CN115125565A

CN115125565A - Method for resisting electrolytic seawater anodic corrosion

Info

Publication number: CN115125565A
Application number: CN202210756550.0A
Authority: CN
Inventors: 邝允; 孙晓明; 刘威; 辛慧军; 余佳格
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: 2022-09-30
Anticipated expiration: 2042-06-29
Also published as: CN115125565B

Abstract

The invention belongs to the technical field of inorganic advanced nano materials, and particularly relates to a method for resisting anodic corrosion of electrolytic seawater. The electrolyte for electrolyzing the seawater contains sodium chloride and alkali, and the method comprises at least one of the following two schemes: in the first scheme, the anode catalytic material for electrolyzing seawater is as follows: a metal ferrocyanide, a metal ferricyanide, a metal ferrocyanide support material, or a metal ferricyanide support material; and in the second scheme, one or more of ferrocyanide and ferricyanide are added into the electrolyte for electrolyzing the seawater. The two schemes have the same action mechanism, and the ferricyanate and the chloride ions have the same charge, so that the ferricyanate and the chloride ions have a repulsive action to the chloride ions, and the chloride ions are difficult to approach the surface of the foam nickel base of the electrode, thereby improving the stability of the electrode.

Description

Method for resisting electrolytic seawater anodic corrosion

Technical Field

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

Background

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

However, when seawater is used as the electrolyte, chloride ions therein tend to move to the vicinity of the anode under the influence of the electric field force, and the high concentration of chloride ions causes corrosion of the current collector of the electrolysis system. The net reaction of the anode and the cathode of the electrolysis system only consumes water, and the supplemented fresh electrolyte is still seawater, so that the concentration of chloride ions in the electrolyte is further increased after the electrolysis is carried out for a long time, and further, the electrode is inactivated.

Disclosure of Invention

The invention develops a method for resisting seawater electrolytic anode corrosion, which resists high salinity seawater corrosion by using specific materials and anodes and adding additives.

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

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

and in the second scheme, one or more of ferrocyanide and ferricyanide are added into the electrolyte for electrolyzing the seawater.

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

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

the metal ferrocyanide support material is selected from: a composite material of metal ferrocyanide and phosphide, a composite material of metal ferrocyanide and sulfide, a composite material of metal ferrocyanide and boride, a composite material of metal ferrocyanide and nitride or a composite material of metal ferrocyanide and selenide; in the material, a metal ferrocyanide inner layer 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 for 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, an 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.

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

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

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

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

Preferably, after one or more of ferrocyanide and ferricyanide are added into the electrolyte for electrolyzing seawater, the electrolyte is:

the concentration of the ferrocyanide is as follows: 0.1-100 mg per ml;

or the concentration of the iron cyanide is as follows: 0.1-100 mg per ml;

or the total concentration of the ferrocyanide or the ferricyanide is as follows: 0.1 to 100 mg per ml.

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, electrolytes of other sodium hydroxide and sodium chloride concentrations may be selected, and other alkali metal hydroxides may be selected in place of sodium hydroxide, for example: one or more of lithium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.

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

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

the invention has the following beneficial effects:

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

In addition, the invention unexpectedly discovers that when one or more of ferrocyanide and ferricyanide are added into the electrolyte for electrolyzing the seawater in the seawater electrolyzing process, the corrosion resistance of the anode material is also improved.

The two schemes have the same action mechanism, and the ferricyanate and the chloride ions have the same charge, so that the ferricyanate and the chloride ions have a repulsive action to the chloride ions, and the chloride ions are difficult to approach the surface of the foam nickel base of the electrode, thereby improving the stability of the electrode.

When the potassium ferricyanide or potassium ferrocyanide electrolyte additive is used, the electrolyte additive can be anchored in an anode double electric layer under the action of electric field force, and the higher valence state and larger ion volume of ferricyanide effectively inhibit the adsorption of chloride ions on the surface of the electrode, thereby greatly improving the corrosion resistance stability of the electrolytic seawater anode.

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

Drawings

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

FIG. 2 is a scanning electron micrograph of a potassium cobalt ferrocyanide electrode of example 1.

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

FIG. 4 shows the electrolyte of example 3, which is a foam nickel electrode (solid sphere) and a cobalt potassium ferrocyanide electrode (hollow sphere) at 200mAcm ^-2 Constant current curve at current density.

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

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

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

FIG. 8 shows the results of example 6 in the electrolyte using a nickel foam electrode (solid sphere) and a cobalt potassium ferrocyanide/cobalt phosphide electrode (hollow sphere) at 200mA cm ^-2 Constant current curve at current density.

