CN115125565B

CN115125565B - Method for resisting electrolytic seawater anode corrosion

Info

Publication number: CN115125565B
Application number: CN202210756550.0A
Authority: CN
Inventors: 邝允; 刘威; 辛慧军; 余佳格; 孙晓明
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2022-06-29
Filing date: 2022-06-29
Publication date: 2024-03-26
Anticipated expiration: 2042-06-29
Also published as: CN115125565A

Abstract

The invention belongs to the technical field of inorganic advanced nano materials, and particularly relates to a method for resisting corrosion of an electrolytic seawater anode. The electrolyte for electrolyzing seawater contains sodium chloride and alkali, and the method comprises at least one of the following two schemes: in a first scheme, the anode catalytic material for electrolyzing seawater is as follows: metal ferrocyanide, metal ferricyanide, metal ferrocyanide-supported material, or metal ferricyanide-supported material; in the second scheme, one or more of ferrous cyanide and ferric cyanide are added into the electrolyte of the electrolyzed seawater. The action mechanisms of the two schemes are the same, and the ferric cyanide has the same charge with the chloride ion, so that the ferric cyanide can repel the chloride ion, and the chloride ion is difficult to approach the surface of the foam nickel substrate of the electrode, so that the stability of the electrode is improved.

Description

Method for resisting electrolytic seawater anode corrosion

Technical Field

The invention belongs to the technical field of inorganic advanced nano materials, and particularly relates to a method for resisting corrosion of an electrolytic seawater anode.

Background

The demand of human beings for hydrogen energy is gradually increasing, and the traditional ash hydrogen and blue hydrogen industries are extremely easy to cause environmental pollution and aggravated greenhouse effect. Therefore, the hydrogen production by water electrolysis has received a great deal of attention in recent years because of the simple process and no pollutant generation. In nature, the water resources mainly exist in the form of seawater, the proportion of the seawater in the global water resources can reach more than 96%, and if the pure water electrolysis is promoted on a large scale, the global pure water supply pressure is increased, so that the sustainable development is not facilitated. Thus, seawater electrolysis is imperative.

In the case of using seawater as the electrolyte, chloride ions therein tend to move to the vicinity of the anode due to the influence of the electric field force, and high concentration of chloride ions may cause corrosion of the current collector of the electrolysis system. The net reaction of the anode and cathode of the electrolysis system only consumes water, and the replenished fresh electrolyte is still sea water, so that the concentration of chloride ions in the electrolyte can be further increased after long-time electrolysis, and further the electrode is deactivated.

Disclosure of Invention

The present invention develops a method for resisting seawater electrolytic anode corrosion by using specific materials and anodes and adding additives to resist high salinity seawater corrosion.

The first aspect of the invention provides a method for resisting anode corrosion of electrolytic seawater, wherein electrolyte of the electrolytic seawater contains sodium chloride, and the method comprises at least one of the following two schemes:

in a first scheme, the anode catalytic material for electrolyzing seawater is as follows: metal ferrocyanide, metal ferricyanide, metal ferrocyanide-supported material, or metal ferricyanide-supported material;

in the second scheme, one or more of ferrous cyanide and ferric cyanide are added into the electrolyte of the electrolyzed seawater.

Preferably, in scheme one, the metal ferrocyanide is selected from: one or more of vanadium potassium ferricyanate, chromium potassium ferricyanate, manganese potassium ferricyanate, iron potassium ferricyanate, cobalt potassium ferricyanate, nickel cobalt iron ferricyanate;

the ferricyanide of the metal is selected from: one or more of vanadium potassium ferricyanate, chromium potassium ferricyanate, manganese potassium ferricyanate, iron potassium ferricyanate, cobalt potassium ferricyanate, nickel cobalt iron ferricyanate;

the metal ferrocyanide support material is selected from: a composite of metal ferrocyanide and phosphide, a composite of metal ferrocyanide and sulfide, a composite of metal ferrocyanide and boride, a composite of metal ferrocyanide and nitride, or a composite of metal ferrocyanide and selenide; in the material, the inner layer of ferrocyanide of metal is compounded with phosphide, sulfide, boride, nitride or selenide to form a ferrocyanide/phosphide, ferrocyanide/sulfide, ferrocyanide/boride, ferrocyanide/nitride or ferrocyanide/selenide heterostructure;

the ferricyanide support material of the metal is selected from: a composite of metal ferricyanide and phosphide, a composite of metal ferricyanide and sulfide, a composite of metal ferricyanide and boride, a composite of metal ferricyanide and nitride, or a composite of metal ferricyanide and selenide; in the material, the inner layer of metal ferricyanide is composited with phosphide, sulfide, boride, nitride or selenide to form a ferricyanide/phosphide, ferricyanide/sulfide, ferricyanide/boride, ferricyanide/nitride or ferricyanide/selenide heterostructure.

More preferably, in the first aspect, the ferrocyanide supporting material of the metal is cobalt ferrocyanide potassium/cobalt phosphide, vanadium potassium ferrocyanide/vanadium phosphide, chromium potassium ferrocyanide/chromium phosphide, manganese potassium ferrocyanide/manganese phosphide, iron potassium ferrocyanide/iron phosphide, nickel potassium ferrocyanide/nickel phosphide, nickel cobalt iron ferrocyanide/nickel cobalt iron phosphide, cobalt potassium ferrocyanide/cobalt sulfide, cobalt potassium ferrocyanide/cobalt boride, cobalt potassium ferrocyanide/cobalt nitride or cobalt potassium ferrocyanide/cobalt selenide;

the ferrocyanide supporting material of the metal is as follows: cobalt potassium ferricyanate/cobalt phosphide, vanadium potassium ferricyanate/vanadium phosphide, chromium potassium ferricyanate/chromium phosphide, manganese potassium ferricyanate/manganese phosphide, iron potassium ferricyanate/iron phosphide or nickel potassium ferricyanate/nickel cobalt iron phosphide, nickel cobalt iron ferricyanate/nickel cobalt iron phosphide, cobalt potassium ferricyanate/cobalt sulfide, cobalt potassium ferricyanate/cobalt boride, cobalt potassium ferricyanate/cobalt nitride or cobalt potassium ferricyanate/cobalt selenide.

Preferably, the metal ferricyanide supporting material or the metal ferrocyanide supporting material is obtained by reacting cobalt phosphide arrays with potassium ferricyanide or potassium ferrocyanide solution at 60-120 ℃ for 10-40 hours.

Preferably, in scheme two, the ferrocyanide is added in the form of potassium ferrocyanide or sodium ferrocyanide, and the ferrocyanide is added in the form of potassium ferrocyanide or sodium ferrocyanide.

Preferably, after one or more of ferrous cyanide and ferric cyanide is added into the electrolyte of the electrolyzed seawater, the electrolyte is provided with:

the concentration of the ferrocyanide is as follows: 0.1 to 100 milligrams per milliliter;

or the concentration of the ferricyanide is as follows: 0.1 to 100 milligrams per milliliter;

or the total concentration of the ferrocyanide or the ferrocyanide is as follows: 0.1 to 100 milligrams per milliliter.

Preferably, the electrolyte for electrolyzing seawater contains: 6 moles per liter of base and 2.8 moles per liter of (saturated) sodium chloride.

The alkali is one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Of course, other electrolytes of sodium hydroxide and sodium chloride concentration may be selected, and other alkali metal hydroxides may be selected in place of sodium hydroxide, such as: one or more of lithium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.

The technical proposal can be freely combined on the premise of no contradiction.

Compared with the prior art, the invention has the following beneficial effects:

the beneficial effects of the invention are as follows:

1. the present invention surprisingly found that in the electrolysis of seawater, a metal-containing ferrocyanide or a metal-containing ferricyanide-containing material is used as the anode for the electrolysis of seawater, which anode material has corrosion resistance.

