CN113278989A - Electrolyte modification method for improving anode stability in electrolytic hydrogen production process - Google Patents

Electrolyte modification method for improving anode stability in electrolytic hydrogen production process Download PDF

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CN113278989A
CN113278989A CN202110568268.5A CN202110568268A CN113278989A CN 113278989 A CN113278989 A CN 113278989A CN 202110568268 A CN202110568268 A CN 202110568268A CN 113278989 A CN113278989 A CN 113278989A
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anode
electrolyte
stability
hydrogen production
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CN113278989B (en
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陆之毅
马腾飞
徐雯雯
陈亮
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention discloses an electrolyte modification method for improving anode stability in an electrolytic hydrogen production process. The electrolyte modification method comprises the following steps: salt containing high-valence anions is added into the seawater and/or the brine treated by the alkali liquor as the electrolyte to obtain the modified electrolyte. The electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis utilizes the preferential adsorption and the chlorine ion rejection of high-valence anions on the surface of the anode under the action of current in the electrolysis of seawater or brine, so that the corrosion speed of the chlorine ions on the anode material is reduced, and the stability of the anode in the hydrogen production process by electrolysis of seawater and brine is obviously improved.

Description

Electrolyte modification method for improving anode stability in electrolytic hydrogen production process
Technical Field
The invention belongs to the technical field of material and energy catalysis, and particularly relates to an electrolyte modification method for improving anode stability in an electrolytic hydrogen production process.
Background
With the overuse of fossil fuels, the problems of energy shortage and environmental pollution have become more and more serious. The development and utilization of clean and renewable new energy sources are effective means for solving the problems of energy shortage and environmental pollution. Among the developed new energy sources, the calorific value of hydrogen is highest, and combustion products are clean and are ideal clean renewable energy sources. The current major methods for producing hydrogen include: light hydrocarbon steam reforming processes, thermochemical recycle processes and electrochemical processes. The electrochemical method has wider and cleaner energy sources, thereby having more development and popularization advantages. The main raw material for hydrogen production by electrolyzing water is fresh water, the storage amount of the fresh water on the earth only accounts for 2.7% of all water resources, and the problem of shortage of the fresh water resources is not beneficial to large-scale production and popularization of hydrogen production by electrolyzing the fresh water. Compared with fresh water, the seawater reserves are very abundant, and the development of seawater electrolysis technology is favorable for solving the problem of hydrogen production and water shortage.
In the process of electrolyzing seawater to produce hydrogen, the cathode generates hydrogen, the anode generates oxygen, and the stability of the anode is crucial to continuously and stably producing hydrogen by the cathode. The seawater contains a large amount of corrosive chloride ions, and the chloride ions are adsorbed on the surface of the anode in a large amount under the action of current in the electrolysis process, so that the corrosion rate of the anode material is accelerated, the service life of the anode material is shortened in the seawater electrolysis process, and the overall hydrogen production efficiency is reduced, the energy consumption is increased, and the cost is increased. Therefore, it is a very interesting problem to improve the stability of the seawater electrolysis anode.
Disclosure of Invention
The invention mainly aims to provide an electrolyte modification method for improving the stability of an anode in an electrolytic hydrogen production process, which delays the corrosion of chloride ions to the anode by utilizing the competitive adsorption and mutual repulsion of high-valence anions on the surface of the anode, thereby improving the stability of the anode in seawater or brine electrolysis and providing a new idea for the selection of electrolyte in a seawater electrolysis technology.
In order to achieve the above object, the embodiment of the present invention adopts a technical solution comprising:
the embodiment of the invention provides an electrolyte modification method for improving anode stability in an electrolytic hydrogen production process, which comprises the following steps: salt containing high-valence anions is added into the seawater and/or the brine treated by the alkali liquor as the electrolyte to obtain the modified electrolyte.
Further, the salt containing high valence anions comprises any one or a combination of more than two of sulfate, carbonate or phosphate.
