 550mV and the applied time of 22 h.
Example 8
Weighing 85:15 antimony powder and lead powder in a container, grinding for 40 minutes, pouring the ground sample into a crucible, moving into an electric furnace for heating, wherein the heating temperature is 750 ℃, and the heat preservation time is 35 min;
taking a 15cm long conductive wire, coating off a paint coat, clamping in a specific mold, taking out a melted sample from an electric furnace, pouring the melted sample into the mold, taking out the melted sample after cooling, and covering with an acid-resistant coating material.
Preparing 4M sulfuric acid solution as electrolyte, taking the prepared electrode as a working electrode, taking a mercurous sulfate electrode as a reference electrode, taking a platinum electrode as a counter electrode, and carrying out anodic oxidation, wherein the applied potential is 650mV, and the applied time is 17 hours.
Electrochemical performance tests were conducted using the examples of examples 1-8 above and exhibited substantially the same properties as shown in figures 1-3.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (4)
1. The application of the antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system is characterized in that the high-concentration sulfuric acid system is an electrolyte system of an all-vanadium redox flow battery, and the concentration of sulfuric acid in the high-concentration sulfuric acid system is 3-5 mol/L; the antimony-lead anodic oxidation composite reference electrode comprises an electrode body consisting of metal antimony and metal lead, and an oxide film formed on the electrode body, wherein: the electrode body is prepared according to the following method: uniformly mixing metal antimony powder and metal lead powder, heating to 650-750 ℃, and keeping the temperature for 20-40 min to melt a mixture of the two kinds of powder; transferring the molten powder mixture into a mold for cooling; the mass portion ratio of the metal antimony powder to the metal lead powder is (85-95): (5-15);
The oxide thin film is prepared according to the following method: preparing a sulfuric acid aqueous solution as an electrolyte, taking an electrode body as a working electrode, taking a mercurous sulfate electrode as a reference electrode and taking a platinum electrode as a counter electrode, carrying out anodic oxidation to form an oxide film on the electrode body, wherein the applied potential is 500-700mV, the applied time is 5-24 h, and the concentration of sulfuric acid in the sulfuric acid aqueous solution as the electrolyte is 3-5 mol/L.
2. The application of the antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system according to claim 1 is characterized in that the mass parts of the metal antimony powder and the metal lead powder are (90-95): (5-10).
3. The application of the antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system according to claim 1 is characterized in that in the preparation of an electrode body, the temperature is selectively heated to 680-700 ℃, and the heat preservation time is 25-35 min.
4. The application of the antimony-lead anodic oxidation composite reference electrode in a high-concentration sulfuric acid system according to claim 1, wherein in the preparation of the oxide film, the applied potential is 550-680mV, and the application time is 10-20 h.
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| CN201510287703.1A CN106290504B (en) | 2015-05-29 | 2015-05-29 | Antimony lead anodic oxidation composite reference electrode and its preparation method and application |
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| CN100422728C (en) * | 2006-03-28 | 2008-10-01 | 浙江大学 | Metal antimony oxide electrode and method for tracking and detecting medium pH change |
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