In addition, the invention surprisingly found that when one or more of ferrous cyanide and ferric cyanide are added into the electrolyte of the electrolyzed seawater in the process of electrolyzing the seawater, the corrosion resistance of the anode material is also improved.

The action mechanisms of the two schemes are the same, and the ferric cyanide has the same charge with the chloride ion, so that the ferric cyanide can repel the chloride ion, and the chloride ion is difficult to approach the surface of the foam nickel substrate of the electrode, so that the stability of the electrode is improved.

When the potassium ferricyanide or potassium ferrocyanide electrolyte additive is used, the additive is anchored in the double electric layers of the anode under the action of electric field force, and the ferric cyanide has higher valence state and larger ion volume, so that the adsorption of chloride ions on the surface of the electrode is effectively inhibited, and the corrosion resistance stability of the electrolytic seawater anode is greatly improved.

2. Further, when the ferrocyanide of the metal or the inner layer of the ferrocyanide of the metal is compounded with the phosphide to form a heterostructure, the corrosion resistance is better. For example, the electrodes are: the cobalt potassium ferrocyanide/cobalt phosphide is oxidized into iron cyanide ions in the oxygen evolution reaction process, phosphorus is oxidized into phosphate ions and polyphosphate ions, meanwhile, part of the iron ions and cobalt ions are subjected to ion exchange, and the electrode is finally reconstructed into CoOOH and FeOOH. And the ferric cyanide ions and the phosphate ions formed in the reconstruction process can repel the chloride ions in the oxygen evolution reaction process, so that the anode material is further prevented from being corroded. For example, the materials may be: cobalt potassium ferricyanate/cobalt phosphide composite material.

Drawings

FIG. 1 shows the X-ray diffraction pattern of the cobalt potassium ferricyanate electrode of example 1.

Fig. 2 is a scanning electron micrograph of the cobalt potassium ferricyanate electrode of example 1.

FIG. 3 is a linear sweep voltammogram of the cobalt potassium ferricyanate electrode of example 2.

FIG. 4 is a graph of example 3 using a foam nickel electrode (solid spheres) and a cobalt potassium ferricyanate electrode (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current curve at current density.

FIG. 5 is an X-ray diffraction pattern of the cobalt potassium ferricyanate/cobalt phosphide electrode of example 4.

FIG. 6 is a scanning electron micrograph of a cobalt potassium ferricyanate/cobalt phosphide electrode of example 4.

FIG. 7 is a linear sweep voltammogram of a cobalt potassium ferricyanate/cobalt phosphide electrode of example 5.

FIG. 8 is a graph of the electrolyte at 200mA cm using a foam nickel electrode (solid spheres), using a cobalt potassium ferricyanate/cobalt phosphide electrode (hollow spheres) in example 6 ^-2 Constant current curve at current density.

FIG. 9 is a schematic diagram showing the use of a foam nickel electrode according to example 7, in which no potassium ferrocyanide (solid spheres) was added and 0.1 mg/ml potassium ferrocyanide (hollow spheres) was added to the electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 10 shows the use of a foam nickel electrode according to example 8, in which no potassium ferrocyanide (solid spheres) and 10 mg/ml potassium ferrocyanide (hollow spheres) were added to the electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 11 shows the use of a foam nickel electrode according to example 9, in which no potassium ferrocyanide (solid spheres) was added and 100 mg/ml potassium ferrocyanide (hollow spheres) was added to 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 12 shows the use of a foam nickel electrode according to example 10, in which no potassium ferricyanide (solid spheres) and 0.1 mg/ml potassium ferricyanide (hollow spheres) were added to the electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 13 shows the use of a foam nickel electrode according to example 11, in which 10 mg/ml of potassium ferricyanide (hollow spheres) was added to 200mAcm without adding potassium ferricyanide (solid spheres) to the electrolyte ^-2 Constant current profile at current density for 30 hours.

FIG. 14 shows the use of a foam nickel electrode according to example 12, in which no potassium ferricyanide (solid spheres) was added and 100 mg/ml potassium ferricyanide (hollow spheres) was added to 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 15 is a graph of 200mAcm in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a vanadium potassium ferricyanate electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) of example 13 ^-2 Constant current profile at current density for 30 hours.

FIG. 16 is a schematic illustration of example 14 using a foam nickel electrode and without the addition of potassium ferricyanide (solid spheres), using chromium potassium ferricyanate in the electrolyteElectrode and 0.1 mg/ml potassium ferricyanide (hollow sphere) was added at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 17 is a graph of 200mAcm in electrolyte using a nickel foam electrode and without potassium ferricyanide (solid spheres), using a manganese potassium ferricyanate electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) of example 15 ^-2 Constant current profile at current density for 30 hours.

FIG. 18 is a graph of 200mAcm in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a ferripotassium ferricyanate electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in example 16 ^-2 Constant current profile at current density for 30 hours.

FIG. 19 is a graph of 200mAcm in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanate electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) of example 17 ^-2 Constant current profile at current density for 30 hours.

FIG. 20 is a schematic diagram of example 18 in which a foam nickel electrode was used and no potassium ferricyanide (solid spheres) was added, a nickel potassium ferricyanate electrode was used and 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 21 is a schematic diagram of example 19 in which a foam nickel electrode was used and no potassium ferricyanide (solid spheres) was added, a nickel cobalt iron ferricyanate electrode was used and 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 22 shows example 20 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a vanadium potassium ferricyanide electrode and with 0.1 mg/ml potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 23 is a schematic diagram of example 21 in which a foam nickel electrode was used and potassium ferricyanide (solid spheres) was not added to the electrolyte, and ferricyanide was usedChromium potassium electrode and 0.1 mg/ml potassium ferricyanide (hollow sphere) was added at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 24 is a graph of 200mAcm in electrolyte using a nickel foam electrode and without potassium ferricyanide (solid spheres), using a manganese potassium ferricyanide electrode and with 0.1 mg/ml potassium ferricyanide (hollow spheres) for example 22 ^-2 Constant current profile at current density for 30 hours.

FIG. 25 is a graph of 200mAcm in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a ferric potassium ferricyanide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) for example 23 ^-2 Constant current profile at current density for 30 hours.

FIG. 26 is a graph of 200mAcm in electrolyte using a nickel foam electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanide electrode and with 0.1 mg/ml potassium ferricyanide (hollow spheres) for example 24 ^-2 Constant current profile at current density for 30 hours.

FIG. 27 is a graph showing that example 25 uses a foam nickel electrode and no potassium ferricyanide (solid spheres), uses a nickel potassium ferricyanide electrode and 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 28 is a schematic representation of example 26 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a nickel cobalt iron ferricyanide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours. FIG. 29 is a graph of 200mA cm in electrolyte using a foam nickel electrode and without the addition of potassium ferricyanide (solid spheres), using a vanadium potassium ferricyanate/vanadium phosphide electrode and with the addition of 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) for example 27 ^-2 Constant current profile at current density for 30 hours.

FIG. 30 is a schematic illustration of example 28 in an electrolyte using a foam nickel electrode and without the addition of potassium ferricyanide (solid spheres), using a chromium potassium ferricyanate/chromium phosphide electrode and0.1 mg/ml potassium ferricyanide (hollow spheres) was added at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 31 is a schematic representation of example 29 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a manganese ferricyanate/manganese phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 32 is a schematic diagram of example 30 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a ferripotassium ferricyanate/iron phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 33 is a graph of 200mAcm in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanate/cobalt phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) for example 31 ^-2 Constant current profile at current density for 30 hours.