Further, the ratio of the concentration of the high valence anions in the salt containing the high valence anions to the concentration of the chloride ions in the electrolyte is 5-40: 100.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis of seawater or brine utilizes the effects of competitive adsorption and mutual repulsion of anions on the surface of the anode under the action of current in the hydrogen production process by electrolysis of seawater or brine to block the adsorption of chloride ions in the solution on the surface of the anode and achieve the effect of delaying the corrosion of the chloride ions on the anode, thereby improving the stability of the anode in the hydrogen production reaction by electrolysis of seawater or brine; in particular to a method for delaying the corrosion of chloride ions to an anode by competitive adsorption and mutual repulsion of high-valence anions such as sulfate radicals, carbonate radicals, phosphate radicals and the like in the electrolysis of seawater or brine and chloride ions on the surface of the anode, thereby obviously improving the stability of the anode.
(2) The invention relates to an electrolyte modification method for improving anode stability in an electrolytic hydrogen production process, wherein high-valence anions are additionally added into an electrolyte, and the added high-valence anions are preferentially adsorbed on the surface of an electrode under the action of current to play a role of corrosion prevention.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the results of a stability test of a nickel foam anode in example 1 of the present invention.
FIGS. 2a and 2b are graphs showing the corrosion effect of the nickel foam anode in example 1 of the present invention.
Fig. 3 is a graph showing the results of the stability test of the nickel foam anode in example 2 of the present invention.
Figure 4 is a graph of the stability test results for a nickel foam anode of example 3 of the present invention.
Figure 5 is a graph of the stability test results for a nickel foam anode of example 4 of the present invention.
Figure 6 is a graph of the stability test results for a nickel foam anode of example 5 of the present invention.
Figure 7 is a graph of the stability test results for a nickel foam anode of example 6 of the present invention.
FIG. 8 is a graph showing the results of the NiFe-LDH/nickel foam anode stability test in example 7 of the present invention.
FIG. 9 is a graph showing the results of the NiFe-LDH/nickel foam anode stability test in example 8 of the present invention.
FIG. 10 is a graph showing the results of NiFe-LDH/nickel foam anode stability tests in example 9 of the present invention.
FIG. 11 is a graph showing the results of the stability test of the nickel foam anode in the comparative example of the present invention.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the defects of the prior art, the inventor of the present invention has made long-term research and extensive practice to provide the technical scheme of the present invention, which mainly utilizes the competitive adsorption and mutual repulsion of anions on the surface of an anode to delay the corrosion of chloride ions to the anode in the seawater or brine electrolysis so as to improve the stability of the anode in the seawater electrolysis; in particular to a method for delaying the corrosion of chloride ions to an anode by competitive adsorption and mutual repulsion of high-valence anions such as sulfate radicals, carbonate radicals, phosphate radicals and the like in the electrolysis of seawater or brine and chloride ions on the surface of the anode, thereby obviously improving the stability of the anode. The technical solution, its implementation and principles will be further explained as follows.
One aspect of the embodiments of the present invention provides an electrolyte modification method for improving anode stability in an electrolytic hydrogen production process, including: salt containing high-valence anions is added into the seawater and/or the brine treated by the alkali liquor as the electrolyte to obtain the modified electrolyte.
In some preferred embodiments, the electrolyte modification method specifically includes: adding salt containing high-valence anions, namely one or more of sulfate, carbonate and phosphate, with a certain concentration into the seawater treated by the alkali liquor or the brine with any concentration to prepare the modified electrolyte. Under the action of current, high-valence anions in the modified electrolyte can be preferentially adsorbed on the surface of the anode to repel chloride ions, so that the corrosion prevention effect is achieved.
In some preferred embodiments, the salt containing higher anions may include one or more salts selected from the group consisting of sulfate, carbonate, phosphate, and the like, but is not limited thereto.
In some more preferred embodiments, the sulfate may include, but is not limited to, sodium sulfate and/or potassium sulfate.
In some more preferred embodiments, the carbonate may include, but is not limited to, sodium carbonate and/or potassium carbonate.
In some more preferred embodiments, the phosphate may include one or a combination of two or more of sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, and the like, but is not limited thereto.
In some preferred embodiments, the ratio of the concentration of higher anions in the higher anion containing salt to the concentration of chloride ions in the electrolyte is 5-40: 100. That is, in another aspect, the concentration of the salt containing higher anions is 5% to 40% of the chloride ion concentration in the bulk electrolyte.
In some preferred embodiments, the electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis comprises the following steps: dissolving alkaline substance and seawater in water to form alkali solution treated seawater.
In some more preferred embodiments, the concentration of the alkaline substance is 1mol/L to 6mol/L, and preferably, the alkaline substance may include, but is not limited to, sodium hydroxide or potassium hydroxide.
In some preferred embodiments, the electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis comprises the following steps: the alkaline material and salt are dissolved in water to form a lye-treated brine.
In some more preferred embodiments, the brine has a concentration of 0.5mol/L to 2.5 mol/L.
The embodiment of the invention also provides the modified electrolyte prepared by the method.
In some preferred embodiments, the electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis comprises the following steps: an anode NiFe-LDH/foamed nickel catalytic material for electrolytic hydrogen production reaction is prepared by a one-step hydrothermal method.
In some more preferred embodiments, the electrolyte modification method for improving the stability of the anode in the hydrogen production process by electrolysis comprises the following steps:
cutting 1cm × 3cm of foamed nickel, and respectively cleaning with hydrochloric acid, ethanol and deionized water to serve as a substrate for catalyst deposition;
dissolving FeIII、NiIIDissolving salt and a precipitator in a certain amount of deionized water, placing the obtained solution and the cleaned foamed nickel in a polytetrafluoroethylene high-pressure reaction kettle together, heating at 180 ℃ for 4-24h to convert Ni and Fe salts into a NiFe-LDH catalyst and densely coating the NiFe-LDH catalyst on the surface of the foamed nickel, and preparing the anode NiFe-LDH/foamed nickel catalytic material for electrolytic hydrogen production reaction.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.25mol of Na2SO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The results of the anode stability test are shown in fig. 1. The corrosion effect on the anode under the two electrolyte systems is shown in fig. 2a and fig. 2b, the modified electrolyte can obviously prolong the working time of the foamed nickel anode in brine electrolysis, and obviously slow down the corrosion effect of chloride ions on the foamed nickel anode.
Example 2
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.25mol of K2SO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test results of the anode are shown in fig. 3, and the modified electrolyte can significantly prolong the working time of the foamed nickel anode in the brine electrolysis.
Example 3
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.25mol of Na2CO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test results of the anode are shown in fig. 4, and the modified electrolyte can significantly prolong the working time of the foamed nickel anode in the brine electrolysis.
Example 4
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.25mol of Na2HPO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test results of the anode are shown in fig. 5, and the modified electrolyte can significantly prolong the working time of the foamed nickel anode in the brine electrolysis.
Example 5
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.125mol of Na2SO4(5% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test results of the anode are shown in fig. 6, and the modified electrolyte can significantly prolong the working time of the foamed nickel anode in the brine electrolysis.
Example 6
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 1.0mol of Na2SO4(40% of the concentration of chloride ions) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test results of the anode are shown in fig. 7, and the modified electrolyte can significantly prolong the working time of the foamed nickel anode in the brine electrolysis.
Example 7
(1) Cutting the foamed nickel into a strip shape of 1cm multiplied by 3cm, and respectively washing the strip shape with hydrochloric acid, ethanol and deionized water to be used as a substrate for catalyst deposition.
(2) 0.5mmol of ferric nitrate nonahydrate, 0.5mmol of nickel nitrate hexahydrate and 10mmol of urea are dissolved in 35ml of deionized water and dissolved by stirring to form a transparent solution A.
(3) And (3) placing the foamed nickel treated in the step (1) and the transparent solution A in the step (2) in a 50ml polytetrafluoroethylene reaction kettle, heating to react for 12 hours at the temperature of 120 ℃, and then naturally cooling to room temperature to prepare the anode NiFe-LDH/foamed nickel catalytic material for the brine electrolysis hydrogen production reaction.
(4) And (4) taking out the anode NiFe-LDH/foamed nickel prepared in the step (3), ultrasonically cleaning the anode NiFe-LDH/foamed nickel for 3-5 times by using deionized water, cleaning the anode NiFe-LDH/foamed nickel for 2-3 times by using ethanol, and drying the anode NiFe-LDH/foamed nickel in an oven at the temperature of 60 ℃ for 12 hours.
(5) 1mol of NaOH and 0.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(6) 1mol of NaOH, 0.5mol of NaCl and 0.05mol of Na are added2SO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(7) And (3) taking the NiFe-LDH/foamed nickel dried in the step (4) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (5) and the step (6) as electrolytes, and testing the stability of the anode under the two electrolyte systems by adopting a two-electrode system under the constant current of 400 mA. The stability test results of the anode are shown in fig. 8, and the modified electrolyte can significantly prolong the working time of the NiFe-LDH/foamed nickel anode in brine electrolysis.
Example 8
(1) Cutting the foamed nickel into a strip shape of 1cm multiplied by 3cm, and respectively washing the strip shape with hydrochloric acid, ethanol and deionized water to be used as a substrate for catalyst deposition.
(2) 0.5mmol of ferric nitrate nonahydrate, 0.5mmol of nickel nitrate hexahydrate and 10mmol of urea are dissolved in 35ml of deionized water and dissolved by stirring to form a transparent solution A.
(3) And (3) placing the foamed nickel treated in the step (1) and the transparent solution A in the step (2) in a 50ml polytetrafluoroethylene reaction kettle, heating to react for 12h at the temperature of 120 ℃, and then naturally cooling to room temperature to prepare the anode NiFe-LDH/foamed nickel catalytic material for seawater electrolytic hydrogen production reaction.
(4) Taking out the anode NiFe-LDH/foamed nickel prepared in the step (3), ultrasonically cleaning the anode NiFe-LDH/foamed nickel with deionized water for 3-5 times, cleaning the anode NiFe-LDH/foamed nickel with ethanol for 2-3 times, and drying the anode NiFe-LDH/foamed nickel in an oven at the temperature of 60 ℃ for 12 hours.
(5) Dissolving 1.2mol of NaOH in 1L of seawater, filtering and precipitating to prepare seawater electrolyte.
(6) 1.2mol of NaOH and 0.05mol of Na2SO4(about 10% of the concentration of chloride ions in seawater) was dissolved in 1L of seawater, and the precipitate was filtered to prepare a modified electrolyte.
(7) And (3) taking the dried NiFe-LDH/foamed nickel in the step (4) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (5) and the step (6) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 400 mA. The stability test result of the anode is shown in fig. 9, and the modified electrolyte can obviously prolong the working time of the NiFe-LDH/foamed nickel anode in seawater electrolysis.
Example 9
(1) Cutting the foamed nickel into a strip shape of 1cm multiplied by 3cm, and respectively washing the strip shape with hydrochloric acid, ethanol and deionized water to be used as a substrate for catalyst deposition.
(2) 0.5mmol of ferric nitrate nonahydrate, 0.5mmol of nickel nitrate hexahydrate and 10mmol of urea are dissolved in 35ml of deionized water and dissolved by stirring to form a transparent solution A.
(3) And (3) placing the foamed nickel treated in the step (1) and the transparent solution A in the step (2) in a 50ml polytetrafluoroethylene reaction kettle, heating to react for 12h at the temperature of 120 ℃, and then naturally cooling to room temperature to prepare the anode NiFe-LDH/foamed nickel catalytic material for seawater electrolytic hydrogen production reaction.
(4) Taking out the anode NiFe-LDH/foamed nickel prepared in the step (3), ultrasonically cleaning the anode NiFe-LDH/foamed nickel with deionized water for 3-5 times, cleaning the anode NiFe-LDH/foamed nickel with ethanol for 2-3 times, and drying the anode NiFe-LDH/foamed nickel in an oven at the temperature of 60 ℃ for 12 hours.
