Electrochemical probes for detecting amorphous manganese oxyhydroxide in manganese oxide sols and methods of making same

Abstract

The application discloses an electrochemical probe for detecting amorphous manganese oxyhydroxide in a manganese oxide sol and a preparation method thereof. The electrochemical probe is prepared by the following method: placing a conductive fiber into an electrolytic tank containing a manganese salt electrolyte, applying a voltage to pre-oxidize the conductive fiber to coat the surface of the conductive fiber with oxides; then performing pickling on the conductive fiber coated with the oxides; taking the pickled conductive fiber as an anode, coating a water-absorbing material on a strip-shaped structure cathode, and then immersing the strip-shaped structure cathode in an electrolyte containing manganese ions or a sol containing manganese ions to obtain the electrochemical probe through a brush plating process. The application utilizes the electrochemical balance between the manganese oxide sol on the surface of the electrochemical probe and the sol in a detection solution, and then detects the amorphous manganese oxyhydroxide in the detection solution. The probe prepared by the application has the advantages of high sensitivity, high selectivity, simple preparation method and the like.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical probe technology, specifically relating to an electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol and its preparation method. Background Technology

[0002] The electro-oxidation process of manganese salt solutions is widely used in the electrochemical preparation of manganese dioxide and the charging and discharging of manganese-based batteries. It manifests as the oxidation of Mn(III) ions to higher-valence manganese ions. Among these processes, Mn(III) ions and their amorphous manganese oxide sol are highly reactive intermediates with significant oxidizing activity, profoundly affecting the final structure of the product, electrolytic energy consumption, and battery charging and discharging efficiency. Therefore, developing an in-situ detection technology for amorphous manganese oxide in manganese oxide sol during the electro-oxidation process of manganese salts is crucial. However, currently, there is no technology capable of rapidly detecting the micelle chemical composition of amorphous manganese oxide sol during the reaction.

[0003] Currently, there are many methods for detecting intermediates in solution, including particle size analysis, ultramicroscopy, and cyclic voltammetry. Particle size analysis can detect the size of particles in solution but cannot characterize the valence state and composition of particles; ultramicroscopy can show the Brownian motion of luminescent spots representing sol ions, but cannot dynamically observe the chemical composition of the sol; cyclic voltammetry can determine the possibility of sol intermediate formation during electrode reactions and related chemical reactions, but lacks specific probes and cannot accurately quantify the chemical composition of specific reaction intermediates. These problems make in-situ monitoring of amorphous manganese hydroxide in manganese-containing micelles under operating conditions and in small reaction regions extremely difficult. Therefore, developing an electrochemical probe that can monitor the presence of intermediates in situ and analyze their composition is particularly important. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide an electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol and its preparation method. This electrochemical method rapidly detects complex reaction behaviors such as interconversion and bridging between manganese ions of different valence states.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol, characterized in that it is prepared according to the following method: one end of a conductive fiber is placed in an electrolytic cell containing a manganese salt electrolyte, and the other end of the conductive fiber is coated with an insulating material. A voltage is applied for pre-oxidation to coat the surface of the conductive fiber with oxide. Then, the oxide-coated conductive fiber is acid-washed. The acid-washed conductive fiber is used as the anode, and a strip structure coated with a water-absorbing material is used as the cathode. The water-absorbing material is fully immersed in an electrolyte containing manganese ions or a sol containing manganese ions. After a brush plating process, the electrochemical probe can be obtained.

[0006] In the above scheme: the conductive fiber is one of copper wire, titanium wire, platinum wire, silver wire, zinc wire, nickel wire, stainless steel wire, and carbon fiber, and the diameter of the conductive fiber is less than 3mm.

[0007] In the above scheme, the concentration of manganese ions in the manganese salt electrolyte used during pre-oxidation is 0.1 mol / L-2.8 mol / L.

[0008] In the above scheme: the current density during pre-oxidation is 0.1-100 A / cm. 2 The temperature ranges from 5 to 90℃.

[0009] In the above scheme: the pickling process uses oxalic acid solution with an acid concentration of 0.01mol / L-1.5mol / L and a pickling time of 0-1h.

[0010] In the above scheme: During brush plating, the acid-washed conductive fiber is used as the anode, and the strip-shaped conductive material is used as the cathode. First, the absorbent material is coated onto the strip-shaped cathode. Then, the absorbent material is fully impregnated with an electrolyte or sol containing manganese ions. A voltage is then applied between the anode and cathode, allowing the cathode to contact the anode through the absorbent material and be repeatedly moved for plating multiple times. During the brush plating process, the metal ions in the absorbent material, under the influence of the electric field, undergo an oxidation-reduction reaction and deposit onto the anode to form an oxide gel layer.