FIG. 34 shows example 32 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a nickel potassium ferricyanate/nickel phosphide electrode and with 0.1 mg/ml potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 35 is a schematic diagram of example 33 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a nickel cobalt iron ferricyanate/nickel cobalt iron phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 36 is a schematic representation of example 34 using a foam nickel electrode and without added potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanate/cobalt sulfide electrode and with added 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 37 is a schematic illustration of example 35 in an electrolyte using a foam nickel electrodeAnd without adding potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanide/cobalt boride electrode and adding 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 38 is a schematic representation of example 36 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanate/cobalt nitride electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 39 is a schematic diagram of example 37 in which a foam nickel electrode was used and no potassium ferricyanide (solid spheres) was added, a cobalt potassium ferricyanate/cobalt selenide electrode was used and 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) was added to an electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours. FIG. 40 is a graph of example 38 using a foam nickel electrode and without the addition of potassium ferricyanide (solid spheres), using a vanadium potassium ferricyanide/vanadium phosphide electrode and with the addition of 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 41 is a schematic diagram of example 39 in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a chromium potassium ferricyanide/chromium phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 42 is a schematic representation of example 40 using a foam nickel electrode and without added potassium ferricyanide (solid spheres), using a manganese ferricyanide/manganese phosphide electrode and with added 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mAcm in an electrolyte ^-2 Constant current profile at current density for 30 hours.

FIG. 43 is a schematic representation of example 41 using a foam nickel electrode and without added potassium ferricyanide (solid spheres), using a ferripotassium ferricyanide/iron phosphide electrode and with added 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 44 shows example 42 in the electrolysisIn the solution, a foam nickel electrode was used without adding potassium ferricyanide (solid spheres), a cobalt potassium ferricyanide/cobalt phosphide electrode was used with adding 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 45 is a schematic diagram of example 43 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a nickel potassium ferricyanide/nickel phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 46 is a schematic diagram of example 44 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a nickel cobalt iron ferricyanide/nickel cobalt iron phosphide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 47 is a graph of 200mAcm using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanide/cobalt sulfide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte for example 45 ^-2 Constant current profile at current density for 30 hours.

FIG. 48 shows example 46 using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanide/cobalt boride electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 Constant current profile at current density for 30 hours.

FIG. 49 shows example 47A 200mAcm thick foam nickel electrode without added potassium ferricyanide (solid spheres), cobalt potassium ferricyanide/cobalt nitride electrode with added 0.1 mg/ml potassium ferricyanide (hollow spheres) in an electrolyte ^-2 Constant current profile at current density for 30 hours.

FIG. 50 is a graph of example 48 in electrolyte using a foam nickel electrode and without potassium ferricyanide (solid spheres), using a cobalt potassium ferricyanide/cobalt selenide electrode and with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres), at 200mAcm ^-2 Constant current profile for 30 hours at current density。

FIG. 51 is a schematic representation of example 49 using a foam nickel electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) added to 6 moles/liter lithium hydroxide and 2.8 moles/liter sodium chloride electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 52 shows the use of a foam nickel electrode in example 50, in which 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to 6 moles/l potassium hydroxide and 2.8 moles/l sodium chloride electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 53 shows the use of a foam nickel electrode in example 51, in which 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to 6 moles/liter of rubidium hydroxide and 2.8 moles/liter of sodium chloride electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 54 shows the use of a foam nickel electrode in example 52, in which 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to 6 moles/liter cesium hydroxide and 2.8 moles/liter sodium chloride electrolyte at 200mA cm ^-2 Constant current profile at current density for 30 hours.

FIG. 55 shows a cobalt potassium ferricyanide electrode of example 53 in a mixed electrolyte of 6 moles per liter of sodium hydroxide and 2.8 moles per liter of sodium chloride, and in the above electrolyte to which 0.1 mg per ml of potassium ferricyanide or potassium ferrocyanide was added, at 200mAcm ^-2 A constant current curve under.

FIG. 56 shows a cobalt potassium ferricyanide/cobalt phosphide electrode of example 54 in a mixed electrolyte of 6 moles per liter of sodium hydroxide and 2.8 moles per liter of sodium chloride, and in the above-mentioned electrolyte to which 0.1 mg per milliliter of potassium ferricyanide or potassium ferrocyanide was added, at 200mAcm ^-2 A constant current curve under.

Detailed Description

The present invention will be described in further detail with reference to examples.

It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The materials or equipment used are conventional products available from commercial sources, not identified to the manufacturer.

As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless expressly stated otherwise, as understood by those skilled in the art. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "coupled" to another element, it can be directly coupled to the other element or intervening elements may also be present. Further, "coupled" as used herein may include wirelessly coupled.

In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more. The orientation or state relationship indicated by the terms "inner", "upper", "lower", etc. are orientation or state relationship based on the drawings, are merely for convenience of description and simplification of description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the invention.

In the description of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the terms "mounted," "coupled," and "provided" are to be construed broadly, and may be, for example, fixedly coupled, detachably coupled, or integrally coupled; can be mechanically or electrically coupled; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in the present invention is understood by those of ordinary skill in the art according to the specific circumstances.

It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

The method for preparing the cobalt potassium ferrocyanate and the cobalt potassium ferrocyanate/cobalt phosphide is self-made.

Example 1 preparation of Potassium vanadium ferricyanate electrode, potassium chromium ferricyanate electrode, potassium manganese ferricyanate electrode, potassium iron ferricyanate electrode, potassium cobalt ferricyanate electrode, nickel Potassium ferricyanate electrode, nickel cobalt iron ferrocyanate electrode, potassium vanadium ferricyanate electrode, potassium chromium ferricyanate electrode, potassium manganese ferricyanate electrode, potassium iron ferricyanate electrode, cobalt Potassium ferricyanate electrode, nickel cobalt iron ferricyanate electrode

The following method is used to prepare cobalt potassium ferricyanate in this example, which can of course be adjusted by those skilled in the art with reference to the prior art:

(1) 30 ml of solution, namely 0.6 g of urea and 0.3 g of cobalt nitrate hexahydrate, is prepared, the solution is poured into a 50 ml reaction kettle, the washed foam nickel is soaked into the solution, and the solution is put into an oven, wherein the reaction temperature is 120 ℃ and the reaction time is 12 hours. The resulting material was washed 3 times with water and ethanol, respectively, and dried in vacuo at 60℃for 10 hours. Thus obtaining the cobalt hydroxide hydrotalcite array material.

(2) 30 ml of solution was prepared: 1g of potassium ferrocyanide, soaking the obtained cobalt hydroxide hydrotalcite array into the solution, and putting the solution into an oven, wherein the reaction temperature is 90 ℃ and the reaction time is 24 hours. The resulting material was washed 3 times with water and ethanol, respectively, and dried in vacuo at 60℃for 10 hours. Namely the ferrous cobalt potassium cyanate electrode (with a foam nickel substrate).

Other conditions are not changed, and cobalt nitrate hexahydrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate. The preparation method can be respectively used for preparing the following components: a vanadium potassium ferricyanate electrode, a chromium potassium ferricyanate electrode, a manganese potassium ferricyanate, a ferric potassium ferricyanate electrode, a nickel potassium ferricyanate electrode, and a nickel cobalt iron ferricyanate electrode.

Other conditions are unchanged, and potassium ferrocyanide with equimolar numbers can be prepared by replacing potassium ferrocyanide: cobalt potassium ferricyanate electrode.

Other conditions are not changed, and cobalt nitrate hexahydrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, ferric nitrate nonahydrate, nickel nitrate hexahydrate or nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate mixed salt with the mol ratio of 1:1:2; and the potassium ferrocyanide is replaced by potassium ferricyanide with the same mole number. The preparation method can be respectively used for preparing the following components: vanadium potassium ferricyanate electrode, chromium potassium ferricyanate electrode, manganese potassium ferricyanate electrode, iron potassium ferricyanate electrode, nickel cobalt iron ferricyanate electrode.