FIG. 9 shows the results of example 7 using a nickel foam electrode in which potassium ferrocyanide (solid spheres) was added to the electrolyte at 200 mA/cm in a volume of 0.1 mg/ml potassium ferrocyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 10 shows the results of example 8 using a nickel foam electrode without potassium ferrocyanide (solid spheres) and with 10 mg/ml potassium ferrocyanide (hollow spheres) in the electrolyte at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 11 shows the results of example 9 using a nickel foam electrode in an electrolyte without the addition of potassium ferrocyanide (solid spheres) and with the addition of 100 mg per ml of potassium ferrocyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 12 shows the results of example 10 using a nickel foam electrode in which potassium ferricyanide (solid spheres) was not added and 0.1 mg/ml potassium ferricyanide (hollow spheres) was added to the electrolyte at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 13 shows a nickel foam electrode in electrolyte used in example 11In the method, potassium ferricyanide (solid spheres) and 10 mg/ml potassium ferricyanide (hollow spheres) were added at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 14 shows the results obtained for example 12 using a nickel foam electrode without potassium ferricyanide (solid spheres) and with 100 mg/ml potassium ferricyanide (hollow spheres) in an electrolyte at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 15 shows example 13 in electrolyte solution, using foam nickel electrode and without potassium ferricyanide (solid spheres), using vanadium potassium ferricyanide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 16 shows example 14 in an electrolyte solution of 200mAcm with a foamed nickel electrode without potassium ferricyanide (solid spheres), a chromium potassium ferrocyanide electrode with 0.1 mg per ml potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 17 is a graph of example 15 using a nickel foam electrode with no potassium ferricyanide (solid spheres), a potassium manganese ferricyanate electrode with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) in an electrolyte of 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 18 shows the results obtained for example 16 in an electrolyte solution using a nickel foam electrode without potassium ferricyanide (solid spheres), using a potassium ferricyanate electrode with 0.1 mg per ml of potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 19 shows example 17 in electrolyte solution, using foam nickel electrode and without potassium ferricyanide (solid spheres), using potassium cobalt ferrocyanide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 20 shows the results of example 18 in which a foam nickel electrode is used in the electrolyte without potassium ferricyanide (solid spheres) and potassium nickel ferrocyanide is usedElectrodes and 0.1 mg/ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 21 shows example 19 in an electrolyte solution with a foamed nickel electrode without potassium ferricyanide (solid spheres), with a nickel ferrocyanide cobalt iron electrode with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 22 shows example 20 in electrolyte solution, using foam nickel electrodes without potassium ferricyanide (solid spheres), using vanadium potassium ferricyanide electrodes with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 23 shows example 21 in electrolyte solution, using foam nickel electrodes without potassium ferricyanide (solid spheres), using ferrocyanide potassium ferrocyanide electrodes with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 24 shows the results obtained for example 22 in an electrolyte solution at 200mAcm using a foamed nickel electrode without potassium ferricyanide (solid spheres), a potassium manganese ferricyanide electrode with 0.1 mg per ml of potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 25 shows example 23 in electrolyte solution, with foamed nickel electrode and without potassium ferricyanide (solid spheres), with potassium ferricyanide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 26 shows example 24 in electrolyte solution, with foamed nickel electrode and without potassium ferricyanide (solid spheres), with potassium cobalt ferricyanide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 27 shows example 25 using a nickel foam electrode in electrolyte and without potassium ferricyanide (solid spheres) and a potassium nickel ferricyanate electrodeAnd 0.1 mg/ml potassium ferricyanide (hollow spheres) was added at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 28 shows the results of example 26 in electrolyte solution, with foam nickel electrode and without potassium ferricyanide (solid spheres), with nickel cobalt iron ferricyanate electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mA cm ^-2 30 hour galvanostatic curve at current density. FIG. 29 shows example 27 in electrolyte solution, using foam nickel electrodes and without potassium ferricyanide (solid spheres), using potassium vanadium ferrocyanide/vanadium phosphide electrodes and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 30 shows example 28 in electrolyte solution, using foam nickel electrodes and without potassium ferricyanide (solid spheres), using potassium ferrocyanide/chromium phosphide electrodes and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 31 is a graph of example 29 in electrolyte using a foamed nickel electrode without the addition of potassium ferricyanide (solid spheres), using a potassium manganese ferrocyanide/manganese phosphide electrode with the addition of 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 32 shows the results of example 30 in electrolyte solution, using a nickel foam electrode and without potassium ferricyanide (solid spheres), using a potassium ferricyanate/iron phosphide electrode and with the addition of 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 33 is a graph of example 31 in electrolyte using a foamed nickel electrode without potassium ferricyanide (solid spheres), using a potassium cobalt ferrocyanide/cobalt phosphide electrode with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 34 shows the electrolyte of example 32 with a foam nickel electrode and without the addition of potassium ferricyanide (solid spheres)Nickel potassium ferrocyanide/nickel phosphide electrode and 0.1 mg per ml potassium ferricyanide (hollow sphere) was added at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 35 shows example 33 employing a foamed nickel electrode with no potassium ferricyanide (solid spheres), a nickel cobalt iron ferrocyanide/nickel cobalt iron phosphide electrode with 0.1 mg per ml potassium ferricyanide (hollow spheres) in the electrolyte at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 36 shows example 34 in electrolyte solution at 200mAcm, using a foamed nickel electrode and without potassium ferricyanide (solid spheres), using a potassium cobalt ferrocyanide/cobalt sulfide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 37 shows example 35 in electrolyte solution, using a nickel foam electrode and without potassium ferricyanide (solid spheres), using a potassium cobalt ferrocyanide/cobalt boride electrode and with 0.1 mg/ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 38 shows the results obtained for example 36 in an electrolyte solution using a nickel foam electrode without potassium ferricyanide (solid spheres), a potassium cobalt ferrocyanide/cobalt nitride electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 39 is a graph of example 37 in electrolyte solution, using nickel foam electrodes with no potassium ferricyanide (solid spheres), cobalt potassium ferrocyanide/cobalt selenide electrodes with 0.1 milligrams per milliliter of potassium ferricyanide (hollow spheres) at 200mA cm ^-2 30 hour galvanostatic curve at current density. FIG. 40 shows example 38 in electrolyte solution, using foam nickel electrodes and without potassium ferricyanide (solid spheres), using potassium vanadium ferricyanide/vanadium phosphide electrodes and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 41 shows an example 39 employing a nickel foam electrode in electrolyteAnd no potassium ferricyanide (solid spheres), a potassium ferrocyanide/chromium phosphide electrode and 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 42 shows example 40 in electrolyte solution at 200mAcm, using a foamed nickel electrode and without potassium ferricyanide (solid spheres), using a potassium ferricyanide/manganese phosphide electrode and with the addition of 0.1 mg per ml of potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 43 shows example 41 in electrolyte solution, using foam nickel electrode and without potassium ferricyanide (solid spheres), using potassium ferricyanate/iron phosphide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 44 is a graph of example 42 in electrolyte using a foamed nickel electrode without potassium ferricyanide (solid spheres), using a potassium cobalt ferricyanide/cobalt phosphide electrode with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 45 shows example 43 in electrolyte solution, using foam nickel electrode and without potassium ferricyanide (solid spheres), using nickel potassium ferricyanide/nickel phosphide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 46 shows example 44 in electrolyte solution, with foamed nickel electrode and without potassium ferricyanide (solid spheres), with nickel ferrocyanide ferrocobalt/nickel ferrocyanide phosphide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 47 shows example 45 in electrolyte solution at 200mAcm, using a foamed nickel electrode and without potassium ferricyanide (solid spheres), using a potassium cobalt ferricyanide/cobalt sulfide electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 48 shows example 46 in electrolyte solution, using foam nickel electrodes and without potassium ferricyanide (solid spheres), using potassium ferricyanide/cobalt boride electrodes and with 0.1 mg per ml potassium ferricyanide (hollow spheres) at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 49 shows example 47 in electrolyte solution, with foamed nickel electrode and without potassium ferricyanide (solid spheres), with potassium ferricyanide/cobalt nitride electrode and with 0.1 mg per ml potassium ferricyanide (hollow spheres), at 200mAcm ^-2 30 hour galvanostatic curve at current density.