(5) 6mol of NaOH and 2.3mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(6) 6mol of NaOH, 2.3mol of NaCl and 0.23mol of Na2SO4(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(7) And (3) taking the dried NiFe-LDH/foamed nickel in the step (4) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (5) and the step (6) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 400 mA. The stability test results of the anode are shown in fig. 10, and the modified electrolyte can significantly prolong the working time of the NiFe-LDH/foamed nickel anode in brine electrolysis.
Comparative example
(1) Two pieces of foam nickel are cut into strips of 1cm multiplied by 3cm, are respectively washed by hydrochloric acid, ethanol and deionized water, and are naturally dried in the air to be used as the anode of the brine electrolysis hydrogen production reaction.
(2) 1mol of NaOH and 2.5mol of NaCl are dissolved in 1L of deionized water to prepare the salt-water electrolyte.
(3) 1mol of NaOH, 2.5mol of NaCl and 0.25mol of NaNO3(10% of the chloride ion concentration) was dissolved in 1L of deionized water to prepare a modified electrolyte.
(4) And (3) taking the foamed nickel in the step (1) as an anode and a Pt electrode as a cathode, respectively taking the solutions prepared in the step (2) and the step (3) as electrolytes, and testing the stability of the anode in two electrolyte systems by adopting a two-electrode system under the constant current of 100 mA. The stability test result of the anode is shown in fig. 11, the working time of the foamed nickel in the brine electrolysis is not significantly prolonged by adding the nitrate-modified electrolyte, and the monovalent anion does not have the characteristic that the high-valence anion is preferentially adsorbed on the surface of the anode, so that the anode cannot be protected from corrosion.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. An electrolyte modification method for improving anode stability in an electrolytic hydrogen production process is characterized by comprising the following steps:
salt containing high-valence anions is added into the seawater and/or the brine treated by the alkali liquor as the electrolyte to obtain the modified electrolyte.
2. The method for modifying the electrolyte for improving the stability of the anode in the process of electrolytic hydrogen production according to claim 1, wherein the method comprises the following steps: the salt containing high valence anions comprises any one or combination of more than two of sulfate, carbonate or phosphate.
3. The method for modifying the electrolyte for improving the stability of the anode in the process of electrolytic hydrogen production according to claim 2, wherein the method comprises the following steps: the sulfate salt comprises sodium sulfate and/or potassium sulfate.
4. The method for modifying the electrolyte for improving the stability of the anode in the process of electrolytic hydrogen production according to claim 2, wherein the method comprises the following steps: the carbonate comprises sodium carbonate and/or potassium carbonate.
5. The method for modifying the electrolyte for improving the stability of the anode in the process of electrolytic hydrogen production according to claim 2, wherein the method comprises the following steps: the phosphate comprises any one or the combination of more than two of sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium monohydrogen phosphate or potassium dihydrogen phosphate.
6. The method for modifying an electrolyte for improving the stability of an anode in an electrolytic hydrogen production process according to any one of claims 1 to 5, wherein the method comprises the following steps: the ratio of the concentration of the high valence anions in the salt containing the high valence anions to the concentration of the chloride ions in the electrolyte is 5-40: 100.
7. The method for modifying an electrolyte for improving the stability of an anode in an electrolytic hydrogen production process according to any one of claims 1 to 5, characterized by comprising: dissolving alkaline substances in 1L of seawater to form alkali liquor treated seawater;
and/or the concentration of the alkaline substance is 1mol/L-6mol/L, and preferably, the alkaline substance comprises sodium hydroxide or potassium hydroxide.
8. The method for modifying an electrolyte for improving the stability of an anode in an electrolytic hydrogen production process according to any one of claims 1 to 5, comprising: the alkaline material and salt are dissolved in water to form a lye-treated brine.
9. The method for modifying the electrolyte for improving the stability of the anode in the process of electrolytic hydrogen production according to claim 8, wherein the method comprises the following steps: the concentration of the saline water is 0.5mol/L-2.5 mol/L.
10. A modified electrolyte prepared by the method of any one of claims 1-9.
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