The above-mentioned cobalt potassium ferricyanate electrode was placed in a glass vial containing 10 ml of water, sonicated in an ultrasonic cleaner for 15 minutes, and then the resulting turbid liquid was centrifuged, and the resulting powder was dried in vacuo at 60 ℃ for 10 hours. The powder was subjected to X-ray diffraction, the X-ray diffraction pattern (XRD) was shown in fig. 1, and was consistent with the standard card of cobalt potassium ferricyanate, demonstrating successful synthesis of cobalt potassium ferricyanate. The Scanning Electron Microscope (SEM) pattern of the electrode material is shown in fig. 2, and the cobalt potassium ferricyanate is in a cubic block shape.

Example 2 oxygen evolution reactivity test

The electrolytic seawater electrolysis catalytic oxygen evolution performance of the cobalt potassium ferricyanate electrode obtained in example 1 was tested by a three-electrode system: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is a cobalt potassium ferricyanate electrode or a foam nickel electrode with an effective area of 1*1 square centimeters, the electrolyte adopts a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, and cyclic voltammetry scanning is firstly carried out within the range of 1-2 Vvs RHE until the electrode reaches a stable state. Then changing new electrolyte, and carrying out linear scanning at 2mV/s within the range of 1-2V vs RHE. The resulting linear sweep voltammogram is shown in figure 3.

As can be seen from FIG. 3, ferricyanic acidCobalt potassium at 10mAcm ^-2 The overpotential at current density was 330mV.

EXAMPLE 3 Corrosion resistance test

The corrosion resistance stability of the seawater electrolysis anode of the cobalt potassium ferricyanate electrode is tested by a three-electrode system: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is a cobalt potassium ferricyanate electrode or a foam nickel electrode with an effective area of 1*1 square centimeters, the electrolyte adopts a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, a constant current test of 200 milliamperes per square centimeter is carried out, and the obtained constant current curve is shown in figure 4. It can be seen from fig. 4 that the use of the cobalt potassium ferricyanate electrode is effective in preventing corrosion, and thus the anode stability can be maintained for a longer period of time, up to about 45 hours (hollow circles in fig. 4).

Example 4 preparation of cobalt Fecyanate/cobalt phosphide, vanadium Fecyanate/vanadium phosphide, chromium Fecyanate/chromium phosphide, manganese Fecyanate/manganese phosphide, iron Fecyanate/iron phosphide, nickel Fecyanate/nickel phosphide, nickel Fecyanate/cobalt phosphide, cobalt Fecyanate/cobalt sulfide, cobalt Fecyanate/cobalt boride, cobalt ferricyanate/cobalt nitride, cobalt Fecyanate/cobalt selenide, cobalt Fecyanate/cobalt phosphide, vanadium Fecyanate/vanadium phosphide, chromium Fecyanate/chromium phosphide, manganese Fecyanate/manganese phosphide, iron ferricyanate/iron phosphide, nickel Fecyanate/nickel phosphide, cobalt Fecyanate/cobalt boride, cobalt Fecyanate/cobalt nitride, cobalt Fecyanate/cobalt selenide

The following method is used to prepare the potassium cobalt ferricyanate/cobalt phosphide in this example, which can of course be adjusted by those skilled in the art with reference to the prior art:

(1) 30 ml of solution, 0.6 g of urea and 0.291 g of cobalt nitrate, is prepared, poured into a 50 ml reaction kettle, soaked into the solution, and put into an oven, wherein the reaction temperature is 120 ℃ and the reaction time is 12 hours. The obtained material is washed with water and ethanol for 3 times respectively, and vacuum dried for 10 hours at 60 ℃ to obtain the cobalt hydroxide hydrotalcite array loaded on the foam nickel.

(2) And (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and sodium hypophosphite in a tube furnace (500 mg sodium hypophosphite), heating to 300 ℃, and preserving heat for 2 hours to obtain the cobalt phosphide array growing on the foam nickel substrate.

(3) 30 ml of solution was prepared: 1g of potassium ferricyanide, immersing the obtained cobalt phosphide array loaded on the foam nickel into the solution, and putting the solution into an oven, wherein the reaction temperature is 90 ℃ and the reaction time is 24 hours. The resulting material was washed 3 times with water and ethanol, respectively, and dried in vacuo at 60℃for 10 hours. Namely the cobalt potassium ferricyanate/cobalt phosphide electrode.

(with foam Nickel base)

The above electrode was placed in a glass vial containing 10 ml of water, sonicated in an ultrasonic cleaner for 15 minutes, and then the resulting cloudy solution was centrifuged, and the resulting powder was dried in vacuo at 60℃for 10 hours. The powder was subjected to X-ray diffraction, the X-ray diffraction pattern (XRD) is shown in fig. 5, and is consistent with standard cards of potassium cobalt ferricyanate and cobalt phosphide, demonstrating successful synthesis of the potassium cobalt ferricyanate/cobalt phosphide heterostructure. The scanning electron microscope pattern (SEM) of the electrode material is shown in fig. 6, and the cobalt potassium ferricyanate/cobalt phosphide heterostructure is also in the shape of a cubic block.

Changing the conditions, preparing other materials: other conditions are not changed, and cobalt nitrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate. The preparation method can be respectively used for preparing the following components: vanadium potassium ferricyanate/vanadium phosphide electrode, chromium potassium ferricyanate/chromium phosphide electrode, manganese potassium ferricyanate/manganese phosphide electrode, iron potassium ferricyanate/iron phosphide electrode, nickel potassium ferricyanate/nickel phosphide electrode, nickel cobalt potassium ferrocyanate/nickel cobalt iron phosphide electrode.

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and sublimed sulfur into a tube furnace (500 mg sublimed sulfur), heating to 300 ℃, and preserving heat for 2 hours to obtain the cobalt sulfide array growing on the foam nickel substrate. And (3) obtaining the cobalt potassium ferricyanate/cobalt sulfide electrode.

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in sodium borohydride solution (20 millimoles per liter of sodium borohydride), and carrying out ice bath for 24 hours to obtain the cobalt boride array growing on the foam nickel substrate. And (3) obtaining the cobalt potassium ferricyanate/cobalt boride electrode.

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in a tubular furnace (20% ammonia gas and air flow speed of 20 sccm) under the atmosphere of ammonia gas and argon gas, heating to 450 ℃, and preserving heat for 3 hours to obtain the cobalt nitride array growing on the foam nickel substrate. And (3) obtaining the cobalt potassium ferricyanate/cobalt nitride electrode.

The other steps are unchanged, and the step (2) is replaced by: and (3) adding the cobalt hydroxide hydrotalcite array and selenium powder (3.75 mmol), sodium hydroxide (7.5 mmol), hydrazine (0.14 mL) and N, N-dimethylformamide (25 mL) which are obtained in the step (1) and loaded on the foam nickel into 50mL of mixed aqueous solution, and carrying out hydrothermal reaction in a hydrothermal reaction kettle at 180 ℃ for 1 hour to obtain the cobalt selenide array growing on the foam nickel substrate. And (3) obtaining the cobalt potassium ferricyanate/cobalt selenide electrode. Other conditions are unchanged, and the potassium ferrocyanide is changed into potassium ferrocyanide with the same mole number, so that the preparation method can be used for preparing the potassium ferrocyanide: cobalt potassium ferricyanate/cobalt phosphide electrode loaded on foam nickel.

