KR20200127490A - Preparation Method for Reverse Current Protector - Google Patents

Abstract

The present invention relates to a manufacturing method of a reverse current protector. The reverse current protector manufactured by the manufacturing method has a porous surface to smoothly react with an electrolyte in an oxidation reduction manner under a condition of generating a reverse current, thereby having an excellent reverse current protecting effect. To this end, the manufacturing method of a reverse current protector includes the following steps of: physically etching a metal base material; chemically etching the physically etched metal base material; and immersing and plating the metal base material in a plating solution.

Description

Manufacturing method for reverse current protector {Preparation Method for Reverse Current Protector}

The present invention relates to a method of manufacturing a reverse current protector capable of effectively preventing an increase in cathode potential in a reverse current generation situation, and a reverse current protector manufactured using the same.

A technology for producing hydroxide, hydrogen and chlorine by electrolyzing inexpensive brine such as seawater is widely known. Such an electrolysis process is commonly referred to as a chlor-alkali process, and it can be said that the performance and reliability of technology have been proven through commercial operation for several decades.

In the electrolysis of such brine, an ion exchange membrane is installed inside the electrolyzer to divide the electrolyzer into a cation chamber and an anion chamber, and the ion exchange membrane method that obtains chlorine gas from the anode and hydrogen and caustic soda from the cathode using brine as an electrolyte is currently the most widely used. This is the method being used.

Meanwhile, the electrolysis process of brine is performed through a reaction as shown in the following electrochemical reaction formula.

Oxidation electrode (anode) _{^{reaction: 2Cl - → Cl 2 + 2e}} - (E 0 = +1.36 V)

Reduction electrode (cathode) ^{_{reaction: 2H 2 O + 2e - →}} 2OH - + H 2 (E 0 = -0.83 V)

Total _{^{reaction: 2Cl - + 2H 2 O →}} 2OH - + Cl 2 + H 2 (E 0 = -2.19 V)

The most important factor to be considered when performing electrolysis of brine is the electrolytic potential, which is the theoretically required voltage, overvoltage of the oxidation and reduction electrodes, voltage due to the resistance of the ion exchange membrane, and the distance between the oxidation and reduction electrodes. All voltages caused by must be considered. If the electrolytic potential can be reduced, the energy required for the entire process operation can be reduced to more efficiently produce chlorine gas and hydrogen gas.In particular, when the overvoltage caused by the electrode can be reduced, it is a great help to the efficiency of the entire process. do.

Relatedly, in the case of the negative electrode among the electrodes, the active material coated on the electrode surface is eliminated due to the shutdown phenomenon occurring during the process, which is normal because the battery shape is realized by the electrolyte remaining inside the electrolytic cell. This is due to a phenomenon in which current flows in the opposite direction to that during operation, that is, a reverse current phenomenon. When such a reverse current phenomenon occurs, an oxidation reaction rather than reduction occurs at the cathode, and accordingly, the cathode potential rises in the positive direction, resulting in elution of the metal component of the coating layer on the cathode surface. Thus, the cathode can be permanently damaged. Therefore, there is a need to develop a reverse current protector capable of suppressing a potential rise in a reverse current generation situation and an electrolytic cell having the same.

KR 2011-0094055 A

It is an object of the present invention to provide a method for preparing a reverse current protector capable of protecting a negative electrode by sacrificially participating in a redox reaction instead of a negative electrode under conditions of generating a reverse current, and a reverse current protector prepared therefrom.

The present invention is a step of physically etching a metal substrate (S1), a step of chemically etching the metal substrate subjected to physical etching (S2), and with Co, Cu, In, Fe, Ni, W. Zn, Te, Sn and Ti It provides a method of manufacturing a reverse current protector comprising the step (S3) of plating by immersing a metal substrate in a plating solution including a metal precursor and an electrolyte selected from the group consisting of.

The reverse current protector manufactured by the manufacturing method of the present invention has improved surface characteristics and can easily sacrificially participate in the redox reaction under conditions of generating reverse current, and thus the effect of maintaining the potential below the elution potential of the active ingredient of the negative electrode coating layer. Can be remarkably improved.

1 is a view of the surface of Example 1 through SEM (x200).
2 is a view of the surface of Example 1 through SEM (x5K).
3 is an observation of the surface of Comparative Example 2 through SEM (x200).
4 is a view of the surface of Comparative Example 2 through SEM (x5K).

Hereinafter, the present invention will be described in more detail.

The terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Method of manufacturing reverse current protector

The present invention is a step of physically etching a metal substrate (S1), a step of chemically etching the metal substrate subjected to physical etching (S2), and with Co, Cu, In, Fe, Ni, W. Zn, Te, Sn and Ti It provides a method of manufacturing a reverse current protector comprising the step (S3) of plating by immersing a metal substrate in a plating solution including a metal precursor and an electrolyte selected from the group consisting of.

Physical etching step (S1)

In the method of manufacturing a reverse current protector of the present invention, the step of physically etching a metal substrate constituting the main structure of the reverse current protector is performed first. Roughness can be applied to the surface of the metal substrate through physical etching in this step, and when roughness is applied to the metal substrate, plating in a later step can be easily performed. In particular, when metal is plated on the surface of a metal substrate having roughness, it helps to improve the adhesion between the plated layer and the substrate, thereby improving the physical durability of the plated layer and the two layers of the substrate.

For the physical etching, a method such as sand blasting, wet blasting, bead blasting, or wheel blasting may be used.In addition to the methods listed above, if a method capable of imparting sufficient roughness to the surface of a metal substrate, within a range known to those skilled in the art. Can be used without restrictions. In addition, a person skilled in the art may appropriately adjust equipment used for physical etching, specific methods, materials, and processes of etching in consideration of the degree of desired illuminance or continuity with subsequent manufacturing steps.

Chemical etching step (S2)

In the method for manufacturing a reverse current protector of the present invention, the step of chemically etching the physically etched metal substrate is performed second. Chemical etching in this step may be performed using a strong acid or strong base. When chemical etching is performed on a metal substrate to which roughness is applied through physical etching, impurities or oxide films remaining on the surface of the metal substrate may be removed, and through this, a plating layer to be formed may be smoothly operated.

Chemical etching in the present invention is preferably performed after physical etching, which is economical to remove impurities that may occur in the physical etching step through chemical etching, and if chemical etching is performed first, it is used for chemical etching. This is because the process can be inefficient in that the treatment of the acid or base must be preceded prior to physical etching. When physical etching and chemical etching are performed in this order, it is particularly easy to form a plating layer on the metal substrate, and the performance of the reverse current protector manufactured therefrom may also be excellent.

The chemical etching may involve heating. When heating is performed together during the chemical etching process, it is efficient in that it can perform etching to a desired degree within a short time. In the case of performing heating, the temperature range may be less than 100°C, preferably 80 to 95°C. If the heating temperature is higher than this, the etching may not proceed smoothly due to the evaporation of water in the aqueous solution containing acid or base. If the temperature is lower than this, the technical advantage that can be obtained by heating compared to the energy consumed for heating As such, the manufacturing process of the reverse current protector is inefficient.

Plating step (S3)

In the method for manufacturing a reverse current protector of the present invention, the step of electroplating the metal substrate with a metal of a kind suitable for use as a reverse current protector is finally performed.

Specifically, the plating step is a step of plating by immersing a metal substrate in a plating solution containing a metal precursor and an electrolyte selected from the group consisting of Co, Cu, In, Fe, Ni, W. Zn, Te, Sn, and Ti. .

The reverse current protection layer is formed on the surface of the metal substrate through plating in this step, and the reverse current protection layer formed through this method is porous and has a large surface area to facilitate oxidation-reduction reaction with the electrolyte. Therefore, the reverse current protector can participate in the redox reaction particularly smoothly under the conditions of generating a reverse current in which the redox reaction preferentially reacts to the coating layer of the negative electrode, and even if the condition for generating the reverse current lasts a long time, the electrode can be continuously protected.

The type of metal included in the plating solution in this step is preferably selected from the group consisting of Co, Cu, In, Fe, Ni, W. Zn, Te, Sn, and Ti. The metals listed above have a property that the metal can be preferentially eluted under conditions below the potential at which the active ingredient of the negative electrode coating layer is eluted, and such a property is an essential condition for use as a reverse current protector. In addition, when the above-described metal is used as a plating layer, it is preferable in terms of durability of a reverse current protector and a cell including the same.

When considering the durability of the plating layer, it is preferable that the metal is Ni. When Ni is used as the plating layer, nickel, a metal commonly used in the base material, and its composition are the same, so that the bonding strength between the plating layer and the base material can be increased. It is preferable in that it is possible to suppress an uneven redox reaction that may occur at the time when the reverse current protective layer partially disappears during the reduction reaction. On the other hand, in terms of the performance of the reverse current protector, it may be preferable that the metal is Co. When Co is applied as the metal of the plating layer, the absolute amount of reverse current that can be absorbed can be greatly increased. However, there is an aspect that the durability of Ni is relatively inferior to that used in that Ni may be cracked on the surface of the plating layer after the reverse current generation condition.

The precursor included in the plating solution is preferably a chloride, nitrate or carbonate of the metal, and particularly preferably a chloride. For example, when nickel is used as the metal, nickel chloride (NiCl ₂ ), nickel nitrate (Ni(NO ₃ ) ₂ ), nickel carbonate (NiCO ₃ ) can be used, and when cobalt is used as the metal, cobalt chloride ( CoCl ₂ ), cobalt nitrate (Co(NO ₃ ) ₂ ), cobalt carbonate (CoCO ₃ ) can be used. In addition, the precursor may be used in the form of a precursor or a hydrate. For example, in the case of nickel chloride, it can be used in the form of hexahydrate. When the above chloride, nitride, and carbonate are used as precursors in this step, the plating layer may be formed more smoothly in the plating step.

In the manufacturing method of the present invention, the plating solution contains an electrolyte. The electrolyte plays a role of smoothing the current applied for electroplating, and a person of ordinary skill in the art has the plating potential of metal among the electrolytes that can be used for electroplating in the technical field of the present invention, and types of metal precursors included in the plating solution. B. Considering plating conditions, etc., an appropriate electrolyte can be selected and used. Specifically, it may be preferable to use an ammonium salt such as ammonium chloride, ammonium nitrate or ammonium carbonate. If, for example, nickel or cobalt precursor is used as a metal precursor, and nickel or cobalt is to be plated on the plating layer, in addition to the above-described ammonium salt electrolyte, potassium nitrate, potassium carbonate, potassium chloride, calcium chloride, calcium carbonate, magnesium carbonate, magnesium chloride, Sodium chloride, sodium carbonate, etc. can also be used. When selecting and using such an appropriate electrolyte, there is an advantage in that a desired metal plating layer can be easily manufactured.

Plating of the reverse current protection layer may be performed for 0.1 to 5 minutes, preferably 0.5 to 3 minutes at a current density of 0.1 to 5 A/cm ² , preferably 0.5 to 2.5 A/cm ² . A person skilled in the art can plate a desired degree of metal layer by adjusting the current density and plating time within the above-described range. If the current density is lower or the plating time is shorter than this, the desired amount of plating will be performed. There is a problem that the performance of the manufactured reverse current protector is degraded, and if the current density is higher or the plating time is higher than this, the cost of manufacturing the reverse current protector is excessive compared to the desired level of plating layer. Therefore, there is a problem that it is not economical

The concentration of metal cations contained in the plating solution may be 5 to 100 g/L, preferably 10 to 50 g/L. If the concentration of the metal cation is lower than this, plating may not be sufficiently performed, and if the concentration of the metal cation is higher than this, not only economical efficiency is lowered, but a non-uniform structure may be formed during plating due to the high concentration of the metal cation.

The concentration of the electrolyte contained in the plating solution may be 10 to 200 g/L, and preferably 50 to 150 g/L. If the concentration of the electrolyte is greater than this, the manufacturing process of the reverse current protector is not economical, and if it is less than this, it is insufficient to smoothly perform the role of the electrolyte.

Anode electrolytic degreasing step (S2-1)

The method of manufacturing a reverse current protector of the present invention may further include anodic electrolytic degreasing of the metal substrate after physical etching and chemical etching. The anode electrolytic degreasing serves to remove impurities other than metal salts or oxides on the surface of the metal substrate that may remain after etching. A person skilled in the art may perform the anodic electrolytic degreasing step in order to further smooth the plating in a later step.In particular, when the anodic electrolytic degreasing step is passed, the adhesion between the plating layer and the metal substrate increases, resulting in a reverse current that is finally produced. The durability of the protector can be further improved.

Specifically, the anodic electrolytic degreasing may be performed by using the metal substrate as an anode, immersing it in an acid aqueous solution such as sulfuric acid, and passing a current to generate gas on the surface of the metal substrate.

The acid aqueous solution used in the anodic electrolytic degreasing step may have a concentration of 50 to 90% by weight, preferably 60 to 80% by weight, more preferably 65 to 75% by weight. If the concentration of the acid aqueous solution is higher than this, the risk of the process may be increased and economic feasibility may be deteriorated. If the concentration of the acid aqueous solution is lower than this, the degreasing effect may be insignificant due to insufficient gas generation on the surface of the metal substrate.

The voltage and current density in the anodic electrolytic degreasing step may be 6 to 12V and 10 to 200mA/cm ² , respectively, and a person of ordinary skill in the art sets the voltage and current density within the above-described range according to the degree of electrolytic degreasing. Can be adjusted accordingly.

Strike plating step (S2-2)

The method for manufacturing a reverse current protector of the present invention may further include strike plating the etched metal substrate with the same type of metal as the substrate.

The strike plating may be performed to improve adhesion and coating power of plating to be performed later, and refers to a method of performing plating within a short time by using a bath property. The bath used for strike plating may have a large negative polarization and excellent uniform electrodeposition by setting the concentration of metal ions lower than the salt concentration. The metal to be plated may be electrodeposited while removing the oxide film that may remain on the surface of the metal substrate through the strike plating through reduction.

The strike plating step is performed after the physical etching and chemical etching steps and before the plating step, and if the anode electrolytic degreasing step is included, after the anode electrolytic degreasing step, and before the reverse current protection layer is plated in the plating step. This is a pre-plating step containing the same kind of metal. The strike plating is particularly effective when an oxide film is easily formed on a metal surface.

In the strike plating step of the present invention, by forming a layer containing the same type of metal as the metal layer to be formed later, the durability of the reverse current protector manufactured by further increasing the adhesion between the reverse current protection layer to be formed and the metal base layer Can improve.

Specifically, the strike plating may be performed in an aqueous solution containing a metal precursor and hydrochloric acid. The metal included in the metal precursor is of the same type as the metal of the base layer, and when strike plating is performed with the same type of metal, the effect of increasing the adhesion between the reverse current protection layer and the metal base layer can be maximized.

The strike plating may be performed under conditions known to a person skilled in the art, and a person skilled in the art may plate a desired degree of strike plating layer by adjusting plating conditions, such as current density and plating time, within an appropriate range.

Reverse current protector

The present invention provides a reverse current protector manufactured by the above-described manufacturing method.

The reverse current protective body manufactured through the above-described manufacturing method includes a metal substrate and a plating layer, that is, a reverse current protective layer.In particular, the reverse current protective layer is porous and can smoothly participate in the redox reaction under the conditions of generating a reverse current. Thus, it is possible to protect the electrode even under a large reverse current or a reverse current condition over a long period of time.

Electrolytic cell

The present invention provides an electrolytic cell including the reverse current protector. The electrolytic cell provided by the present invention may include a cathode chamber, an anode chamber, and a membrane, and the cathode chamber may include a cathode, a mattress, a current collector, a reverse current protector, and an electrolyte, and the anode chamber includes a cathode and an electrolyte. Can include.

In the electrolytic cell provided by the present invention, the cathode chamber and the anode chamber are separated by a membrane, and the cathode included in the cathode chamber and the anode included in the anode chamber are electrically connected. In addition, the reverse current protector, the negative electrode, and the current collector included in the negative electrode chamber are also electrically connected. The above-described mattress may be disposed between the negative electrode and the current collector, and the positive electrode chamber and the negative electrode chamber may contain an electrolyte. The reverse current protector of the present invention may be independent from the above-described mattress or current collector, or may be a part of the mattress and the current collector. A person skilled in the art will appropriately change the structure of the electrolytic cell provided by the present invention, particularly the position or connection relationship of the reverse current protector, by referring to the structure of a general electrolytic cell and common technical knowledge known in the art within the scope of the purpose of the present invention. Can be used.

Hereinafter, examples and experimental examples will be described in more detail to describe the present invention in detail, but the present invention is not limited by these examples and experimental examples. The embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Example 1

A nickel mesh substrate (manufacturer: Ildong gold mesh, 40 mesh, wire diameter: 200 μm) was prepared, and the substrate was cut into a 1 cm ² square, followed by sandblasting treatment. Then, it was etched at 90° C. for 3 minutes using a 50% by weight aqueous sulfuric acid solution, washed with distilled water, and placed in an oven at 100° C. and dried. Finally, after immersing the metal substrate in 0.4 L of an aqueous solution in which NiCl ₂ ·6H ₂ O (23.7 g/L) as a metal precursor and NH ₄ Cl (106.7 g/L) as an electrolyte are mixed, -1.8 A/cm ² Plating was performed at a current density of 1 minute to obtain a final reverse current protector.

Example 2

A reverse current protector was obtained in the same manner as in Example 1 except that the current density of plating was set to 1.0A/cm ² .

Example 3

A reverse current protector was obtained in the same manner as in Example 1 except that the current density of plating was 2.5A/cm ² .

Example 4

A reverse current protector was obtained in the same manner as in Example 1, except that the plating time was 2 minutes.

Example 5

A reverse current protector was obtained in the same manner as in Example 1 except that the plating time was set to 3 minutes.

Example 6

In Example 1, except that the concentration of NiCl ₂ was 11.8 g/L, the same was carried out to obtain a reverse current protector.

Example 7

In Example 1, except that the concentration of NiCl ₂ was 35.4 g/L, it was carried out in the same manner to obtain a reverse current protector.

Example 8

In Example 1, a reverse current protector was obtained by performing the same procedure except that CoCl ₂ was used at the same concentration instead of NiCl ₂ .

Example 9

In Example 1, CoCl ₂ was used instead of NiCl ₂ at the same concentration, except that the plating time was 2 minutes, and a reverse current protector was obtained.

Comparative Example 1

A reverse current protector was obtained in the same manner as in Example 1, except that nickel plating was performed immediately without chemical etching and physical etching.

Comparative Example 2

In Example 1, except that only chemical etching and physical etching were treated, and plating was not performed, a reverse current protector was obtained.

Comparative Example 3

All of the chemical etching, physical etching, and plating were not performed, and the nickel metal substrate itself was used as a reverse current protector.

The parts having differences among the manufacturing methods of the above-described Examples and Comparative Examples are summarized and summarized in Table 1 below.

number Whether to be etched Plated physical
etching Chemical
etching Plating or not Plated metal Current density
(A/cm ² ) time
(minute) Metal precursor concentration
(g/L) Example 1 O O O Ni 1.8 One 23.7 Example 2 O O O Ni 1.0 One 23.7 Example 3 O O O Ni 2.5 One 23.7 Example 4 O O O Ni 1.8 2 23.7 Example 5 O O O Ni 1.8 3 23.7 Example 6 O O O Ni 1.8 One 11.8 Example 7 O O O Ni 1.8 One 35.4 Example 8 O O O Co 1.8 One 23.7 Example 9 O O O Co 1.8 2 23.7 Comparative Example 1 X X O Ni 1.8 One 23.7 Comparative Example 2 O O X - - - - Comparative Example 3 X X X - - - -

Experimental Example 1. Measurement of potential holding time under reverse current generation conditions

An experiment simulating the occurrence of reverse current was performed for the reverse current protector prepared in the above Examples and Comparative Examples. After constructing a three-electrode system using the manufactured reverse current protector as a working electrode, a platinum conductor as a counter electrode, and an Hg/HgO electrode as a reference electrode, a 32% by weight aqueous sodium hydroxide solution was placed in the chamber equipped with the working electrode and the counter electrode. Was introduced into an electrolytic solution, and the temperature was set to 90°C. Separately from the chamber, a glass with a reference electrode was prepared, and a 32% by weight aqueous sodium hydroxide solution was added thereto, and the glass and the chamber were connected with a salt bridge. After that, after passing a current for 1 hour at a current density of 0.62 A/cm ² so that a reduction reaction can occur at the working electrode, the direction of the current is changed so that the potential of the working electrode rises while the oxidation reaction occurs. Current was applied with a current density of cm ² . In this process, the time to reach -0.1V (compared to the reference electrode) when the elution of ruthenium, which is generally used as the active material of the negative electrode, starts and the amount of charge per unit area accumulated in the reverse current protector during that time, that is, the absorbed reverse current The amount of charge was measured, and it is summarized in Table 2 below.

Reach time (minutes) Cumulative electric charge (C/m ² ) Example 1 9.7 29100 Example 2 3.9 11700 Example 3 11.4 34200 Example 4 20.4 61100 Example 5 21.8 65250 Example 6 5.1 15250 Example 7 17.3 51950 Example 8 109.1 327250 Example 9 200.4 601150 Comparative Example 1 6.6 19650 Comparative Example 2 2.2 6700 Comparative Example 3 0.9 2550

The arrival time and the amount of charge measured through the above experiment are indexes that can estimate the amount of reverse current that can be absorbed under the condition of generating the reverse current.The longer and larger the time and charge, the longer the cathode will be protected from a large amount of charge. Because it can be used, this means that the reverse current protection performance is excellent.

When comparing Example 1 and Comparative Example 1, which differ only in chemical etching and physical etching, the reverse current protector of Example 1 subjected to the chemical etching and physical etching steps was compared to the reverse current protector of Comparative Example 1 without the chemical etching and physical etching steps. It was confirmed that it has about 1.5 times the reverse current protection performance. In addition, it was confirmed that the performance of the manufactured reverse current protector improved as the metal concentration and plating time of the plating solution increased within the range of the examples. In the case of Comparative Examples 2 and 3 without introducing a plating layer, although the metal substrate was nickel Despite being a material, it was confirmed that the reverse current protection performance was extremely insignificant. In addition, it was confirmed that when cobalt metal was used as the plating layer, that is, Examples 8 and 9 showed superior reverse current protection performance compared to nickel metal. However, when the cobalt metal was used as the plating layer, the surface was separated after the experiment and the powder fell off, and from this, it was confirmed that durability is lower than when the same type of metal is used for the base layer and the plating layer.

When the above experimental results are summarized, it can be seen that the reverse current protector according to the embodiment of the present invention has particularly excellent performance when applied to an electrolytic cell capable of generating a reverse current.

Experimental Example 2. Surface observation of reverse current protector

In order to confirm the shape of the plating layer among the manufactured reverse current protectors, the surfaces of the reverse current protectors of Example 1 in which the plating layer was introduced and Comparative Example 2 without the plating layer were introduced through an electron scanning microscope (SEM). It was observed, and the surfaces of Example 1 are shown in FIGS. 1 (x200) and 2 (x5K), and the surfaces of Comparative Example 2 are shown in FIGS. 3 (x200) and 4 (x5K).

As can be seen in FIGS. 1 and 2, in the case of the reverse current protector manufactured through the manufacturing method of the present invention, the surface is porous, so that it can smoothly participate in the redox reaction under the condition of generating the reverse current, while FIGS. 3 and 4 As can be seen, the reverse current protector manufactured through the manufacturing method of Comparative Example 2 has a smooth surface, so that it cannot react smoothly under the conditions of generating a relatively reverse current, and thus the reverse current protection performance is degraded. Confirmed.

Claims (9)

Physically etching the metal substrate (S1);
Chemically etching the physically etched metal substrate (S2); And
Reversing including: Co, Cu, In, Fe, Ni, W. Zn, Te, Sn, and Ti by immersing a metal substrate in a plating solution containing a metal precursor and an electrolyte selected from the group consisting of Ti (S3); Method of manufacturing a class protection body. The method of claim 1, wherein the metal precursor is a metal chloride, nitrate or carbonate. The method of claim 1, wherein the electrolyte contains an ammonium salt. The method of claim 1,
A method of manufacturing a reverse current protector further comprising the step of anodic electrolytic degreasing of the physically etched metal substrate (S2-1) or strike plating with the same type of metal as the substrate (S2-2). The method of claim 1,
A method of manufacturing a reverse current protector further comprising anodic electrolytic degreasing of the physically etched metal substrate (S2-1) and strike plating with the same type of metal as the substrate (S2-2). The method of claim 5,
The strike plating is a method of manufacturing a reverse current protector to be performed in an aqueous solution containing a metal precursor and hydrochloric acid. The method of claim 1,
The plating in step S3 is a method of manufacturing a reverse current protector that is performed at a current density of 0.1 to 5 A/cm ² . The method of claim 1,
The method of manufacturing a reverse current protector in which the plating in step S3 is performed for 0.1 to 5 minutes. The method of claim 1,
The method of manufacturing a reverse current protector in which the concentration of metal cations in the plating solution is 5 to 100 g/L.

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