FIG. 50 shows example 48 in electrolyte solution at 200mAcm, using a foamed nickel electrode and without potassium ferricyanide (solid spheres), using a potassium cobalt ferricyanide/cobalt selenide electrode and with the addition of 0.1 mg per ml of potassium ferricyanide (hollow spheres) ^-2 30 hour galvanostatic curve at current density.

FIG. 51 shows the results of example 49 using a nickel foam electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) added to 6 moles/l lithium hydroxide and 2.8 moles/l sodium chloride electrolyte at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 52 shows the results of example 50 using a nickel foam electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) added to 6 moles/l KOH and 2.8 moles/l NaCl electrolyte at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 53 shows the results of example 51 using a nickel foam electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) added to 6 moles/l rubidium hydroxide and 2.8 moles/l sodium chloride electrolyte at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 54 shows the results obtained in example 52 using a nickel foam electrode with 0.1 mg/ml potassium ferricyanide (hollow spheres) added to 6 moles/l cesium hydroxide and 2.8 moles/l NaCl electrolyte at 200mA cm ^-2 30 hour galvanostatic curve at current density.

FIG. 55 shows an example 53 electrode of potassium cobalt ferricyanate6 mol/L sodium hydroxide and 2.8 mol/L sodium chloride mixed electrolyte, and in the above electrolyte 0.1 mg/mL potassium ferricyanide or potassium ferrocyanide is added, at 200mAcm ^-2 Lower constant current curve.

FIG. 56 shows the results of example 54. cobalt potassium ferricyanate/cobalt phosphide electrodes in a mixed electrolyte of 6 moles per liter sodium hydroxide and 2.8 moles per liter sodium chloride, and in the above electrolyte with the addition of 0.1 mg per ml potassium ferricyanide or potassium ferrocyanide at 200mAcm ^-2 Lower constant current curve.

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 invention only and should not be taken as limiting the scope of the invention. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.

As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. 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, "a plurality" means two or more unless otherwise specified. The terms "inner," "upper," "lower," and the like, refer to an orientation or a state relationship based on that shown in the drawings, which is for convenience in describing and simplifying the description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention.

In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted", "coupled" and "provided" are to be interpreted broadly, for example, as being either fixedly coupled, detachably coupled, or integrally coupled; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention are understood as specific cases by those of ordinary skill in the art.

It will be understood by those skilled in the art that, unless otherwise defined, all terms including technical and scientific terms used herein 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 potassium cobalt ferrocyanide and the potassium cobalt ferrocyanide/cobalt phosphide are prepared by self-preparation methods.

Example 1-preparation of vanadium potassium ferrocyanide electrode, chromium potassium ferrocyanide electrode, manganese potassium ferrocyanide, iron potassium ferrocyanide electrode, cobalt potassium ferrocyanide electrode, nickel cobalt iron ferrocyanide electrode, vanadium potassium ferricyanate electrode, chromium potassium ferricyanate electrode, manganese potassium ferricyanate electrode, iron potassium ferricyanate electrode, cobalt potassium ferricyanate electrode, nickel cobalt iron cyanate electrode

The following method is adopted in this example to prepare potassium cobalt ferrocyanide, and the skilled person can adjust the method by referring to the prior art:

(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 50ml reaction kettle, soaking the washed foamed nickel into the solution, and putting the solution into an oven, wherein the reaction temperature is 120 ℃ and the reaction time is 12 hours. The obtained material was washed with water and ethanol for 3 times, respectively, and vacuum dried 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 obtained material was washed with water and ethanol for 3 times, respectively, and vacuum dried at 60 ℃ for 10 hours. Namely a potassium cobalt ferrocyanide electrode (with a foamed nickel substrate).

Changing the cobalt nitrate hexahydrate in the step (1) to the equimolar amount of the following components: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, or a mixture of the following in mole number 1:1:2 nickel nitrate hexahydrate, cobalt nitrate hexahydrate and iron nitrate nonahydrate. Respectively preparing the following components: vanadium potassium ferrocyanide electrode, chromium potassium ferrocyanide electrode, manganese potassium ferrocyanide, iron potassium ferrocyanide electrode, nickel cobalt iron ferrocyanide electrode.

The potassium ferricyanide with equal mole number is transposed and the other conditions are not changed, and the following can be prepared: cobalt potassium ferricyanate electrode.