Other conditions are not changed, and cobalt nitrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate mixed salt; and the potassium ferrocyanide is replaced by potassium ferricyanide with the same mole number. The preparation method can be respectively used for preparing the following components: vanadium potassium ferricyanate/vanadium phosphide electrode, chromium potassium ferricyanate/chromium phosphide electrode, manganese potassium ferricyanate/manganese phosphide electrode, iron potassium ferricyanate/iron phosphide electrode, nickel potassium ferricyanate/nickel phosphide electrode, nickel cobalt potassium ferricyanate/nickel cobalt iron phosphide electrode.

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and sublimed sulfur into a tube furnace (500 mg sublimed sulfur), heating to 300 ℃, and preserving heat for 2 hours to obtain the cobalt sulfide array growing on the foam nickel substrate. And (3) replacing the potassium ferrocyanide with the same mole number, and obtaining the cobalt potassium ferrocyanide/cobalt sulfide electrode after the step (3).

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in sodium borohydride solution (20 millimoles per liter of sodium borohydride), and carrying out ice bath for 24 hours to obtain the cobalt boride array growing on the foam nickel substrate. And (3) replacing the potassium ferrocyanide with the same mole number, and obtaining the cobalt potassium ferrocyanide/cobalt boride electrode after the step (3).

The other steps are unchanged, and the step (2) is replaced by: and (3) placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in a tubular furnace (20% ammonia gas and air flow speed of 20 sccm) under the atmosphere of ammonia gas and argon gas, heating to 450 ℃, and preserving heat for 3 hours to obtain the cobalt nitride array growing on the foam nickel substrate. And (3) replacing the potassium ferrocyanide with the same mole number, and obtaining the cobalt potassium ferrocyanide/cobalt nitride electrode after the step (3).

The other steps are unchanged, and the step (2) is replaced by: and (3) adding the cobalt hydroxide hydrotalcite array and selenium powder (3.75 mmol), sodium hydroxide (7.5 mmol), hydrazine (0.14 mL) and N, N-dimethylformamide (25 mL) which are obtained in the step (1) and loaded on the foam nickel into 50mL of mixed aqueous solution, and carrying out hydrothermal reaction in a hydrothermal reaction kettle at 180 ℃ for 1 hour to obtain the cobalt selenide array growing on the foam nickel substrate. And (3) replacing the potassium ferrocyanide with the same mole number, and obtaining the cobalt potassium ferrocyanide/cobalt selenide electrode after the step (3).

Example 5 oxygen evolution reactivity test

Test methods referring to example 2, the working electrode was changed to potassium cobalt ferricyanate/cobalt phosphide. The resulting linear sweep voltammogram is shown in FIG. 7. As can be seen from a comparison of FIGS. 7 and 3, the ratio of potassium cobalt ferricyanate/cobalt phosphide is 10mAcm ^-2 The overpotential under the current density is 297mV, and the electrocatalytic oxygen evolution reaction activity is higher than that of the cobalt potassium ferricyanate electrode.

EXAMPLE 6 electrode Corrosion resistance test

Test methods referring to example 3, the working electrode was changed to potassium cobalt ferricyanate/cobalt phosphide. The resulting constant current curve is shown in fig. 8. It can be seen from fig. 8 that the anode stability is superior to that of the cobalt potassium ferrocyanate electrode and far superior to that of the nickel foam electrode after the cobalt potassium ferrocyanate/cobalt phosphide electrode is adopted. It is demonstrated that the cobalt potassium ferricyanate/cobalt phosphide electrode is effective in corrosion protection and thus can maintain anode stability for a longer period of time, up to 140 hours (open circles in fig. 8).

EXAMPLE 7 additive-Corrosion resistance test of electrolyte

The reason why the cobalt potassium ferricyanate/cobalt phosphide electrode is anti-corrosion is mainly that it is formed of iron cyanate, phosphate and polyphosphate during the anodic reaction. Therefore, the invention further can effectively inhibit corrosion by adding ferricyanide or ferricyanide into the electrolyte.

The additive-containing seawater electrolysis anode of the invention was tested for corrosion resistance stability using a three electrode system: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is commercial foam nickel with an effective area of 1*1 square centimeters, 0.1 milligram per milliliter of potassium ferrocyanide is added into a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, the mixed solution is used as electrolyte to perform a constant current test of 200 milliamperes per square centimeter, the comparative example has no potassium ferrocyanide additive, and the obtained constant current curve is shown in figure 9. It can be seen from fig. 9 that the electrolyte after potassium ferricyanide addition has a better corrosion resistance effect, and thus can maintain anode stability for a long period of time (30 hours) (open circles of fig. 9), and cathode stability thereof is superior to that of the control sample without additives (solid circles of fig. 9).

EXAMPLE 8 additive-Corrosion resistance test of electrolyte

Test methods see example 7, changing from adding 0.1 milligrams per milliliter of potassium ferrocyanide to adding 10 milligrams per milliliter of potassium ferrocyanide. The resulting constant current curve is shown in fig. 10. It can be seen from fig. 10 that the addition of 10 mg/ml of potassium ferrocyanide to the electrolyte effectively inhibited corrosion, and thus maintained the anode stability for a longer period of time (30 hours) (open circles in fig. 10).

EXAMPLE 9 additive-Corrosion resistance test of electrolyte

Test methods see example 7, changing from adding 0.1 milligrams per milliliter of potassium ferrocyanide to adding 100 milligrams per milliliter of potassium ferrocyanide. The resulting constant current curve is shown in FIG. 11. It can be seen from fig. 11 that the addition of 100 mg/ml of potassium ferrocyanide to the electrolyte effectively inhibited corrosion, and thus maintained the anode stability for a longer period of time (30 hours) (open circles in fig. 11).

EXAMPLE 10 additive-testing of Corrosion resistance of electrolytes

Test methods see example 7, changing from adding 0.1 milligrams per milliliter of potassium ferrocyanide to adding 0.1 milligrams per milliliter of potassium ferricyanide. The resulting constant current curve is shown in fig. 12. It can be seen from fig. 12 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte effectively inhibited corrosion, and thus maintained the anode stability for a longer period of time (30 hours) (open circles in fig. 12).

EXAMPLE 11 additive-Corrosion resistance test of electrolyte

Test methods see example 7, changing from adding 0.1 milligrams per milliliter of potassium ferrocyanide to adding 10 milligrams per milliliter of potassium ferricyanide. The resulting constant current curve is shown in fig. 13. It can be seen from fig. 13 that the addition of 10 mg/ml of potassium ferricyanide to the electrolyte effectively inhibited corrosion, and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 13).

Example 12 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods see example 7, changing from adding 0.1 milligrams per milliliter of potassium ferrocyanide to adding 100 milligrams per milliliter of potassium ferricyanide. The resulting constant current curve is shown in fig. 14. It can be seen from fig. 14 that the addition of 100 mg/ml of potassium ferricyanide to the electrolyte effectively inhibited corrosion, and thus maintained the anode stability for a longer period of time (30 hours) (open circles of fig. 14).

Example 13 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium vanadium ferricyanate electrode. The resulting constant current curve is shown in fig. 15. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 15 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium vanadium ferricyanate electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period of time (30 hours) (open circles in fig. 15).

Example 14 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium chromium ferricyanate electrode. The resulting constant current curve is shown in fig. 16. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 16 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the chromium potassium ferricyanate electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period of time (30 hours) (open circles in fig. 16).

Example 15 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium manganese ferricyanate electrode. The resulting constant current curve is shown in fig. 17. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 17 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a potassium manganese ferricyanate electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 17) was maintained for a longer period of time (30 hours).

EXAMPLE 16 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium iron ferricyanate electrode. The resulting constant current curve is shown in fig. 18. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 18 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium ferricyanate electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 18) was maintained for a longer period of time (30 hours).

EXAMPLE 17 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate electrode. The resulting constant current curve is shown in FIG. 19. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 19 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 19) was maintained for a longer period of time (30 hours).