[0011] In the above scheme, the absorbent material used can be absorbent cotton cloth, absorbent non-woven fabric, absorbent cotton paper, etc.

[0012] In the above scheme, the concentration of manganese ions in the electrolyte or sol containing manganese ions used during brush plating is 0.1 mol / L-2.8 mol / L.

[0013] In the above scheme: the voltage between the anode and cathode is 0-10V during brush plating, and the number of brush plating cycles is 1-100.

[0014] The electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol prepared by the above method is an electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol.

[0015] This invention utilizes the electrochemical equilibrium between the manganese oxide sol on the surface of an electrochemical probe and the sol in the detection solution to detect amorphous manganese hydroxyl oxide in the solution. The probe prepared by this invention has the advantages of high sensitivity, high selectivity, and simple preparation method. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the structure of an electrochemical probe.

[0017] In the figure, 1 is the conductive substrate, 2 is the insulating material (insulating varnish), and 3 is the oxide gel layer.

[0018] Figure 2 This is a linear voltammetric scan of the electrochemical probe in Example 1.

[0019] Figure 3 This is a linear voltammetric scan of the electrochemical probe in Example 2.

[0020] Figure 4 This is a linear voltammetric scan of the electrochemical probe in Example 3.

[0021] Figure 5 This is a linear voltammetric scan of the electrochemical probe in Example 4.

[0022] Figure 6 This is a linear voltammetric scan of the electrochemical probe in Example 5.

[0023] Figure 7 This is a linear voltammetric scan of the electrochemical probe in Example 6.

[0024] Figure 8 This is a linear voltammetric scan of the electrochemical probe in Example 7.

[0025] Figure 9 This is a linear voltammetric scan of the electrochemical probe in Example 8.

[0026] Figure 10 This is a linear voltammetric scan of the electrochemical probe in Example 9.

[0027] Figure 11 This is a linear voltammetric scan of the electrochemical probe in Example 10. Detailed Implementation

[0028] The present invention will now be further described with reference to the accompanying drawings and embodiments.

[0029] Example 1

[0030] 1) Take about 10cm of platinum wire with a diameter of 0.1mm. Of this, reserve 1cm of platinum wire for the reaction (the rest is encapsulated with insulating varnish) to serve as the conductive substrate for the anode of the electrochemical probe.

[0031] 2) Take approximately 10cm of stainless steel wire with a diameter of 0.2mm. Of this, reserve 1cm of stainless steel wire for the reaction (the remaining part is encapsulated with insulating varnish) to serve as the cathode.

[0032] 3) Using an Ag / AgCl electrode as the reference electrode in conjunction with the anode and cathode prepared in steps 1 and 2, a linear voltammetric scan was performed in a 0.1 mol / L manganese sulfate solution at 5 °C, with a scan rate of 0.15 V / s and a current density of 1 A / cm². 2 An anode with an oxide coating can be obtained.

[0033] 4) Immerse the anode with the oxide coating obtained in step 3 in 0.1 mol / L oxalic acid solution for 2 seconds, and then rinse it with pure water to obtain the acid-washed electrode.

[0034] 5) Use the electrode obtained in step 4 as the anode and the stainless steel wire (10mm*0.2mm) as the cathode. Wrap the absorbent cotton cloth around the cathode and then let the absorbent material fully immerse itself in an electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.1mol / L manganese sulfate solution as the electroplating solution, brush plating is performed 10 times at an electroplating voltage of 3V to form an oxide gel layer on the anode, thus obtaining an electrochemical probe.

[0035] 6) The electrochemical probe obtained in step 5 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0036] Example 2

[0037] 1) Take about 10cm of platinum wire with a diameter of 0.5mm. Of this, reserve 2cm of platinum wire for the reaction (the rest is encapsulated with insulating varnish) to serve as the conductive substrate for the anode of the electrochemical probe.

[0038] 2) Using an Ag / AgCl electrode as the reference electrode, and a stainless steel sheet (10mm*10mm*0.2mm) as the cathode in conjunction with the anode prepared in step 1, a linear voltammetric scan of 0-3V was performed in a 0.15mol / L manganese sulfate solution at 30℃, with a current density of 0.1A / cm². 2 With a scan rate of 0.10 V / s, an anode with an oxide coating on its surface can be obtained.

[0039] 3) Immerse the anode with oxide coating obtained in step 2 in 0.15 mol / L oxalic acid solution for 1 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0040] 4) Use the electrode obtained in step 3 as the anode and the stainless steel strip (10mm*0.2mm) as the cathode. Wrap the absorbent non-woven fabric around the cathode and then allow the absorbent material to fully immerse itself in an electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.15mol / L manganese sulfate solution as the electroplating solution, perform 20 brush plating passes at an electroplating voltage of 5V to obtain the electrochemical probe.

[0041] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0042] Example 3

[0043] 1) Take about 10cm of titanium wire with a diameter of 0.2mm. Of this, reserve 1cm of titanium wire for the reaction (the rest is encapsulated with insulating varnish) to serve as the conductive substrate for the anode of the electrochemical probe.

[0044] 2) Take approximately 10cm of stainless steel wire with a diameter of 0.5mm. Of this, reserve 1cm of stainless steel wire for the reaction (the remaining part is encapsulated with insulating varnish) to serve as the cathode.

[0045] 3) Using an Ag / AgCl electrode as a reference electrode in conjunction with the anode and cathode prepared in steps 1 and 2, a linear voltammetric scan of 0-10 V was performed in a 0.20 mol / L manganese sulfate solution at 40 °C, with a current density of 10 A / cm². 2 With a scan rate of 0.15V / s, an anode with an oxide coating on its surface can be obtained.

[0046] 4) Immerse the anode with the oxide coating obtained in step 3 in 0.1 mol / L oxalic acid solution for 2 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0047] 5) Use the electrode obtained in step 4 as the anode and the stainless steel strip (10mm*0.3mm) as the cathode. Wrap the absorbent cotton paper around the cathode and then let the absorbent material fully immerse itself in the electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.20mol / L manganese sulfate solution as the electroplating solution, brush plating is performed 50 times at an electroplating voltage of 10V to obtain the electrochemical probe.

[0048] 6) The electrochemical probe obtained in step 5 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0049] Example 4

[0050] 1) Take about 10cm of copper wire with a diameter of 0.3mm. Reserve 2cm of the copper wire for the reaction (encapsulate the rest with insulating varnish) to make the conductive substrate of the electrochemical probe anode.

[0051] 2) Using an Ag / AgCl electrode as the reference electrode, and a stainless steel sheet (20mm*20mm*0.2mm) as the cathode in conjunction with the anode prepared in step 1, a linear voltammetric scan of 0-3V was performed in a 0.30mol / L manganese sulfate solution at 50℃, with a current density of 100A / cm². 2 At a scan rate of 0.10 V / s, an anode with an oxide coating on its surface can be obtained.

[0052] 3) Immerse the anode with oxide coating obtained in step 3 in 0.15 mol / L oxalic acid solution for 3 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0053] 4) Use the electrode obtained in step 3 as the anode and the stainless steel strip (10mm*0.3mm) as the cathode. Wrap the absorbent cotton cloth around the cathode and then let the absorbent material fully immerse itself in the electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.30mol / L manganese sulfate solution as the electroplating solution, brush plating is performed 10 times at an electroplating voltage of 3V to obtain the electrochemical probe.

[0054] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0055] Example 5

[0056] 1) Take about 10cm of silver wire with a diameter of 0.3mm. Of this, reserve 1cm of silver wire for the reaction (the rest is encapsulated with insulating varnish) to serve as the conductive substrate for the anode of the electrochemical probe.

[0057] 2) Using a stainless steel sheet (10mm*10mm*0.2mm) as the cathode and combined with the anode prepared in step 1, oxidation was carried out in a 0.90mol / L manganese sulfate solution at 60℃ under constant voltage of 10V and a current density of 3A / cm². 2 An anode with an oxide coating on its surface can be obtained.

[0058] 3) Immerse the anode with oxide coating obtained in step 2 in 0.15 mol / L oxalic acid for 30 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0059] 4) Use the electrode obtained in step 3 as the anode and the stainless steel strip (10mm*0.3mm) as the cathode. Wrap the absorbent cotton cloth around the cathode and then let the absorbent material fully immerse itself in the electrolyte or sol containing manganese ions. Using a commercial brush plating instrument, with a 0.90mol / L manganese sulfate solution as the electroplating solution, perform 20 brush plating passes at an electroplating voltage of 5V to obtain the electrochemical probe.

[0060] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0061] Example 6

[0062] 1) Take about 10cm of platinum wire with a diameter of 0.1mm. Reserve 1cm of the platinum wire for the reaction (encapsulate the rest with insulating varnish) to make the conductive substrate of the electrochemical probe anode.

[0063] 2) Using a stainless steel sheet (10mm*10mm*0.2mm) as the cathode and combined with the anode prepared in step 1, oxidation was carried out in a 0.90mol / L manganese sulfate solution at 70℃ under constant voltage of 5V and a current density of 2A / cm². 2 An anode with an oxide coating on its surface can be obtained.

[0064] 3) Immerse the anode with oxide coating obtained in step 2 in 0.10 mol / L oxalic acid solution for 1 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0065] 4) Use the electrode obtained in step 3 as the anode, stainless steel (10mm*0.2mm) as the cathode, and wrap the cathode with absorbent cotton cloth. Then, allow the absorbent material to fully immerse itself in an electrolyte or sol containing manganese ions. Using a commercial brush plating instrument, with a 2.8mol / L manganese sulfate solution as the plating solution, perform brush plating 10 times at a plating voltage of 3V to obtain an electrochemical probe.

[0066] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0067] Example 7

[0068] 1) Take about 10cm of platinum wire with a diameter of 0.1mm. Reserve 1cm of the platinum wire for the reaction (encapsulate the rest with insulating varnish) to make the conductive substrate of the electrochemical probe anode.

[0069] 2) Using an Ag / AgCl electrode as the reference electrode, and a stainless steel sheet (10mm*10mm*0.3mm) as the cathode in conjunction with the anode prepared in step 1, a linear voltammetric scan of 0-6V was performed in a 2.8mol / L manganese sulfate solution at 70℃, with a current density of 5A / cm². 2 With a scan rate of 0.15V / s, an anode with an oxide coating on its surface can be obtained.

[0070] 3) Immerse the anode with oxide coating obtained in step 2 in 0.10 mol / L oxalic acid solution for 1 hour, and then rinse it with pure water to obtain the acid-washed electrode.

[0071] 4) Use the electrode obtained in step 3 as the anode, stainless steel (10mm*0.2mm) as the cathode, and wrap the cathode with absorbent cotton cloth. Then, allow the absorbent material to fully immerse itself in an electrolyte or sol containing manganese ions. Using a commercial brush plating instrument, use a 1.45mol / L manganese sulfate solution as the electroplating solution and perform brush plating 10 times at an electroplating voltage of 3V to obtain an electrochemical probe.

[0072] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0073] Example 8

[0074] 1) Take about 10cm of platinum wire with a diameter of 0.1mm. Reserve 1cm of the platinum wire for the reaction (encapsulate the rest with insulating varnish) to make a conductive substrate for the electrochemical probe.

[0075] 2) Using an Ag / AgCl electrode as the reference electrode, and a stainless steel sheet (10mm*10mm*0.4mm) as the cathode in conjunction with the anode prepared in step 1, a linear voltammetric scan of 0-10V was performed in a 1.0mol / L manganese sulfate solution at 80℃, with a current density of 5A / cm². 2 At a scan rate of 0.10 V / s, an anode with an oxide coating on its surface can be obtained.

[0076] 3) Immerse the anode with oxide coating obtained in step 2 in 0.10 mol / L oxalic acid solution for 10 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0077] 4) Use the electrode obtained in step 3 as the anode, stainless steel (10mm*0.2mm) as the cathode, and wrap the cathode with absorbent cotton cloth. Then, let the absorbent material fully immerse itself in an electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 2.5mol / L manganese sulfate solution as the plating solution, perform 20 brush plating passes at a plating voltage of 4V to obtain an electrochemical probe.

[0078] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0079] Example 9

[0080] 1) Take about 10cm of platinum wire with a diameter of 0.1mm. Of this, reserve 1cm of platinum wire for the reaction (the rest is encapsulated with insulating varnish) to serve as the conductive substrate for the anode of the electrochemical probe.

[0081] 2) Using an Ag / AgCl electrode as the reference electrode, and a stainless steel sheet (10mm*10mm*0.4mm) as the cathode in conjunction with the anode prepared in step 1, a linear voltammetric scan of 0-3V was performed in a 0.90mol / L manganese sulfate solution at 50℃, with a current density of 0.1-100A / cm². 2 At a scan rate of 0.5 V / s, an anode with an oxide coating on its surface can be obtained.

[0082] 3) Immerse the anode with oxide coating obtained in step 2 in 0.90 mol / L oxalic acid solution for 5 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0083] 4) Use the electrode obtained in step 3 as the anode, a stainless steel sheet (3mm*10mm*0.2mm) as the cathode, and wrap the cathode with absorbent cotton cloth. Then, allow the absorbent material to fully immerse itself in an electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.90mol / L manganese sulfate solution as the electroplating solution, perform 20 brush plating passes at an electroplating voltage of 10V to obtain an electrochemical probe.

[0084] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0085] Example 10

[0086] 1) Take about 10cm of platinum wire with a diameter of 0.1mm, reserve 1cm for the reaction length, and encapsulate the rest with insulating varnish to make an electrochemical probe anode conductive substrate.

[0087] 2) Using an Ag / AgCl electrode as the reference electrode, a stainless steel sheet (10mm*10mm*0.4mm) as the cathode, combined with the anode prepared in step 1, a linear voltammetric scan of 0-3V was performed in a 0.90mol / L manganese sulfate solution at 90℃, with a scan rate of 0.25V / s and a current density of 1A / cm². 2 An anode with an oxide coating on its surface can be obtained.

[0088] 3) Immerse the anode with oxide coating obtained in step 2 in 0.5 mol / L oxalic acid solution for 15 min, and then rinse it with pure water to obtain the acid-washed electrode.

[0089] 4) Use the electrode obtained in step 3 as the anode, stainless steel (10mm*0.4mm) as the cathode, and wrap the cathode with absorbent cotton cloth. Then, let the absorbent material fully immerse itself in an electrolyte or sol containing manganese ions. Using a handheld brush plating instrument, with a 0.90mol / L manganese sulfate solution as the electroplating solution, perform 50 brush plating passes at an electroplating voltage of 3V to obtain an electrochemical probe.

[0090] 5) The electrochemical probe obtained in step 4 is subjected to linear voltammetry in a sol containing manganese ions to obtain the reduction peak corresponding to amorphous manganese hydroxyoxide, i.e., peak ②.

[0091] Figure 2-11 The figures show the linear voltammetric scans of the electrochemical probes used in Examples 1-10. As can be seen from the figures, the prepared electrochemical probes can detect the reduction peak corresponding to manganese hydroxide, i.e., reduction peak ②. This indicates that it can be used for the detection of amorphous manganese hydroxide in gels.

[0092] This invention is not limited to the above embodiments. Those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this invention. The scope of this invention is defined by the claims and their equivalents.

Claims

1. A method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxyapatite in manganese oxide sol, characterized in that, The preparation method is as follows: One end of a conductive fiber is placed in an electrolytic cell containing a manganese salt electrolyte, and the other end of the conductive fiber is coated with an insulating material. A voltage is applied for pre-oxidation to coat the surface of the conductive fiber with oxides. Then, the oxide-coated conductive fiber is acid-washed. The acid-washed conductive fiber is used as the anode, and a strip structure coated with absorbent material is used as the cathode. The absorbent material is fully immersed in an electrolyte or sol containing manganese ions. After a brush plating process, an electrochemical probe can be obtained. During brush plating, the acid-washed conductive fiber is used as the anode, and the strip structure conductive material is used as the cathode. First, the absorbent material is coated on the strip structure cathode. Then, the absorbent material is fully immersed in an electrolyte or sol containing manganese ions. A voltage is applied between the anode and cathode, and the cathode is repeatedly moved to contact the anode through the absorbent material and coated multiple times. During the brush plating process, the metal ions in the absorbent material are deposited on the anode through an oxidation-reduction reaction under the action of the electric field to form an oxide gel layer.

2. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 1, characterized in that: The conductive fiber is one of the following: copper wire, titanium wire, platinum wire, silver wire, zinc wire, nickel wire, stainless steel wire, or carbon fiber. The diameter of the conductive fiber is less than 3 mm.

3. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 1, characterized in that: The concentration of manganese ions in the manganese salt electrolyte used during pre-oxidation is 0.1 mol / L-2.8 mol / L.

4. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 3, characterized in that: The current density during pre-oxidation is 0.1-100 A / cm. 2 The temperature ranges from 5 to 90℃.

5. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 1, characterized in that: The pickling process uses oxalic acid solution with an acid concentration of 0.01 mol / L-1.5 mol / L and a pickling time of 0-1 h.

6. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 1, characterized in that: The absorbent material used is one of the following: absorbent cotton cloth, absorbent non-woven fabric, or absorbent paper.

7. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 6, characterized in that: During brush plating, the concentration of manganese ions in the electrolyte or sol containing manganese ions is 0.1 mol / L-2.8 mol / L.

8. The method for preparing an electrochemical probe capable of detecting amorphous manganese hydroxide in manganese oxide sol according to claim 7, characterized in that: During brush plating, the voltage between the anode and cathode is 0-10V, and the number of brush plating cycles is 1-100.

9. An electrochemical probe capable of detecting amorphous manganese hydroxyl oxide in manganese oxide sol, prepared by any one of claims 1-8.

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