Changing the cobalt nitrate hexahydrate in the step (1) to the equimolar amount of the following components: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate or mixed salts of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and iron nitrate nonahydrate with the molar number of 1:1: 2; and replacing potassium ferrocyanide with equal molar number of potassium ferricyanide. Respectively preparing the following components: vanadium potassium iron cyanate electrode, chromium potassium iron cyanate electrode, manganese potassium iron cyanate electrode, iron potassium iron cyanate electrode, nickel cobalt iron cyanate electrode.

The cobalt potassium ferrocyanide electrode is placed in a glass vial filled with 10 ml of water, ultrasonic treatment is carried out in an ultrasonic cleaning agent for 15 minutes, then the obtained turbid liquid is centrifuged, and the obtained powder is dried in vacuum for 10 hours at the temperature of 60 ℃. The powder was subjected to X-ray diffraction, the X-ray diffraction pattern (XRD) is shown in FIG. 1, which is consistent with the standard card of potassium cobalt ferrocyanide, indicating the successful synthesis of potassium cobalt ferrocyanide. The Scanning Electron Microscope (SEM) pattern of the electrode material is shown in fig. 2, and the potassium cobalt ferrocyanide is in a cubic block shape.

Example 2 oxygen evolution reactivity test

The electrolytic seawater electrocatalytic oxygen evolution performance of the potassium cobalt ferrocyanide electrode obtained in example 1 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 ferrocyanide electrode or a foamed nickel electrode with the effective area of 1 x 1 square centimeter, 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. And then, replacing a new electrolyte, and performing linear scanning by using 2mV/s within the range of 1-2V vs RHE. The resulting linear scan voltammogram is shown in FIG. 3.

As shown in FIG. 3, the amount of potassium cobalt ferrocyanide is 10mAcm ^-2 The overpotential at the current density was 330 mV.

Example 3 Corrosion resistance testing

The three-electrode system is used for testing the corrosion resistance stability of the seawater electrolysis anode of the cobalt potassium ferrocyanide electrode of the invention: the reference electrode is a calomel electrode, the counter electrode is a platinum sheet electrode, the working electrode is a potassium cobalt ferrocyanide electrode or a foamed nickel electrode with the effective area of 1 x 1 square centimeter, 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 a constant current test of 200 milliampere 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 cobalt potassium ferrocyanide electrode can effectively prevent corrosion, so that the anode stability can be maintained for a longer time, and the maximum time reaches about 45 hours (the hollow circle in fig. 4).

Example 4-cobalt potassium ferrocyanide/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, cobalt potassium ferrocyanide/cobalt selenide, cobalt potassium ferrocyanide/cobalt phosphide, vanadium potassium ferrocyanide/vanadium phosphide, chromium potassium ferrocyanide/chromium phosphide, manganese potassium ferricyanate/manganese phosphide, iron potassium ferricyanate/iron phosphide, nickel potassium ferricyanate/nickel phosphide electrode, nickel cobalt iron cyanate/nickel cobalt iron phosphide, cobalt potassium ferricyanate/cobalt sulfide, cobalt potassium ferrocyanide/cobalt boride, Preparation of cobalt potassium ferricyanate/cobalt nitride, cobalt potassium ferricyanate/cobalt selenide

The following method is adopted in this example to prepare potassium cobalt ferrocyanide/cobalt phosphide, and the skilled person can, of course, make adjustments with reference to the prior art:

(1) preparing 30 ml of solution, namely 0.6 g of urea and 0.291 g of cobalt nitrate, pouring the solution into a 50ml reaction kettle, soaking the washed foam nickel into the solution, and putting the solution into an oven, wherein the reaction temperature is 120 ℃ and the reaction time is 12 hours. The obtained material is washed by water and ethanol for 3 times respectively, and is dried in vacuum for 10 hours at the temperature of 60 ℃, and then the cobalt hydroxide hydrotalcite array loaded on the foamed nickel is obtained.

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

(3) 30 ml of solution was prepared: 1g of potassium ferricyanide, soaking the obtained cobalt phosphide array loaded on the foamed 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 obtained material was washed with water and ethanol 3 times, respectively, and vacuum dried at 60 ℃ for 10 hours. Namely the cobalt potassium ferrocyanide/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 turbid solution was centrifuged, and the resulting powder was vacuum-dried at 60 ℃ for 10 hours. The powder was subjected to X-ray diffraction, and the X-ray diffraction pattern (XRD) is shown in fig. 5, which is consistent with the standard cards of cobalt potassium ferrocyanide and cobalt phosphide, indicating the successful synthesis of the cobalt potassium ferrocyanide/cobalt phosphide heterostructure. The Scanning Electron Microscope (SEM) pattern of the electrode material is shown in fig. 6, and the potassium cobalt ferrocyanide/cobalt phosphide heterostructure is also in a cubic block shape.

The conditions were changed to prepare other materials: changing the cobalt nitrate in the step (1) into the following components with equal molar numbers respectively without changing other conditions: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, or a mixture of the following in mole number 1:1:2 nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate. Respectively preparing the following components: vanadium potassium ferrocyanide/vanadium phosphide electrode, chromium potassium ferrocyanide/chromium phosphide electrode, manganese potassium ferrocyanide/manganese phosphide electrode, iron potassium ferrocyanide/iron phosphide electrode, nickel potassium ferrocyanide/nickel phosphide electrode, nickel cobalt iron potassium ferrocyanide/nickel cobalt phosphide electrode.

And (3) changing the step (2) into the following steps without changing other steps: and (2) putting the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) and sublimed sulfur into a tubular furnace (500 mg of sublimed sulfur), heating to 300 ℃, and preserving heat for 2 hours to obtain the cobalt sulfide array growing on the foamed nickel substrate. And (4) obtaining the cobalt potassium ferrocyanide/cobalt sulfide electrode after the step (3).

And (3) changing the step (2) into the following steps without changing other steps: and (2) placing the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) into a sodium borohydride solution (20 millimole per liter of sodium borohydride), and carrying out ice bath for 24 hours to obtain the cobalt boride array growing on the foamed nickel substrate. And (4) obtaining the potassium cobalt ferrocyanide/cobalt boride electrode after the step (3).

Changing the step (2) to the following step without changing other steps: and (2) placing the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) in a tubular furnace (20% ammonia gas, the gas flow rate is 20sccm) in 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 foamed nickel substrate. And (4) obtaining the potassium cobalt ferrocyanide/cobalt nitride electrode after the step (3).

Changing the step (2) to the following step without changing other steps: and (2) adding the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1), selenium powder (3.75mmol), sodium hydroxide (7.5mmol), hydrazine (0.14mL) and N, N-dimethylformamide (25mL) 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 foamed nickel substrate. And (4) obtaining the cobalt potassium ferrocyanide/cobalt selenide electrode after the step (3). Other conditions are not changed, and the potassium ferrocyanide is changed into potassium ferricyanide with equal mole number, so that the preparation method can obtain the following components: cobalt potassium ferricyanate/cobalt phosphide electrode supported on foamed nickel.

Changing the cobalt nitrate in the step (1) into the following components with equal molar numbers respectively without changing other conditions: vanadium sulfate heptahydrate, chromium nitrate nonahydrate, manganese nitrate tetrahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, or a mixture of the following in mole number 1:1:2, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ferric nitrate nonahydrate mixed salt; and replacing potassium ferrocyanide with equal molar number of potassium ferricyanide. Respectively 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 iron potassium ferricyanate/nickel cobalt iron phosphide electrode.

And (3) changing the step (2) into the following steps without changing other steps: and (2) putting the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) and sublimed sulfur into a tubular furnace (500 mg of sublimed sulfur), heating to 300 ℃, and preserving heat for 2 hours to obtain the cobalt sulfide array growing on the foamed nickel substrate. And (3) replacing potassium ferrocyanide with potassium ferricyanide with equal mole number, and obtaining the cobalt potassium ferrocyanide/cobalt sulfide electrode after the step (3).

Changing the step (2) to the following step without changing other steps: and (2) placing the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) into a sodium borohydride solution (20 millimole per liter of sodium borohydride), and carrying out ice bath for 24 hours to obtain the cobalt boride array growing on the foamed nickel substrate. And (4) replacing potassium ferrocyanide with potassium ferricyanide with equal mole number, and obtaining the cobalt potassium ferrocyanide/cobalt boride electrode after the step (3).

And (3) changing the step (2) into the following steps without changing other steps: and (2) placing the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1) in a tubular furnace (20% ammonia gas, the gas flow rate is 20sccm) in 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 foamed nickel substrate. And (3) replacing potassium ferrocyanide with potassium ferricyanide with equal mole number, and obtaining the cobalt potassium ferrocyanide/cobalt nitride electrode after the step (3).

And (3) changing the step (2) into the following steps without changing other steps: and (2) adding the cobalt hydroxide hydrotalcite array loaded on the foamed nickel obtained in the step (1), selenium powder (3.75mmol), sodium hydroxide (7.5mmol), hydrazine (0.14mL) and N, N-dimethylformamide (25mL) 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 foamed nickel substrate. And (3) replacing potassium ferrocyanide with potassium ferricyanide with equal mole number, and obtaining the potassium cobalt 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 ferrocyanide/cobalt phosphide. The linear sweep voltammogram obtained is shown in FIG. 7. As can be seen from a comparison of FIGS. 7 and 3, the ratio of potassium cobalt ferrocyanide/cobalt phosphide was at 10mAcm ^-2 The overpotential under the current density is 297mV, and the activity of the electrocatalytic oxygen evolution reaction is higher than that of a cobalt potassium ferrocyanide electrode.

Example 6 testing of the Corrosion resistance of the electrodes

Test methods referring to example 3, the working electrode was changed to potassium cobalt ferrocyanide/cobalt phosphide. The resulting galvanostatic curve is shown in fig. 8. It can be seen from fig. 8 that the anode stability is better than that of the cobalt potassium ferrocyanide electrode and far better than that of the nickel foam electrode after the cobalt potassium ferrocyanide/cobalt phosphide electrode is adopted. It is demonstrated that the potassium cobalt ferrocyanide/cobalt phosphide electrode can effectively prevent corrosion, thus maintaining the anode stability for a longer time, up to 140 hours (the hollow circle in fig. 8).

EXAMPLE 7 Corrosion resistance test of electrolyte with additive

The reason for corrosion resistance of the potassium cobalt ferrocyanide/cobalt phosphide electrode is mainly due to the formation of ferricyanide, phosphate and polyphosphate in the anodic reaction process. Therefore, the invention further can effectively inhibit the corrosion by adding ferricyanate or ferrocyanide into the electrolyte.

The corrosion resistance stability of the additive-containing seawater electrolysis anode is tested by a three-electrode system: the reference electrode was a calomel electrode, the counter electrode was a platinum sheet electrode, the working electrode was commercial nickel foam having an effective area of 1 × 1 cm square, 0.1 mg/ml potassium ferrocyanide was added to a mixed solution of 6.0 mol/l sodium hydroxide and 2.8 mol/l sodium chloride, and the mixed solution was used as an electrolyte to conduct a constant current test of 200 milliamps/cm square, and the constant current curve obtained without the potassium ferrocyanide additive was shown in fig. 9. It can be seen from fig. 9 that the electrolyte after adding potassium ferricyanide has better corrosion resistance, so that the anode stability (open circle in fig. 9) can be maintained for a long time (30 hours), and the cathode stability is better than that of the comparative sample without additive (closed circle in fig. 9).

EXAMPLE 8 Corrosion resistance test of electrolyte with additive

Test methods referring to example 7, the addition of 0.1 mg per ml of potassium ferrocyanide was changed to 10 mg per ml of potassium ferrocyanide. The resulting galvanostatic curve is shown in FIG. 10. It can be seen from fig. 10 that the electrolyte solution added with 10 mg/ml potassium ferrocyanide can effectively inhibit corrosion, thus maintaining the anode stability for a longer time (30 hours) (the open circles of fig. 10).

EXAMPLE 9 Corrosion resistance test of electrolyte with additive

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

EXAMPLE 10 Corrosion resistance test of electrolyte with additive

Test methods referring to example 7, the addition of 0.1 mg per ml of potassium ferrocyanide was changed to 0.1 mg per ml of potassium ferricyanide. The resulting galvanostatic curve is shown in fig. 12. It can be seen from fig. 12 that 0.1 mg/ml potassium ferricyanide was added to the electrolyte to effectively inhibit corrosion and thus maintain anode stability (open circles in fig. 12) for a longer period of time (30 hours).

EXAMPLE 11 Corrosion resistance testing of an electrolyte with additives

Test methods referring to example 7, the addition of 0.1 mg per ml of potassium ferrocyanide was changed to 10 mg per ml of potassium ferricyanide. The resulting galvanostatic curve is shown in fig. 13. It can be seen from fig. 13 that the electrolyte solution added with 10 mg per ml of potassium ferricyanide is effective in inhibiting corrosion, and thus can maintain anode stability for a longer period of time (30 hours) (open circles in fig. 13).

EXAMPLE 12 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the addition of 0.1 mg per ml of potassium ferrocyanide was changed to 100 mg per ml of potassium ferricyanide. The resulting galvanostatic curve is shown in fig. 14. It can be seen from fig. 14 that 100 mg/ml potassium ferricyanide was added to the electrolyte to effectively inhibit corrosion, and thus anode stability (open circles in fig. 14) was maintained for a longer period of time (30 hours).

EXAMPLE 13 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

As can be seen from fig. 15, after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a potassium vanadium ferricyanate electrode is used, corrosion can be effectively inhibited, and thus anode stability can be maintained for a longer time (30 hours) (hollow circles in fig. 15).

EXAMPLE 14 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

It can be seen from fig. 16 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a potassium ferrocyanide electrode can effectively inhibit corrosion, and thus can maintain anode stability for a longer period (30 hours) (the hollow circle in fig. 16).

EXAMPLE 15 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

As can be seen from fig. 17, after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a potassium manganese ferrocyanide electrode is used, corrosion can be effectively inhibited, and thus anode stability (the hollow circle in fig. 17) can be maintained for a longer time (30 hours).

EXAMPLE 16 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

As can be seen from fig. 18, after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a potassium ferricyanate electrode is used, corrosion can be effectively inhibited, and thus anode stability can be maintained for a longer period of time (30 hours) (the open circle in fig. 18).

EXAMPLE 17 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium cobalt ferrocyanide electrode. The resulting galvanostatic curve is shown in fig. 19. Comparative example was a foamed nickel electrode and no potassium ferricyanide (solid spheres) was added.

As can be seen from fig. 19, after 0.1 mg/ml of potassium ferricyanide is added to the electrolyte and a potassium cobalt ferrocyanide electrode is used, corrosion can be effectively inhibited, and thus anode stability can be maintained for a longer period of time (30 hours) (the hollow circle in fig. 19).

EXAMPLE 18 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

As can be seen from fig. 20, after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a potassium nickel ferrocyanide electrode is used, corrosion can be effectively inhibited, and thus anode stability can be maintained for a longer time (30 hours) (the hollow circle in fig. 20).

EXAMPLE 19 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferrocyanide electrode. The resulting galvanostatic curve is shown in FIG. 21. Comparative example was a foamed nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 21 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a ferrocyanide nickel cobalt iron electrode can effectively inhibit corrosion, and thus can maintain anode stability for a longer period (30 hours) (the hollow circle in fig. 21).

EXAMPLE 20 seawater electrolytic Corrosion resistance test with electrode coupling additives

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. 22. Comparative example was a foamed 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 potassium ferricyanide to the electrolyte and the use of a potassium vanadium ferricyanate electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 22).

EXAMPLE 21 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

It can be seen from fig. 23 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and used with the electrode of chromium potassium ferricyanate can effectively inhibit corrosion, thus maintaining the anode stability for a longer period of time (30 hours) (the open circle in fig. 23).

EXAMPLE 22 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium manganese ferricyanate electrode. The resulting galvanostatic curve is shown in FIG. 24. Comparative example was a foamed nickel electrode and no potassium ferricyanide (solid spheres) was added.

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

EXAMPLE 23 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium iron ferricyanate electrode. The resulting galvanostatic curve is shown in FIG. 25. Comparative example was a foamed nickel electrode and no potassium ferricyanide (solid spheres) was added.

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

EXAMPLE 24 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium cobalt ferricyanate electrode. The resulting galvanostatic curve is shown in fig. 26. Comparative example was a foamed 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 potassium ferricyanide to the electrolyte and the use of a potassium cobalt ferricyanate electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 26).

EXAMPLE 25 seawater electrolytic Corrosion resistance test with electrode coupling additives

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. 27. Comparative example was a foamed nickel electrode and no potassium ferricyanide (solid spheres) was added.

It can be seen from fig. 27 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a nickel potassium ferricyanate electrode can effectively inhibit corrosion, thus maintaining the anode stability for a longer period (30 hours) (the open circles in fig. 27).

EXAMPLE 26 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a nickel cobalt iron ferricyanate. The resulting galvanostatic curve is shown in fig. 28. Comparative example was a foamed 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 potassium ferricyanide to the electrolyte and the use of a nickel cobalt iron ferricyanate effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 28). EXAMPLE 27 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in fig. 29. It can be seen from fig. 29 that after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a potassium vanadium ferrocyanide/vanadium phosphide electrode is used, corrosion can be effectively inhibited, so that anode stability can be maintained for a longer time (30 hours) (hollow circle in fig. 29).

EXAMPLE 28 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in FIG. 30. It can be seen from fig. 30 that after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a ferrocyanide potassium/chromium phosphide electrode is used, corrosion can be effectively inhibited, so that anode stability can be maintained for a longer time (30 hours) (the hollow circle in fig. 30).

EXAMPLE 29 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium manganese ferrocyanide/manganese phosphide electrode. Comparative example was a foamed 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 electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a potassium manganese ferrocyanide/manganese phosphide electrode can effectively inhibit corrosion, and thus can maintain anode stability (the hollow circle in fig. 31) for a longer period of time (30 hours).

EXAMPLE 30 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in fig. 32. It can be seen from fig. 32 that the electrolyte solution added with 0.1 mg per ml of potassium ferricyanide and using a ferripotassium ferrocyanide/iron phosphide electrode can effectively inhibit corrosion, and thus can maintain anode stability for a longer period of time (30 hours) (the hollow circle in fig. 32).

EXAMPLE 31 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

The resulting galvanostatic curve is shown in FIG. 33. It can be seen from fig. 33 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a potassium cobalt ferrocyanide/cobalt phosphide electrode can effectively inhibit corrosion, and thus can maintain anode stability for a longer period (30 hours) (the hollow circle in fig. 33).

EXAMPLE 32 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in fig. 34. It can be seen from fig. 34 that the electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a potassium nickel ferrocyanide/nickel phosphide electrode can effectively inhibit corrosion, and thus can maintain anode stability (the hollow circle in fig. 34) for a longer period of time (30 hours).

EXAMPLE 33 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in FIG. 35. As can be seen from fig. 35, after 0.1 mg/ml of potassium ferricyanide is added to the electrolyte and a nickel cobalt iron ferrocyanide/nickel cobalt iron phosphide electrode is used, corrosion can be effectively inhibited, and thus anode stability (the hollow circle in fig. 35) can be maintained for a longer period of time (30 hours).

EXAMPLE 34 seawater electrolytic Corrosion resistance test of electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium cobalt ferrocyanide/cobalt sulfide electrode. Comparative example was a foamed 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 electrolyte solution added with 0.1 mg/ml potassium ferricyanide and using a potassium cobalt ferrocyanide/cobalt sulfide electrode can effectively inhibit corrosion, and thus can maintain anode stability (the hollow circle in fig. 36) for a longer period of time (30 hours).

EXAMPLE 35 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

The resulting constant current curve is shown in fig. 37. As can be seen from fig. 37, after 0.1 mg/ml of potassium ferricyanide is added to the electrolyte and a potassium cobalt ferrocyanide/cobalt boride electrode is used, corrosion can be effectively inhibited, and thus anode stability (the hollow circle in fig. 37) can be maintained for a longer period of time (30 hours).

EXAMPLE 36 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

The resulting galvanostatic curve is shown in fig. 38. As can be seen from fig. 38, after 0.1 mg/ml of potassium ferricyanide is added to the electrolyte and a cobalt ferrocyanide/cobalt nitride electrode is used, corrosion can be effectively inhibited, and thus anode stability can be maintained for a longer period of time (30 hours) (the open circle in fig. 38).

EXAMPLE 37 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

The resulting galvanostatic curve is shown in FIG. 39. It can be seen from fig. 39 that after 0.1 mg/ml potassium ferricyanide is added to the electrolyte and a cobalt potassium ferrocyanide/cobalt selenide electrode is used, corrosion can be effectively inhibited, and thus anode stability (the hollow circle in fig. 39) can be maintained for a longer time (30 hours). EXAMPLE 38 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

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

EXAMPLE 39 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium chromium ferricyanate/chromium phosphide electrode. Comparative example was a foamed 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 electrolyte solution added with 0.1 mg/ml potassium ferricyanide and employing a chromium potassium ferricyanate/chromium phosphide electrode can effectively inhibit corrosion, thus maintaining the anode stability for a longer period of time (30 hours) (the hollow circle in fig. 41).

EXAMPLE 40 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

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

EXAMPLE 41 seawater electrolytic Corrosion resistance test with electrode coupling additive

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a ferric potassium cyanate/iron phosphide electrode. Comparative example was a foamed 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 per ml of potassium ferricyanide to the electrolyte and the use of a ferripotassium ferricyanate/iron phosphide electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 43).

EXAMPLE 42 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

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

EXAMPLE 43 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

The resulting galvanostatic curve is shown in FIG. 45. It can be seen from fig. 45 that the electrolyte solution containing 0.1 mg/ml potassium ferricyanide and employing a potassium nickel ferricyanate/nickel phosphide electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (the open circles in fig. 45).

Example 44 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

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

EXAMPLE 45 seawater electrolytic Corrosion resistance test of electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium cobalt ferricyanate/cobalt sulfide electrode. Comparative example was a foamed 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 potassium ferricyanide to the electrolyte and the use of a potassium cobalt ferricyanate/cobalt sulfide electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 47).

EXAMPLE 46 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

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

EXAMPLE 47 seawater electrolytic Corrosion resistance test of electrode coupling additives

Test methods referring to example 7, the working electrode was changed from a commercial nickel foam to a potassium cobalt ferricyanate/cobalt nitride electrode. Comparative example was a foamed 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 potassium ferricyanide to the electrolyte and the use of a potassium cobalt ferricyanate/cobalt nitride electrode effectively inhibited corrosion and thus maintained anode stability for a longer period of time (30 hours) (open circles in fig. 49).

EXAMPLE 48 seawater electrolytic Corrosion resistance test of electrode coupling additives

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

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

EXAMPLE 49 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the electrolyte was changed to 6 moles per liter of a lithium hydroxide and saturated sodium chloride mixed solution. The resulting galvanostatic curve is shown in FIG. 51. It can be seen from fig. 51 that the electrolyte added with 0.1 mg per ml of potassium ferricyanide has a good corrosion resistance effect, and thus can maintain the anode stability for a long time (30 hours) (the open circles of fig. 51).

EXAMPLE 50 seawater electrolytic Corrosion resistance test with electrode coupling additives

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

EXAMPLE 51 seawater electrolytic Corrosion resistance test with electrode coupling additive

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

EXAMPLE 52 seawater electrolytic Corrosion resistance test with electrode coupling additives

Test methods referring to example 7, the electrolyte was changed to a 6 mole per liter solution of cesium hydroxide and saturated sodium chloride. The resulting constant current curve is shown in fig. 54. It can be seen from fig. 54 that the electrolyte solution added with 0.1 mg per ml of potassium ferricyanide has a good corrosion resistance effect, and thus can maintain anode stability for a long time (30 hours) (the open circles of fig. 54).

EXAMPLE 53 seawater electrolytic Corrosion resistance test with electrode coupling additive

The seawater electrolysis anode corrosion resistance stability of the cobalt potassium ferricyanate electrode coupling additive is tested by a three-electrode system: the reference electrode was a calomel electrode, the counter electrode was a platinum sheet electrode, the working electrode was a 1 × 1 cm square cobalt potassium ferrocyanide electrode prepared in example 1, and the electrolytes were used respectively: to a mixed solution of 6.0 mol/l of sodium hydroxide and 2.8 mol/l of sodium chloride, a mixed solution of 6.0 mol/l of sodium hydroxide and 2.8 mol/l of sodium chloride was added in an amount of 0.1 mg/ml of potassium ferrocyanide, and a mixed solution of 6.0 mol/l of sodium hydroxide and 2.8 mol/l of sodium chloride was added in an amount of 0.1 mg/ml of potassium ferricyanide. The three mixed solutions were used as electrolytes to perform a constant current test of 200 milliamps per square centimeter, and the obtained constant current curve is shown in fig. 55. As can be seen from fig. 55, when 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 the corrosion inhibition is more effective, so that the anode stability (the hollow circles and hollow triangles in fig. 55) can be maintained for a longer period (up to 200 hours).

EXAMPLE 54 seawater electrolytic Corrosion resistance test with electrode coupling additives

The corrosion resistance stability of the seawater electrolysis anode of the cobalt potassium ferricyanate/cobalt phosphide 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 ferricyanide/cobalt phosphide electrode with the effective area of 1 x 1 square centimeter, and the electrolyte respectively adopts 6.0 mol/L sodium hydroxide and 2.8 mol/L sodium chloride mixed solution, 6.0 mol/L sodium hydroxide and 2.8 mol/L sodium chloride mixed solution added with 0.1 mg/mL potassium ferrocyanide, and 6.0 mol/L sodium hydroxide and 2.8 mol/L sodium chloride mixed solution added with 0.1 mg/mL potassium ferricyanide. The three mixed solutions were used as electrolytes to perform a constant current test of 200 milliamps per square centimeter, and the obtained constant current curve is shown in fig. 56. As can be seen from fig. 56, after 0.1 mg/ml of potassium ferrocyanide or potassium ferricyanide is added to the electrolyte, the durability of the potassium cobalt ferrocyanide/cobalt phosphide electrode can be further improved, and the electrode is more effective in inhibiting corrosion, so that the anode stability (the hollow circles and hollow triangles in fig. 56) can be maintained for a longer time (up to 200 hours).

Claims

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

2. The method of claim 1, wherein in scheme one, the ferrocyanide of the metal is selected from the group consisting of: one or more of potassium vanadium ferrocyanide, potassium chromium ferrocyanide, potassium manganese ferrocyanide, potassium iron ferrocyanide, potassium cobalt ferrocyanide, potassium nickel ferrocyanide, and iron cobalt nickel ferrocyanide;

the ferrocyanide support material of the metal is selected from: a composite material of metal ferrocyanide and phosphide, a composite material of metal ferrocyanide and sulfide, a composite material of metal ferrocyanide and boride, a composite material of metal ferrocyanide and nitride or a composite material of metal ferrocyanide and selenide; in the material, a metal ferrocyanide inner layer 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 for 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, an 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.

3. The method of claim 1, wherein in scheme one, the metallic ferrocyanide loading material is cobalt potassium ferrocyanide/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 load material of the metal is as follows: cobalt potassium ferrocyanide/cobalt phosphide, vanadium potassium ferrocyanide/vanadium phosphide, chromium potassium ferrocyanide/chromium phosphide, manganese potassium ferrocyanide/manganese phosphide, iron potassium ferrocyanide/iron phosphide or 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.

4. The method of claim 1, wherein in scheme two, the ferrocyanide is added in the form of potassium ferrocyanide or sodium ferrocyanide, and the ferricyanide is added in the form of potassium ferricyanide or sodium ferricyanide.

5. The method as claimed in claim 4, wherein after one or more of ferrocyanide and ferricyanide is added into the electrolyte for electrolyzing seawater, the electrolyte is prepared by:

the concentration of the ferrocyanide is as follows: 0.1-100 mg per ml;

or the concentration of the iron cyanide is as follows: 0.1-100 mg per ml;

6. The method of claim 1, wherein the electrolyte that electrolyzes seawater comprises: 6 moles per liter of base and 2.8 moles per liter of sodium chloride.

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