Example 18 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium nickel ferricyanate electrode. The resulting constant current curve is shown in fig. 20. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 20 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a nickel potassium ferricyanate electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 20) was maintained for a longer period of time (30 hours).

EXAMPLE 19 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferricyanate electrode. The resulting constant current curve is shown in fig. 21. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 21 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a nickel cobalt iron ferricyanate electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 21) was maintained for a longer period of time (30 hours).

EXAMPLE 20 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a vanadium potassium ferricyanate electrode. The resulting constant current curve is shown in fig. 22. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 22 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the vanadium potassium ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 22) was maintained for a longer period of time (30 hours).

EXAMPLE 21 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a chromium potassium ferricyanate electrode. The resulting constant current curve is shown in FIG. 23. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 23 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the chromium potassium ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 23) was maintained for a longer period of time (30 hours).

EXAMPLE 22 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium manganese ferricyanide electrode. The resulting constant current curve is shown in fig. 24. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 24 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a potassium manganese ferricyanide electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period of time (30 hours) (open circles in fig. 24).

EXAMPLE 23 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium iron ferricyanide electrode. The resulting constant current curve is shown in fig. 25. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 25 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 25) was maintained for a longer period of time (30 hours).

EXAMPLE 24 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide electrode. The resulting constant current curve is shown in fig. 26. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 26 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 26) was maintained for a longer period of time (30 hours).

EXAMPLE 25 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel potassium ferricyanide electrode. The resulting constant current curve is shown in FIG. 27. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 27 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a nickel potassium ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 27) was maintained for a longer period of time (30 hours).

EXAMPLE 26 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferricyanide electrode. The resulting constant current curve is shown in FIG. 28. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 28 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a nickel cobalt iron ferricyanide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 28) was maintained for a longer period of time (30 hours). Example 27 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium vanadium ferricyanate/vanadium phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 29. It can be seen from fig. 29 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium vanadium ferricyanate/vanadium phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 29) was maintained for a longer period of time (30 hours).

EXAMPLE 28 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium chromite ferricyanate/chromium phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 30. It can be seen from fig. 30 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium chromium ferricyanate/chromium phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 30) was maintained for a longer period of time (30 hours).

Example 29 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium manganese ferricyanate/manganese phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 31. It can be seen from fig. 31 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a potassium manganese ferricyanate/manganese phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 31) was maintained for a longer period of time (30 hours).

EXAMPLE 30 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium ferricyanate/iron phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in fig. 32. It can be seen from fig. 32 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium ferricyanate/iron phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 32) was maintained for a longer period of time (30 hours).

Example 31 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate/cobalt phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 33. It can be seen from fig. 33 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate/cobalt phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 33) was maintained for a longer period of time (30 hours).

Example 32 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel potassium ferricyanate/nickel phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in fig. 34. It can be seen from fig. 34 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the nickel potassium ferricyanate/nickel phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 34) was maintained for a longer period of time (30 hours).

Example 33 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferricyanate/nickel cobalt iron phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 35. It can be seen from fig. 35 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the nickel cobalt iron ferricyanate/nickel cobalt iron phosphide electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period (30 hours) (open circles of fig. 35).

Example 34 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate/cobalt sulfide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in fig. 36. It can be seen from fig. 36 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate/cobalt sulfide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 36) was maintained for a longer period of time (30 hours).

Example 35 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate/cobalt boride electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in fig. 37. It can be seen from fig. 37 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate/cobalt boride electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 37) was maintained for a longer period of time (30 hours).

Example 36 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate/cobalt nitride electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 38. It can be seen from fig. 38 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate/cobalt nitride electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 38) was maintained for a longer period of time (30 hours).

Example 37 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanate/cobalt selenide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 39. It can be seen from fig. 39 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanate/cobalt selenide electrode effectively inhibited corrosion, and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 39). EXAMPLE 38 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a vanadium potassium ferricyanate/vanadium phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 40. It can be seen from fig. 40 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the vanadium potassium ferricyanide/vanadium phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 40) was maintained for a longer period of time (30 hours).

Example 39 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium chromite ferricyanide/chromium phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 41. It can be seen from fig. 41 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium chromium ferricyanide/chromium phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 41) was maintained for a longer period of time (30 hours).

EXAMPLE 40 seawater electrolytic Corrosion resistance test of electrode coupling additive

The resulting constant current curve is shown in fig. 42. It can be seen from fig. 42 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium ferricyanide/manganese phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 42) was maintained for a longer period of time (30 hours).

Example 41 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium ferricyanide/iron phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 43. It can be seen from fig. 43 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the potassium ferricyanide/iron phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 43) was maintained for a longer period of time (30 hours).

Example 42 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide/cobalt phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 44. It can be seen from fig. 44 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanide/cobalt phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 44) was maintained for a longer period of time (30 hours).

EXAMPLE 43 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel potassium ferricyanide/nickel phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 45. It can be seen from fig. 45 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the nickel potassium ferricyanide/nickel phosphide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 45) was maintained for a longer period of time (30 hours).

EXAMPLE 44 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferricyanide/nickel cobalt iron phosphide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in fig. 46. It can be seen from fig. 46 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the nickel cobalt iron ferricyanide/nickel cobalt iron phosphide electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period of time (30 hours) (open circles in fig. 46).

EXAMPLE 45 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide/cobalt sulfide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 47. It can be seen from fig. 47 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanide/cobalt sulfide electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 47) was maintained for a longer period of time (30 hours).

Example 46 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide/cobalt boride electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 48. It can be seen from fig. 48 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanide/cobalt boride electrode effectively inhibited corrosion, and thus the anode stability was maintained for a longer period of time (30 hours) (open circles in fig. 48).

Example 47 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide/cobalt nitride electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 49. It can be seen from fig. 49 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of the cobalt potassium ferricyanide/cobalt nitride electrode effectively inhibited corrosion, and thus the anode stability (open circles of fig. 49) was maintained for a longer period of time (30 hours).

Example 48 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a cobalt potassium ferricyanide/cobalt selenide electrode. The comparative example was a foam nickel electrode and no potassium ferricyanide (solid spheres) was added.

The resulting constant current curve is shown in FIG. 50. It can be seen from fig. 50 that the addition of 0.1 mg/ml of potassium ferricyanide to the electrolyte and the use of a cobalt potassium ferricyanide/cobalt selenide electrode effectively inhibited corrosion, and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 50).

Example 49 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods see example 7, the electrolyte was changed to a mixed solution of 6 moles per liter of lithium hydroxide and saturated sodium chloride. The resulting constant current curve is shown in FIG. 51. From fig. 51, it can be seen that the electrolyte after 0.1 mg/ml of potassium ferricyanide was added has a good anti-corrosion effect, and thus can maintain anode stability for a long period of time (30 hours) (open circles of fig. 51).

Example 50 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods referring to example 7, the electrolyte was changed to a mixed solution of 6 moles per liter of potassium hydroxide and saturated sodium chloride. The resulting constant current curve is shown in fig. 52. From fig. 52, it can be seen that the electrolyte after 0.1 mg/ml of potassium ferricyanide is added has a good anti-corrosion effect, and thus can maintain anode stability for a long period of time (30 hours) (open circles of fig. 52).

Example 51 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test method referring to example 7, the electrolyte was changed to a mixed solution of 6 moles per liter of rubidium hydroxide and saturated sodium chloride. The resulting constant current curve is shown in FIG. 53. It can be seen from fig. 53 that the electrolyte after 0.1 mg/ml of potassium ferricyanide was added has a good anti-corrosion effect, and thus can maintain anode stability for a long period of time (30 hours) (open circles of fig. 53).

