阅读说明：本技术 一种基于碱性电解水的制氢工艺中提升材料寿命的方法 (Method for prolonging service life of material in hydrogen production process based on alkaline electrolyzed water ) 是由 李太斌 张冲 程莹 涂维党 庞飞 敬一枫 袁志镭 马星 粟丽蓉 郭荣鑫 周心怡 于 2021-09-29 设计创作，主要内容包括：本发明公开了一种基于碱性电解水的制氢工艺中提升材料寿命的方法,所述方法包括以下步骤：S1：电极原料准备→S2：电极制备→S3：电极预处理→S4：全电解水催化电极制备→S5：电极使用中保护。本发明通过釜中的物质在气相和液相溶剂的临界状态下反应使成品表面合成出过渡金属纳米材料,将表面合成出过渡金属纳米材料的成品与次磷酸钠放入研磨机研磨,次磷酸钠受热分解出的磷化氢气体将前驱体磷化,预处理的电极为过渡金属磷化物催化剂,且表面带有一层过渡金属纳米材料,该方法通过对电极进行两次加工,使电极内部以及表面均具有过渡金属纳米材料进行保护,从而有效地延长电极的使用寿命。(The invention discloses a method for prolonging the service life of a material in a hydrogen production process based on alkaline electrolyzed water, which comprises the following steps: s1: electrode material preparation → S2: electrode preparation → S3: electrode pretreatment → S4: preparation of full electrolysis water catalytic electrode → S5: the electrode is protected in use. The invention synthesizes transition metal nanometer material on the surface of the finished product by the reaction of the substances in the kettle in the critical state of gas phase and liquid phase solvent, the finished product of the transition metal nanometer material synthesized on the surface and sodium hypophosphite are put into a grinder to be ground, phosphine gas decomposed by the heating of the sodium hypophosphite is used for phosphorizing the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nanometer material.)

1. A method for improving material life in a hydrogen production process based on alkaline electrolysis of water, characterized in that the method comprises the following steps:

s1: electrode feedstock preparation

Preparing cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide, soaking the carbon cloth in concentrated nitric acid for 12-14h before use, repeatedly washing with water and ethanol respectively, and drying for later use;

s2: preparing an electrode:

(1) adding 1-2mmol of cobalt nitrate, 0.5-1mmol of nickel nitrate, 6.5-7.5mmol of urea, 3.5-4.5mmol of ammonium fluoride and ferric nitrate with different molar weights into 30-50ml of double distilled water, placing the mixture into a mixing device for mixing, placing the mixture into an ultrasonic device for ultrasonic treatment until the mixture is completely dissolved to obtain a mixed solution, completely immersing the carbon cloth treated in the step S1 into the prepared mixed solution, then transferring the carbon cloth and the solution into a 50ml of polytetrafluoroethylene reaction kettle, cooling the temperature of the reaction kettle to room temperature, taking the carbon cloth with the precursor out of the reaction kettle, repeatedly washing the carbon cloth with water and ethanol, and placing the carbon cloth into an oven for drying for later use;

(2) putting sodium hypophosphite powder as a phosphorus source into the front end of an aluminum oxide square boat, then putting the dried carbon cloth into the rear end of the aluminum oxide square boat, putting the aluminum oxide square boat into a tubular furnace, introducing nitrogen as a protective gas, continuously introducing the nitrogen until the temperature of the tubular furnace is reduced to room temperature, washing the nitrogen with water and ethanol, and then putting the nitrogen into an oven to be dried to obtain a finished product;

s3: electrode pretreatment

(3) Placing the finished product obtained in the step S2 in a reaction kettle, and placing the reaction kettle in a high-temperature environment to enable the kettle to be in a high-temperature and high-pressure environment, wherein substances in the kettle react in a critical state of a gas-phase solvent and a liquid-phase solvent to enable the surface of the finished product to synthesize a transition metal nano material;

(4) grinding the finished product of the transition metal nano material synthesized on the surface and sodium hypophosphite in a grinding machine, then heating the ground substance in a low-temperature box, phosphorizing a precursor by phosphine gas decomposed by heating the sodium hypophosphite, wherein a pretreated electrode is a transition metal phosphide catalyst and is provided with a layer of transition metal nano material on the surface;

s4: preparation of full-electrolysis water catalytic electrode

Shearing the catalyst obtained in the step S3, putting the catalyst into a beaker filled with acetone for ultrasonic treatment, then putting the catalyst into a beaker filled with hydrochloric acid for ultrasonic treatment, finally performing ultrasonic treatment with deionized water, drying the catalyst, simultaneously adding deionized water, absolute ethyl alcohol and a Nafion solution for ultrasonic treatment to obtain a mixed solution, and then dropwise adding the mixed solution to the completely treated catalyst by using a liquid-moving gun for ten times to finish the preparation.

2. The method for prolonging the service life of materials in the hydrogen production process based on alkaline electrolyzed water as claimed in claim 1, wherein in step S1, the purities of cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide are all more than 98%.

3. The method for prolonging the service life of the material in the hydrogen production process based on the alkaline electrolyzed water as claimed in claim 1, wherein in the step S2, the molar weight of the ferric nitrate is respectively 0.2mmol, 0.4mmol, 0.6mmol, 0.8mmol and 1mmol, the temperature of the mixing device is 40-50 ℃, the rotation speed is 500r/min, the working temperature of the reaction kettle is 120 ℃, the hydrothermal time is 6h, and the temperature of the oven is set to 80 ℃.

4. The method of claim 1, wherein in step S2, the distance between the carbon cloth and the sodium hypophosphite powder is 3cm, the gas flow velocity inside the tube furnace is 100cc/min-1, and the gas flow velocity inside the tube furnace is 2 ℃/min^-1Heating to 400 ℃ at the temperature rising speed and keeping the temperature for 1 h.

5. The method for prolonging the service life of the material in the hydrogen production process based on the alkaline electrolyzed water as claimed in claim 1, wherein in the step S3, the reaction kettle is sealed by a clamping device when in use, the internal pressure of the reaction kettle is 1MPa, the temperature is 100 ℃, the heating temperature of the low-temperature box is 10 ℃, and the heating time is 1.5 h.

6. The method for prolonging the service life of a material in an alkaline electrolyzed water-based hydrogen production process according to claim 1, wherein in the step S4, a catalyst is weighed and placed into a beaker, 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution are added at the same time, the beaker is placed into an ultrasonic cleaner for ultrasonic treatment for 1h, a platinum carbon electrode is polished to remove impurities on the electrode, then the difference value of oxidation reduction peaks in potassium ferricyanide solution is represented to be lower than 85mV, and finally a liquid-moving gun is used for sucking 3ul of product solution to be dropped on a polished electrode head with the diameter of 3 cm.

7. The method for prolonging the service life of the material in the hydrogen production process based on the alkaline electrolyzed water as claimed in claim 1, wherein in the step S4, the amount of acetone is 50ml, the ultrasonic time is 30min, the concentration of hydrochloric acid is 6mol/L, the amount of hydrochloric acid is 50ml, the ultrasonic time of deionized water is 10min, 700ul of deionized water, 240ul of absolute ethyl alcohol and 60ul of Nafion solution are added for ultrasonic treatment for 1 h.

8. The method for improving the life of materials in the hydrogen production process based on alkaline electrolysis of water as claimed in claim 1, wherein the method further comprises the following steps of S5: and (3) protecting the electrode in use, periodically taking out the electrode after the electrolytic hydrogen production process is finished, putting the electrode into cleaning equipment, pouring ethanol for soaking for 2 hours, stirring the electrode and the ethanol by the cleaning equipment at a rotating speed of 200r/min for 30 minutes, and drying the electrode in a 45-DEG C oven after the cleaning is finished.

Technical Field

The invention relates to a hydrogen production process, in particular to a method for prolonging the service life of a material in the hydrogen production process based on alkaline electrolyzed water.

Background

The hydrogen energy industry is a strategic industrial system for constructing a low-carbon clean energy system, responding to environmental challenges, promoting energy revolution and ensuring energy safety, hydrogen has the dual property of energy and substance communication, and is an important link for extending electric energy to various industrial fields to deeply replace fossil energy utilization, and the water electrolysis hydrogen production process is one commonly used method for hydrogen production, and in the hydrogen production process, an electrode needs to be placed in water for electricity connection and then water electrolysis is carried out.

The prior art has the following defects: because the electrode is used by being immersed in water for electrolysis, the electrode can be damaged and cannot be used due to poor corrosion resistance of the electrode in the long-term use process.

Disclosure of Invention

The invention provides a method for prolonging the service life of a material in a hydrogen production process based on alkaline electrolyzed water, which aims to solve the problems in the background technology.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the method comprises the following steps:

s1: preparing an electrode raw material: preparing cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide, wherein the purity of the materials is over 98 percent, soaking the carbon cloth in concentrated nitric acid for 12 hours before use, respectively washing with water and ethanol repeatedly, and drying for later use.

S2: preparing an electrode:

(1) adding 1mmol of cobalt nitrate, 0.5mmol of nickel nitrate, 6.5mmol of urea, 3.5mmol of ammonium fluoride and different molar amounts of ferric nitrate (respectively 0.2mmol, 0.4mmol, 0.6mmol, 0.8mmol and 1mmol) into 30ml of double distilled water, mixing the mixture in a mixing device with the temperature of 40 ℃ and the rotating speed of 500r/min, putting the mixture into an ultrasonic device for ultrasonic treatment until the mixture is completely dissolved to obtain a mixed solution, completely immersing the carbon cloth treated in the step S1 into the prepared mixed solution, transferring the carbon cloth and the solution into a 50ml of polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment at the temperature of 120 ℃ for 6h, cooling the temperature of the reaction kettle to room temperature, taking the carbon cloth with the precursor out of the reaction kettle, repeatedly washing the carbon cloth with water and ethanol, and then putting the carbon cloth into an oven with the temperature of 80 ℃ for drying for later use;

(2) putting sodium hypophosphite powder as a phosphorus source into the front end of an aluminum oxide square boat, then putting the dried carbon cloth into the rear end of the aluminum oxide square boat, keeping the distance of 3cm from the sodium hypophosphite powder, putting the aluminum oxide square boat into a tubular furnace, introducing nitrogen as protective gas, wherein the air flow rate is 100cc/min-1, and then putting the tubular furnace at the speed of 2 ℃/min^-1Heating to 400 ℃ at the heating speed, keeping the temperature for 1h, continuously introducing nitrogen in the process until the temperature of the tubular furnace is reduced to room temperature, and flushing with water and ethanolAnd putting the mixture into an oven to be dried after cleaning to obtain a finished product.

S3: electrode pretreatment

(3) Placing the finished product obtained in the step S2 in a reaction kettle, completely sealing the reaction kettle through a clamping device, then placing the reaction kettle in a high-temperature environment, enabling the interior of the reaction kettle to be in a high-temperature and high-pressure environment, wherein the pressure is 1MPa, the temperature is 100 ℃, and substances in the reaction kettle react under the critical state of a gas-phase solvent and a liquid-phase solvent to synthesize a transition metal nano material on the surface of the finished product;

(4) and (2) putting the finished product of the transition metal nano material synthesized on the surface and sodium hypophosphite into a grinding machine for grinding, then putting the ground substance into a low-temperature box for heating, wherein the heating temperature is 10 ℃, the heating time is 1.5h, phosphine gas decomposed by heating the sodium hypophosphite is used for phosphorizing the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nano material.

S4: preparation of full-electrolysis water catalytic electrode

Weighing a catalyst, putting the catalyst into a beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 1h, simultaneously polishing a platinum-carbon electrode to remove impurities on the electrode, then representing the result in potassium ferricyanide solution until the oxidation-reduction peak difference value is lower than 85mV, finally sucking 3ul product solution by using a liquid-transferring gun, dripping the solution on a polished electrode head with the diameter of 3cm, naturally airing the electrode, simultaneously shearing four pieces of 1cm x 1cm catalyst, putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, then putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, finally performing ultrasonic treatment for 10min by using deionized water, drying the electrode head, weighing 10mg compound by using a precise electronic scale, putting the compound into the beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution for ultrasonic treatment for 1h, then dropwise adding 200ul product solution on the catalyst by using a liquid-transferring gun for ten times, and naturally drying the mixture.

S5: electrode in-service protection

After the electrolytic hydrogen production process is finished, the electrode needs to be periodically taken out and put into cleaning equipment, ethanol is poured into the cleaning equipment for soaking for 2 hours, then the cleaning equipment stirs the electrode and the ethanol at the rotating speed of 200r/min, the cleaning time is 30min, and the electrode is put into a 45 ℃ oven for drying after the cleaning is finished.

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

the invention synthesizes transition metal nanometer material on the surface of the finished product by the reaction of the substances in the kettle in the critical state of gas phase and liquid phase solvent, the finished product of the transition metal nanometer material synthesized on the surface and sodium hypophosphite are put into a grinder to be ground, then the ground substance is put into a low temperature box to be heated, the heating temperature is 10 ℃, the heating time is 1.5h, phosphine gas decomposed by the sodium hypophosphite after being heated phosphorizes the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nanometer material.

Detailed Description

The present invention is further illustrated by the following examples, which include, but are not limited to, the following examples.

Example 1

A method for increasing material life in an alkaline electrolyzed water based hydrogen production process, the method comprising the steps of:

s1: preparing an electrode raw material: preparing cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide, wherein the purity of the materials is over 98 percent, soaking the carbon cloth in concentrated nitric acid for 12 hours before use, respectively washing with water and ethanol repeatedly, and drying for later use.

S2: preparing an electrode:

(1) adding 1mmol of cobalt nitrate, 0.5mmol of nickel nitrate, 6.5mmol of urea, 3.5mmol of ammonium fluoride and different molar amounts of ferric nitrate (respectively 0.2mmol, 0.4mmol, 0.6mmol, 0.8mmol and 1mmol) into 30ml of double distilled water, mixing the mixture in a mixing device with the temperature of 40 ℃ and the rotating speed of 500r/min, putting the mixture into an ultrasonic device for ultrasonic treatment until the mixture is completely dissolved to obtain a mixed solution, completely immersing the carbon cloth treated in the step S1 into the prepared mixed solution, transferring the carbon cloth and the solution into a 50ml of polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment at the temperature of 120 ℃ for 6h, cooling the temperature of the reaction kettle to room temperature, taking the carbon cloth with the precursor out of the reaction kettle, repeatedly washing the carbon cloth with water and ethanol, and then putting the carbon cloth into an oven with the temperature of 80 ℃ for drying for later use;

(2) putting sodium hypophosphite powder as a phosphorus source into the front end of an aluminum oxide square boat, then putting the dried carbon cloth into the rear end of the aluminum oxide square boat, keeping the distance of 3cm from the sodium hypophosphite powder, putting the aluminum oxide square boat into a tubular furnace, introducing nitrogen as protective gas, wherein the air flow rate is 100cc/min-1, and then putting the tubular furnace at the speed of 2 ℃/min^-1Heating to 400 ℃ at the heating speed, keeping the temperature for 1h, continuously introducing nitrogen in the process until the temperature of the tubular furnace is reduced to room temperature, washing with water and ethanol, and drying in an oven to obtain the finished product.

S3: electrode pretreatment

(3) Placing the finished product obtained in the step S2 in a reaction kettle, completely sealing the reaction kettle through a clamping device, then placing the reaction kettle in a high-temperature environment, enabling the interior of the reaction kettle to be in a high-temperature and high-pressure environment, wherein the pressure is 1MPa, the temperature is 100 ℃, and substances in the reaction kettle react under the critical state of a gas-phase solvent and a liquid-phase solvent to synthesize a transition metal nano material on the surface of the finished product;

(4) and (2) putting the finished product of the transition metal nano material synthesized on the surface and sodium hypophosphite into a grinding machine for grinding, then putting the ground substance into a low-temperature box for heating, wherein the heating temperature is 10 ℃, the heating time is 1.5h, phosphine gas decomposed by heating the sodium hypophosphite is used for phosphorizing the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nano material.

S4: preparation of full-electrolysis water catalytic electrode

Weighing a catalyst, putting the catalyst into a beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 1h, simultaneously polishing a platinum-carbon electrode to remove impurities on the electrode, then representing the result in potassium ferricyanide solution until the oxidation-reduction peak difference value is lower than 85mV, finally sucking 3ul product solution by using a liquid-transferring gun, dripping the solution on a polished electrode head with the diameter of 3cm, naturally airing the electrode, simultaneously shearing four pieces of 1cm x 1cm catalyst, putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, then putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, finally performing ultrasonic treatment for 10min by using deionized water, drying the electrode head, weighing 10mg compound by using a precise electronic scale, putting the compound into the beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution for ultrasonic treatment for 1h, then dropwise adding 200ul product solution on the catalyst by using a liquid-transferring gun for ten times, and naturally drying the mixture.

S5: electrode in-service protection

After the electrolytic hydrogen production process is finished, the electrode needs to be periodically taken out and put into cleaning equipment, ethanol is poured into the cleaning equipment for soaking for 2 hours, then the cleaning equipment stirs the electrode and the ethanol at the rotating speed of 200r/min, the cleaning time is 30min, and the electrode is put into a 45 ℃ oven for drying after the cleaning is finished.

Example 2

A method for increasing material life in an alkaline electrolyzed water based hydrogen production process, the method comprising the steps of:

s1: preparing an electrode raw material: preparing cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide, wherein the purity of the materials is over 98 percent, putting the carbon cloth into concentrated nitric acid for soaking for 13 hours before use, respectively washing with water and ethanol repeatedly, and drying for later use.

S2: preparing an electrode:

(1) adding 1.5mmol of cobalt nitrate, 0.7mmol of nickel nitrate, 7mmol of urea, 4mmol of ammonium fluoride and different molar amounts of ferric nitrate (respectively 0.2mmol, 0.4mmol, 0.6mmol, 0.8mmol and 1mmol) into 45ml of double distilled water, mixing the mixture in a mixing device with the temperature of 45 ℃ and the rotating speed of 500r/min, putting the mixture into an ultrasonic device for ultrasonic treatment until the mixture is completely dissolved to obtain a mixed solution, completely immersing the carbon cloth treated in the step S1 into the prepared mixed solution, transferring the carbon cloth and the solution into a 50ml of polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment at the temperature of 120 ℃ for 6h, cooling the temperature of the reaction kettle to room temperature, taking out the carbon cloth with the precursor from the reaction kettle, repeatedly washing the carbon cloth with water and ethanol, and then putting the carbon cloth into an oven with the temperature of 80 ℃ for drying for later use;

(2) putting sodium hypophosphite powder as a phosphorus source into the front end of an aluminum oxide square boat, then putting the dried carbon cloth into the rear end of the aluminum oxide square boat, keeping the distance of 3cm from the sodium hypophosphite powder, putting the aluminum oxide square boat into a tubular furnace, introducing nitrogen as protective gas, wherein the air flow rate is 100cc/min-1, and then putting the tubular furnace at the speed of 2 ℃/min^-1Heating to 450 ℃ at the heating speed, keeping the temperature for 1h, continuously introducing nitrogen in the process until the temperature of the tubular furnace is reduced to room temperature, washing with water and ethanol, and drying in an oven to obtain the finished product.

S3: electrode pretreatment

(3) Placing the finished product obtained in the step S2 in a reaction kettle, completely sealing the reaction kettle through a clamping device, then placing the reaction kettle in a high-temperature environment, enabling the interior of the reaction kettle to be in a high-temperature and high-pressure environment, wherein the pressure is 1MPa, the temperature is 100 ℃, and substances in the reaction kettle react under the critical state of a gas-phase solvent and a liquid-phase solvent to synthesize a transition metal nano material on the surface of the finished product;

(4) and (2) putting the finished product of the transition metal nano material synthesized on the surface and sodium hypophosphite into a grinding machine for grinding, then putting the ground substance into a low-temperature box for heating, wherein the heating temperature is 10 ℃, the heating time is 1.5h, phosphine gas decomposed by heating the sodium hypophosphite is used for phosphorizing the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nano material.

S4: preparation of full-electrolysis water catalytic electrode

Weighing a catalyst, putting the catalyst into a beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 1h, simultaneously polishing a platinum-carbon electrode to remove impurities on the electrode, then representing the result in potassium ferricyanide solution until the oxidation-reduction peak difference value is lower than 85mV, finally sucking 3ul product solution by using a liquid-transferring gun, dripping the solution on a polished electrode head with the diameter of 3cm, naturally airing the electrode, simultaneously shearing four pieces of 1cm x 1cm catalyst, putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, then putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, finally performing ultrasonic treatment for 10min by using deionized water, drying the electrode head, weighing 10mg compound by using a precise electronic scale, putting the compound into the beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution for ultrasonic treatment for 1h, then dropwise adding 200ul product solution on the catalyst by using a liquid-transferring gun for ten times, and naturally drying the mixture.

S5: electrode in-service protection

After the electrolytic hydrogen production process is finished, the electrode needs to be periodically taken out and put into cleaning equipment, ethanol is poured into the cleaning equipment for soaking for 2.5 hours, then the cleaning equipment stirs the electrode and the ethanol at the rotating speed of 200r/min, the cleaning time is 30 minutes, and the electrode is put into a 45-DEG C oven for drying after the cleaning is finished.

Example 3

A method for increasing material life in an alkaline electrolyzed water based hydrogen production process, the method comprising the steps of:

s1: preparing an electrode raw material: preparing cobalt nitrate, nickel nitrate, ferric nitrate, ammonium fluoride, urea, sodium hypophosphite and potassium hydroxide, wherein the purity of the materials is over 98 percent, putting the carbon cloth into concentrated nitric acid for soaking for 14 hours before use, respectively washing with water and ethanol repeatedly, and drying for later use.

S2: preparing an electrode:

(1) adding 2mmol of cobalt nitrate, 1mmol of nickel nitrate, 7.5mmol of urea, 4.5mmol of ammonium fluoride and different molar amounts of ferric nitrate (respectively 0.2mmol, 0.4mmol, 0.6mmol, 0.8mmol and 1mmol) into 50ml of double distilled water, mixing the mixture in a mixing device with the temperature of 50 ℃ and the rotating speed of 500r/min, putting the mixture into an ultrasonic device for ultrasonic treatment until the mixture is completely dissolved to obtain a mixed solution, completely immersing the carbon cloth treated in the step S1 into the prepared mixed solution, transferring the carbon cloth and the solution into a 50ml of polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment at the temperature of 120 ℃ for 6h, cooling the temperature of the reaction kettle to room temperature, taking out the carbon cloth with the precursor from the reaction kettle, repeatedly washing the carbon cloth with water and ethanol, and then putting the carbon cloth into an oven with the temperature of 80 ℃ for drying for later use;

(2) sodium hypophosphite powder as a phosphorus source is added with oxygenPlacing the dried carbon cloth at the rear end of the aluminum oxide ark at a distance of 3cm from the sodium hypophosphite powder, placing the aluminum oxide ark in a tubular furnace, introducing nitrogen as protective gas at an air flow rate of 100cc/min-1, and placing the tubular furnace at a speed of 2 ℃/min^-1Heating to 450 ℃ at the heating speed, keeping the temperature for 1h, continuously introducing nitrogen in the process until the temperature of the tubular furnace is reduced to room temperature, washing with water and ethanol, and drying in an oven to obtain the finished product.

S3: electrode pretreatment

(3) Placing the finished product obtained in the step S2 in a reaction kettle, completely sealing the reaction kettle through a clamping device, then placing the reaction kettle in a high-temperature environment, enabling the interior of the reaction kettle to be in a high-temperature and high-pressure environment, wherein the pressure is 1MPa, the temperature is 100 ℃, and substances in the reaction kettle react under the critical state of a gas-phase solvent and a liquid-phase solvent to synthesize a transition metal nano material on the surface of the finished product;

(4) and (2) putting the finished product of the transition metal nano material synthesized on the surface and sodium hypophosphite into a grinding machine for grinding, then putting the ground substance into a low-temperature box for heating, wherein the heating temperature is 10 ℃, the heating time is 1.5h, phosphine gas decomposed by heating the sodium hypophosphite is used for phosphorizing the precursor, the pretreated electrode is a transition metal phosphide catalyst, and the surface is provided with a layer of transition metal nano material.

S4: preparation of full-electrolysis water catalytic electrode

Weighing a catalyst, putting the catalyst into a beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 1h, simultaneously polishing a platinum-carbon electrode to remove impurities on the electrode, then representing the result in potassium ferricyanide solution until the oxidation-reduction peak difference value is lower than 85mV, finally sucking 3ul product solution by using a liquid-transferring gun, dripping the solution on a polished electrode head with the diameter of 3cm, naturally airing the electrode, simultaneously shearing four pieces of 1cm x 1cm catalyst, putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, then putting the electrode head into the beaker containing 50ml acetone for ultrasonic treatment for 30min, finally performing ultrasonic treatment for 10min by using deionized water, drying the electrode head, weighing 10mg compound by using a precise electronic scale, putting the compound into the beaker, simultaneously adding 700ul deionized water, 240ul absolute ethyl alcohol and 60ul Nafion solution for ultrasonic treatment for 1h, then dropwise adding 200ul product solution on the catalyst by using a liquid-transferring gun for ten times, and naturally drying the mixture.

S5: electrode in-service protection

After the electrolytic hydrogen production process is finished, the electrode needs to be periodically taken out and put into cleaning equipment, ethanol is poured into the cleaning equipment for soaking for 2.5 hours, then the cleaning equipment stirs the electrode and the ethanol at the rotating speed of 200r/min, the cleaning time is 30 minutes, and the electrode is put into a 45-DEG C oven for drying after the cleaning is finished.

Example 4

Catalyst performance side test: taking a carrier loaded with a catalyst as an electrode, taking a saturated calomel electrode as a reference electrode, taking the used reference electrode as the saturated calomel electrode, and carrying out iR compensation on obtained data in order to reduce the influence of the self resistance of the catalyst and the resistances of the saturated calomel electrode and an auxiliary electrode;

the compensation formula is as follows: e_{Correction of}In order to facilitate the separation of gas generated by reaction from the surface of the catalyst, nitrogen is introduced into the electrolyte to saturate the gas in the solution before the HER test is performed, and oxygen is introduced into the electrolyte to saturate the dissolved oxygen amount of the solution before the OER test is performed.

The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and any insubstantial changes or modifications made within the spirit and scope of the main design of the present invention will solve the technical problems consistent with the present invention and shall be included in the scope of the present invention.