Example 52 seawater electrolytic Corrosion resistance test of electrode coupling additive

Test methods see example 7, the electrolyte was changed to a mixed solution of 6 moles per liter cesium hydroxide and saturated sodium chloride. The resulting constant current curve is shown in FIG. 54. From fig. 54, it can be seen that the electrolyte after 0.1 mg/ml of potassium ferricyanide was added has a good anti-corrosion effect, and thus can maintain anode stability for a long period of time (30 hours) (open circles of fig. 54).

Example 53 seawater electrolytic Corrosion resistance test of electrode coupling additive

The corrosion resistance stability of the seawater electrolysis anode of the cobalt potassium ferricyanide electrode coupling additive is tested by a three-electrode system: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is a cobalt potassium ferrocyanate electrode with an effective area of 1*1 square centimeters prepared in the embodiment 1, and the electrolyte adopts the following components: to a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride of 0.1 mg per ml of potassium ferrocyanide was added, and a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride of 0.1 mg per ml of potassium ferrocyanide was added. The constant current test of 200 milliamperes per square centimeter was performed with the above three mixed solutions as electrolytes, respectively, and the resulting constant current curves are shown in fig. 55. From fig. 55, it can be seen that after 0.1 mg/ml of potassium ferrocyanide or potassium ferricyanide is added to the electrolyte, the durability of the cobalt potassium ferricyanide electrode can be further improved, and corrosion inhibition is more effective, so that the anode stability (the hollow circles and the hollow triangles of fig. 55) can be maintained for a longer time (up to 200 hours).

Example 54 seawater electrolytic Corrosion resistance test of electrode coupling additive

The seawater electrolysis anode corrosion resistance stability of the cobalt potassium ferricyanide/cobalt phosphide electrode coupling additive of the present invention was tested with a three-electrode system: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is a cobalt potassium ferricyanide/cobalt phosphide electrode with an effective area of 1*1 square centimeters, and the electrolyte is respectively a mixed solution of 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, a mixed solution of 0.1 mg per milliliter of potassium ferrocyanide, 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride, and a mixed solution of 0.1 mg per milliliter of potassium ferricyanide, 6.0 mol per liter of sodium hydroxide and 2.8 mol per liter of sodium chloride. The constant current test of 200 milliamperes per square centimeter was performed with the above three mixed solutions as electrolytes, respectively, and the resulting constant current curves are shown in fig. 56. It can be seen from fig. 56 that after 0.1 mg/ml of potassium ferrocyanide or potassium ferricyanide is added to the electrolyte, the durability of the cobalt potassium ferrocyanide/cobalt phosphide electrode can be further improved, and the inhibition of corrosion prevention is more effective, so that the anode stability (open circles and open triangles of fig. 56) can be maintained for a longer period of time (up to 200 hours).

Claims

1. A method for resisting anodic corrosion of electrolyzed seawater, wherein electrolyte of the electrolyzed seawater contains sodium chloride and alkali, and the method is characterized by comprising at least one of the following two schemes:

adding one or more of ferrous cyanide and ferric cyanide into the electrolyte of the electrolyzed seawater;

in one embodiment, the metal ferrocyanide is selected from the group consisting of: one or more of vanadium potassium ferricyanate, chromium potassium ferricyanate, manganese potassium ferricyanate, iron potassium ferricyanate, cobalt potassium ferricyanate, nickel cobalt potassium ferricyanate;

the ferricyanide of the metal is selected from: one or more of vanadium potassium ferricyanate, chromium potassium ferricyanate, manganese potassium ferricyanate, iron potassium ferricyanate, cobalt potassium ferricyanate, nickel cobalt potassium ferricyanate;

The ferricyanide support material of the metal is selected from: a composite of metal ferricyanide and phosphide, a composite of metal ferricyanide and sulfide, a composite of metal ferricyanide and boride, a composite of metal ferricyanide and nitride, or a composite of metal ferricyanide and selenide; in the material, the inner layer of metal ferricyanide is compounded with phosphide, sulfide, boride, nitride or selenide to form a ferricyanide/phosphide, ferricyanide/sulfide, ferricyanide/boride, ferricyanide/nitride or ferricyanide/selenide heterostructure;

in the first scheme, the ferrocyanide loading material of the metal is cobalt potassium ferrocyanate/cobalt phosphide, vanadium potassium ferrocyanate/vanadium phosphide, chromium potassium ferrocyanate/chromium phosphide, manganese potassium ferrocyanate/manganese phosphide, iron potassium ferrocyanate/iron phosphide, nickel potassium ferrocyanate/nickel phosphide, nickel cobalt iron potassium ferrocyanate/nickel cobalt phosphide, cobalt potassium ferrocyanate/cobalt sulfide, cobalt potassium ferrocyanate/cobalt boride, cobalt potassium ferrocyanate/cobalt nitride or cobalt potassium ferrocyanate/cobalt selenide;

the ferrocyanide supporting material of the metal is as follows: cobalt potassium ferricyanate/cobalt phosphide, vanadium potassium ferricyanate/vanadium phosphide, chromium potassium ferricyanate/chromium phosphide, manganese potassium ferricyanate/manganese phosphide, iron potassium ferricyanate/iron phosphide or nickel potassium ferricyanate/nickel cobalt iron phosphide, cobalt potassium ferricyanate/cobalt sulfide, cobalt potassium ferricyanate/cobalt boride, cobalt potassium ferricyanate/cobalt nitride or cobalt potassium ferricyanate/cobalt selenide;

In the second scheme, the ferrocyanide is added in the form of potassium ferrocyanide or sodium ferrocyanide, and the ferrocyanide is added in the form of potassium ferrocyanide or sodium ferrocyanide;

the preparation method of the corresponding electrode of the vanadium potassium ferricyanate, the chromium potassium ferricyanate, the manganese potassium ferricyanate, the iron potassium ferricyanate, the cobalt potassium ferricyanate, the nickel cobalt iron potassium ferricyanate, the vanadium potassium ferricyanate, the chromium potassium ferricyanate, the manganese potassium ferricyanate, the iron potassium ferricyanate, the cobalt potassium ferricyanate, the nickel potassium ferricyanate and the nickel cobalt iron potassium ferricyanate comprises the following steps:

(1) Preparing 30 ml of solution, namely 0.6 g of urea and 0.3 g of cobalt nitrate hexahydrate, pouring the solution into a 50 ml reaction kettle, soaking the washed foam nickel into the solution, putting the solution into a baking oven, and obtaining the cobalt hydroxide hydrotalcite array material after the reaction temperature is 120 ℃ and the reaction time is 12 hours;

(2) 30 ml of solution was prepared: 1g of potassium ferrocyanide, soaking the obtained cobalt hydroxide hydrotalcite array into the solution, and putting the solution into an oven, wherein the reaction temperature is 90 ℃ and the reaction time is 24 hours, thus obtaining the cobalt potassium ferrocyanide electrode;

other conditions are not changed, and cobalt nitrate hexahydrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate mixed salt can be respectively prepared to obtain: a vanadium potassium ferricyanate electrode, a chromium potassium ferricyanate electrode, a manganese potassium ferricyanate, a ferric potassium ferricyanate electrode, a nickel cobalt ferric potassium ferricyanate electrode;

Other conditions are unchanged, and potassium ferrocyanide with equimolar numbers can be prepared by replacing potassium ferrocyanide: a cobalt potassium ferricyanate electrode;

other conditions are not changed, and cobalt nitrate hexahydrate in the step (1) is respectively changed into equimolar numbers: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, ferric nitrate nonahydrate, nickel nitrate hexahydrate or nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate mixed salt with the mol ratio of 1:1:2; and the potassium ferrocyanide is changed into potassium ferrocyanide with the same mole number, so that the preparation method can be used for respectively preparing the potassium ferrocyanide: a vanadium potassium ferricyanate electrode, a chromium potassium ferricyanate electrode, a manganese potassium ferricyanate electrode, a iron potassium ferricyanate electrode, a nickel cobalt iron potassium ferricyanate electrode;

the preparation methods of the electrodes corresponding to the cobalt potassium ferrocyanate/cobalt phosphide, vanadium potassium ferrocyanate/vanadium phosphide, chromium potassium ferrocyanate/chromium phosphide, manganese potassium ferrocyanate/manganese phosphide, iron potassium ferrocyanate/iron phosphide, nickel potassium ferrocyanate/nickel phosphide, nickel cobalt potassium ferrocyanate/nickel cobalt phosphide, iron cobalt potassium ferrocyanate/cobalt sulfide, iron potassium ferrocyanate/cobalt boride, iron potassium ferrocyanate/cobalt nitride, iron potassium ferrocyanate/cobalt selenide, iron potassium cobalt cyanate/cobalt phosphide, vanadium potassium ferrocyanate/vanadium phosphide, chromium potassium ferrocyanate/chromium phosphide, manganese potassium ferrocyanate/manganese phosphide, iron potassium ferrocyanate/iron phosphide, nickel potassium ferrocyanate/nickel phosphide, iron potassium cobalt phosphide/cobalt sulfide, iron potassium cobalt cyanate/cobalt boride, iron potassium cobalt cyanate/cobalt nitride, iron potassium ferrocyanate/cobalt selenide are as follows:

(1) Preparing 30 ml of solution, namely 0.6 g of urea and 0.291 g of cobalt nitrate, pouring the solution into a 50 ml reaction kettle, soaking the washed foam nickel into the solution, putting the solution into a baking oven, and obtaining a cobalt hydroxide hydrotalcite array loaded on the foam nickel, wherein the reaction temperature is 120 ℃ and the reaction time is 12 hours;

(2) Placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and 500 mg of sodium hypophosphite in a tube furnace together, heating to 300 ℃, and preserving heat for 2 hours to obtain a cobalt phosphide array growing on a foam nickel substrate;

(3) 30 ml of solution was prepared: 1g of potassium ferrocyanide, soaking the obtained cobalt phosphide array loaded on the foam nickel into the solution, putting the solution into an oven, and reacting at 90 ℃ for 24 hours to obtain a cobalt potassium ferrocyanate/cobalt phosphide electrode;

changing the conditions, preparing other materials: other conditions are unchanged, cobalt nitrate in the step (1) is respectively changed into the cobalt nitrate with the equimolar number: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate mixed salt can be respectively prepared to obtain: vanadium potassium ferricyanate/vanadium phosphide electrode, chromium potassium ferricyanate/chromium phosphide electrode, manganese potassium ferricyanate/manganese phosphide electrode, iron potassium ferricyanate/iron phosphide electrode, nickel potassium ferricyanate/nickel phosphide electrode, nickel cobalt potassium ferricyanate/nickel cobalt iron phosphide electrode;

The other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and 500 mg of sublimed sulfur into a tube furnace together, heating to 300 ℃, and preserving heat for 2 hours to obtain a cobalt sulfide array growing on a foam nickel substrate, and obtaining a cobalt potassium ferrocyanate/cobalt sulfide electrode after the step (3);

the other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) into 20 millimoles per liter of sodium borohydride solution, carrying out ice bath for 24 hours to obtain a cobalt boride array growing on a foam nickel substrate, and obtaining a cobalt ferrocyanide potassium/cobalt boride electrode after the step (3);

the other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in a tubular furnace in the atmosphere of 20% ammonia gas and 80% argon gas, heating to 450 ℃ at the air flow speed of 20 sccm, preserving heat for 3 hours to obtain a cobalt nitride array growing on a foam nickel substrate, and obtaining a cobalt potassium ferrocyanate/cobalt nitride electrode after the step (3);

The other steps are unchanged, and the step (2) is replaced by: adding 50mL of mixed aqueous solution into the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1), 3.75mmol of selenium powder, 7.5mmol of sodium hydroxide, 0.14mL of hydrazine and 25mL of N, N-dimethylformamide, and carrying out hydrothermal reaction in a hydrothermal reaction kettle at 180 ℃ for 1 hour to obtain a cobalt selenide array growing on a foam nickel substrate, and obtaining a cobalt potassium ferricyanate/cobalt selenide electrode after the step (3);

other conditions are unchanged, and the potassium ferrocyanide is changed into potassium ferrocyanide with the same mole number, so that the preparation method can be used for preparing the potassium ferrocyanide: a cobalt potassium ferricyanate/cobalt phosphide electrode supported on the nickel foam;

other conditions are unchanged, cobalt nitrate in the step (1) is respectively changed into the cobalt nitrate with the equimolar number: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate mixed salt; and the potassium ferrocyanide is changed into potassium ferrocyanide with the same mole number, so that the preparation method can be used for respectively preparing the potassium ferrocyanide: vanadium potassium ferricyanate/vanadium phosphide electrode, chromium potassium ferricyanate/chromium phosphide electrode, manganese potassium ferricyanate/manganese phosphide electrode, iron potassium ferricyanate/iron phosphide electrode, nickel potassium ferricyanate/nickel phosphide electrode, nickel cobalt potassium ferricyanate/nickel cobalt iron phosphide electrode;

The other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) and 500 mg of sublimed sulfur into a tube furnace together, heating to 300 ℃, preserving heat for 2 hours to obtain a cobalt sulfide array growing on a foam nickel substrate, then changing potassium ferrocyanide into potassium ferricyanide with the same mole number, and obtaining a cobalt potassium ferricyanide/cobalt sulfide electrode after the step (3);

the other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) into 20 millimoles per liter of sodium borohydride solution, carrying out ice bath for 24 hours to obtain a cobalt boride array growing on a foam nickel substrate, then changing potassium ferrocyanide into potassium ferricyanide with the same mole number, and obtaining a cobalt potassium ferricyanide/cobalt boride electrode after the step (3);

the other steps are unchanged, and the step (2) is replaced by: placing the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1) in a tubular furnace in the atmosphere of 20% ammonia gas and 80% argon gas, heating to 450 ℃ at the air flow speed of 20 sccm, preserving heat for 3 hours to obtain a cobalt nitride array growing on a foam nickel substrate, changing potassium ferrocyanide into potassium ferricyanide with the same mole number, and obtaining a cobalt potassium ferricyanide/cobalt nitride electrode after the step (3);

The other steps are unchanged, and the step (2) is replaced by: and (3) adding 50mL of mixed aqueous solution into the cobalt hydroxide hydrotalcite array loaded on the foam nickel obtained in the step (1), 3.75mmol of selenium powder, 7.5mmol of sodium hydroxide, 0.14mL of hydrazine and 25mL of N, N-dimethylformamide, and carrying out hydrothermal reaction in a hydrothermal reaction kettle at 180 ℃ for 1 hour to obtain a cobalt selenide array growing on the foam nickel substrate, and then changing potassium ferrocyanide into potassium ferricyanide with the same mole number, so as to obtain the cobalt potassium ferricyanide/cobalt selenide electrode after the step (3).

2. The method according to claim 1, wherein after one or more of ferrous cyanide and ferric cyanide is added to the electrolyte of the electrolyzed seawater, the electrolyte is prepared by:

3. The method according to claim 1, wherein the electrolyte for electrolyzing seawater comprises: 6 moles per liter of base and 2.8 moles per liter of sodium chloride.

4. The method according to claim 1, wherein the base is one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide.