Preparation method of high-efficiency stable TiNi alloy-based porous composite structure electrocatalytic electrode

Abstract

The application discloses a preparation method of a high-efficiency and stable TiNi alloy-based porous composite structure electrocatalytic electrode, and relates to a preparation method of an electrocatalytic electrode. The application aims at solving the problem that the existing hydrogen evolution electrocatalytic electrode cannot simultaneously have high hydrogen production efficiency, low cost and excellent stability. The preparation method comprises the following steps: firstly, pretreatment of a sodium metaaluminate pore former; secondly, ball milling mixing; thirdly, preparation of a porous TiNi alloy; and fourthly, composite of a catalytic active layer. The application is used for the preparation of the high-efficiency and stable TiNi alloy-based porous composite structure electrocatalytic electrode.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of an electrocatalytic electrode. BACKGROUND

[0002] Under the background of global energy transformation, water electrolysis hydrogen production technology has a broad development space and becomes an important development direction of future energy industry due to its environmental friendliness and simple process. Although hydrogen energy is highly praised due to its clean and efficient characteristics, high electrode material cost and high power cost seriously limit the wide application of water electrolysis hydrogen production technology. Therefore, it is extremely important to develop efficient, stable and low-cost electrocatalysts for the industrial application of water electrolysis hydrogen production. In recent years, researchers have made some progress in the development of non-noble metal and trace noble metal electrocatalysts, but the stability of the electrocatalysts is poor and cannot meet the long-term service activity requirements under working conditions. Therefore, it is urgent to design and develop electrocatalysts with high hydrogen production efficiency, low cost and excellent stability and a preparation method thereof. SUMMARY

[0003] The present application aims to solve the problem that the existing hydrogen evolution electrocatalytic electrode cannot simultaneously have high hydrogen production efficiency, low cost and excellent stability, and further provides a preparation method of a high-efficiency and stable TiNi alloy-based porous composite structure electrocatalytic electrode.

[0004] A preparation method of a high-efficiency and stable TiNi alloy-based porous composite structure electrocatalytic electrode, which is carried out according to the following steps:

[0005] I. Sodium metaaluminate pore-forming agent pretreatment:

[0006] ①The sodium metaaluminate powder is pressed into a block, then high-temperature sintering is carried out in an air atmosphere, and finally the sodium metaaluminate sintered block is taken out after furnace cooling;

[0007] ②The sodium metaaluminate sintered block is ground and sieved to obtain sodium metaaluminate particles;

[0008] II. Ball milling mixing:

[0009] The sodium metaaluminate particles and the metal powder are ball-mixed to obtain a mixed material;

[0010] The particle size of the metal powder is 10-50 μm;

[0011] III. Preparation of porous TiNi-based alloy:

[0012] ①The mixed material is placed in a graphite mold in a spark plasma sintering furnace, and pre-pressed for 5-15 min under a pressure of 30-50 MPa to obtain a pre-pressed mixed material;

[0013] ② Under vacuum or protective atmosphere, the pre-pressed mixture is heated to 1100-1300 DEG C, and kept at the temperature of 1100-1300 DEG C for 10-20 min, and finally cooled with the furnace to obtain TiNi-based alloy block;

[0014] ③ Polishing the TiNi-based alloy block until the metal luster is exposed to obtain the precursor;

[0015] Four, the composite of the catalytically active layer:

[0016] ① The precursor is immersed in dilute hydrochloric acid, and then placed in a high-frequency ultrasonic transducer, and oscillated at a frequency of 0.01-20 kHz for 5-20 min to obtain the precursor covered with catalytically active material on the surface;

[0017] ② The precursor covered with catalytically active material on the surface is washed and dried, and the preparation method of the high-efficiency and stable TiNi alloy-based porous composite structure electrocatalytic electrode is completed.

[0018] The beneficial effects of the present application are:

[0019] 1. The present application uses abundant and low-cost non-noble metal materials as raw materials to prepare HER catalytically active electrodes close to noble metal electrocatalysis, but the cost is much lower than that of Pt, Ir, Ru and other noble metals, achieving the balance between cost and performance, and showing significant economic benefits.

[0020] 2. The present application can control the pore number and pore size of the porous TiNi alloy obtained by adjusting the amount and particle size of sodium metaaluminate, and further control the electrochemical active area, and can also control the loading amount of the electrochemical active material by adjusting the concentration of hydrochloric acid and the action time of the ultrasonic transducer, and further adjust the influence on the HER catalytic performance, so that the preparation method is controllable.

[0021] 3. The electrode obtained by the present application is based on porous TiNi alloy, which has excellent thermodynamic stability and mechanical stability, and the dilute hydrochloric acid solution reacts with the TiNi alloy and the sodium metaaluminate particle composite material substrate, so that the Ti4Ni2O 0.3 , Ti4Ni2O 0.6Both the Ni3Ti layer and these compounds exhibit excellent electrical conductivity, providing a solid foundation for the electrode's superior hydrogen evolution catalytic activity, thereby improving hydrogen production efficiency. This in-situ grown electrocatalyst layer is firmly bonded to the porous TiNi alloy substrate through chemical bonding, and the resulting catalyst layer exhibits a bulk morphology without obvious nanostructures. The morphology is minimally affected during long-term service, thus giving it excellent long-term service stability. Within 200 hours, its HER overpotential only increased by 7mV, indicating broad application prospects.

[0022] 4. The water electrolysis catalytic electrode obtained in this invention has a porous structure, which imparts a high specific surface area to the electrode. Simultaneously, the catalytically active material on the electrode surface is an intermetallic compound with good conductivity, and the bond between the catalytically active material layer on the electrode surface and the porous TiNi-based alloy is strong and requires no organic binder, significantly reducing contact resistance and charge transfer resistance. Excellent conductivity and high specific surface area endow it with superior catalytic activity. The TiNi alloy-based porous composite electrocatalytic electrode prepared in this invention exhibits excellent catalytic activity at 10 mA / cm². 2 With an overpotential of only 72mV, it exhibits excellent hydrogen evolution performance, approaching that of commercial Pt / C electrodes (overpotential of 30mV).

[0023] 5. This invention can also be used to epitaxially grow other TiNi-based alloys, such as ternary or multi-element alloys like TiNiFe, TiNiMo, TiNiCr, and TiNiNb, all of which can be used to prepare electrodes with excellent HER catalytic activity through the method provided by this invention.

[0024] Instruction manual illustrations

[0025] Figure 1 The microstructure of the precursor prepared in step 3③ of Example 1 is shown in the image.

[0026] Figure 2 The image shows the microstructure of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1.

[0027] Figure 3 X-ray diffraction pattern of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1;

[0028] Figure 4 The electrochemical active area of ​​the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 and the commercial TiNi alloy is shown.

[0029] Figure 5 The efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 and the HER polarization curve of a commercial 20% Pt / C electrode.

[0030] Figure 6 The constant current stability test of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 in 1M KOH electrolyte. Detailed Implementation

[0031] Specific Implementation Method 1: This implementation method provides a method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode, which is carried out according to the following steps:

[0032] I. Pretreatment with sodium aluminate pore-forming agent:

[0033] ① The sodium aluminate powder is pressed into blocks, then sintered at high temperature in air atmosphere, and finally cooled in the furnace and taken out to obtain sodium aluminate sintered blocks.

[0034] ② Grind and sieve the sintered sodium aluminate blocks to obtain sodium aluminate microparticles;

[0035] II. Ball milling and mixing:

[0036] Sodium aluminate particles and metal powder were ball-milled and mixed to obtain a mixture;

[0037] The particle size of the metal powder is 10μm to 50μm;

[0038] III. Preparation of porous TiNi-based alloys:

[0039] ① The mixture is placed in a graphite mold in a discharge plasma sintering furnace and pre-pressed for 5 min to 15 min under a pressure of 30 MPa to 50 MPa to obtain the pre-pressed mixture;

[0040] ② Under vacuum or protective atmosphere, the pre-compressed mixture is heated to 1100℃~1300℃ and held at 1100℃~1300℃ for 10min~20min. Finally, it is cooled in the furnace to obtain TiNi-based alloy blocks.

[0041] ③ Polish the TiNi-based alloy block until the metallic luster is exposed to obtain the precursor;

[0042] IV. Composite of the catalytic active layer:

[0043] ① The precursor is immersed in dilute hydrochloric acid and then placed in a high-frequency ultrasonic transducer. Under the condition of 0.01kHz~20kHz, the reaction is oscillated for 5min~20min to obtain a precursor with a surface covered with catalytically active material.

[0044] ② The precursor with catalytically active material on its surface is cleaned and dried, thus completing the preparation method of a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode.

[0045] Principle: Using sodium aluminate (1650℃), which has a melting point higher than TiNi alloy, as a pore-forming agent, a TiNi alloy and sodium aluminate particle composite material was obtained by SPS discharge plasma sintering as a precursor. Subsequently, the TiNi alloy and sodium aluminate particle composite material was immersed in a dilute hydrochloric acid solution. The sodium aluminate on the surface dissolved in the solution, exposing the porous structure of the TiNi alloy surface, providing more active sites for the hydrogen evolution reaction (HER). Simultaneously, because the Ti element in the TiNi alloy reacts more readily with HCl, some Ti atoms on the TiNi alloy surface were dissolved by hydrochloric acid, transforming the surface TiNi phase into the Ni3Ti phase, which has high catalytic activity and high conductivity. At the same time, the reaction of sodium aluminate with hydrochloric acid produces basic aluminum chloride, which has a strong electron-trapping ability. Basic aluminum chloride traps electrons in Ti2Ni, causing the Ti2Ni phase in the TiNi alloy to be oxidized by basic aluminum chloride to generate Ti4Ni2O, which has good conductivity. x (Ti4Ni2O 0.3 Ti4Ni2O 0.6 Highly catalytically active Ni3Ti and Ti4Ni2O x The synergistic effect enables this TiNi alloy-based porous composite electrocatalytic electrode to exhibit excellent HER catalytic activity.

[0046] The beneficial effects of this embodiment are:

[0047] 1. This embodiment uses abundant and inexpensive non-precious metal materials as raw materials to prepare HER catalytic activity close to that of precious metal electrocatalysis, but at a cost far lower than that of precious metals such as Pt, Ir, and Ru, achieving a balance between cost and performance and demonstrating significant economic benefits.

[0048] 2. In this embodiment, the number and size of pores in the porous TiNi alloy obtained by sintering can be controlled by adjusting the amount of sodium aluminate and the particle size. This allows for control of the electrochemical active area. At the same time, the loading of electrochemical active material can be controlled by adjusting the concentration of hydrochloric acid and the action time of the ultrasonic transducer, thereby adjusting the effect on the HER catalytic performance. The preparation method is controllable.

[0049] 3. The electrode obtained in this embodiment uses a porous TiNi-based alloy as a substrate, exhibiting excellent thermodynamic and mechanical stability. Furthermore, the dilute hydrochloric acid solution reacts with the TiNi-based alloy and sodium aluminate particle composite substrate, successfully enabling the in-situ growth of Ti4Ni2O with excellent conductivity and electrocatalytic activity on the porous TiNi alloy surface. 0.3 Ti4Ni2O 0.6Both the Ni3Ti layer and these compounds exhibit excellent electrical conductivity, providing a solid foundation for the electrode's superior hydrogen evolution catalytic activity, thereby improving hydrogen production efficiency. This in-situ grown electrocatalyst layer is firmly bonded to the porous TiNi alloy substrate through chemical bonding, and the resulting catalyst layer exhibits a bulk morphology without obvious nanostructures. The morphology is minimally affected during long-term service, thus giving it excellent long-term service stability. Within 200 hours, its HER overpotential only increased by 7mV, indicating broad application prospects.

[0050] 4. The water electrolysis catalytic electrode obtained in this embodiment has a porous structure, which imparts a high specific surface area to the electrode. Simultaneously, the catalytically active material on the electrode surface is an intermetallic compound with good conductivity, and the bond between the catalytically active material layer on the electrode surface and the porous TiNi-based alloy is strong and requires no organic binder, significantly reducing contact resistance and charge transfer resistance. Excellent conductivity and high specific surface area endow it with superior catalytic activity. The TiNi alloy-based porous composite electrocatalytic electrode prepared in this embodiment exhibits excellent catalytic activity at 10 mA / cm². 2 With an overpotential of only 72mV, it exhibits excellent hydrogen evolution performance, approaching that of commercial Pt / C electrodes (overpotential of 30mV).

[0051] 5. This embodiment can also be used to epitaxially grow other TiNi-based alloys, such as ternary or multi-element alloys like TiNiFe, TiNiMo, TiNiCr, and TiNiNb, all of which can be used to prepare electrodes with excellent HER catalytic activity through the method provided in this embodiment.

[0052] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that: Step One ① is carried out at high temperature for 3 to 4 hours under air atmosphere and temperature conditions of 1000℃~1500℃. Everything else is the same as in Specific Implementation Method One.

[0053] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that the particle size of the sodium aluminate microparticles mentioned in step one, step two, is 100 μm to 300 μm. Everything else is the same as in Specific Implementation Method One or Two.

[0054] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the volume ratio of sodium aluminate particles to metal powder in step two is (0.5-1.1):1. Everything else is the same as in Specific Implementation Methods One to Three.

[0055] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the metal powder mentioned in step two is a mixture of Ti powder, Ni powder, and other element powders; the other element powders are one or a combination of Fe powder, Mo powder, Cr powder, and Nb powder; and the atomic ratio of Ti:Ni:other elements in the mixture of Ti powder, Ni powder, and other element powders is 1:1:(0-0.2). Everything else is the same as in Specific Implementation Methods One to Four.

[0056] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the ball milling mixture described in step two is specifically carried out at a rotation speed of 300 r / min to 500 r / min and a ball-to-material ratio of (2 to 4):1, for 0.5 h to 6 h. Everything else is the same as in Specific Implementation Methods One to Five.

[0057] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the protective atmosphere described in step three ② is a mixture of Ar and H2, or the protective atmosphere is one or a mixture of Ar, N2, and He. Everything else is the same as in Specific Implementation Methods One to Six.

[0058] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: in step three ②, the pre-compressed mixture is heated to 1100℃ to 1300℃ under vacuum or a protective atmosphere at a heating rate of 100℃ / min to 200℃ / min. Everything else is the same as in Specific Implementation Methods One to Seven.

[0059] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the concentration of the dilute hydrochloric acid mentioned in step four ① is 0.005 mol / L to 1 mol / L. Everything else is the same as in Specific Implementation Methods One to Eight.

[0060] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that the cleaning and drying described in step four ② is specifically performed as follows: cleaning with deionized water and ethanol in sequence, followed by drying at a temperature of 25℃~80℃. Everything else is the same as in Specific Implementation Methods One to Nine.

[0061] The beneficial effects of the present invention are verified using the following embodiments:

[0062] Example 1:

[0063] A method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode comprises the following steps:

[0064] I. Pretreatment with sodium aluminate pore-forming agent:

[0065] ① The sodium aluminate powder is pressed into blocks, and then sintered at high temperature for 4 hours in an air atmosphere and at a temperature of 1500℃. Finally, it is cooled in the furnace and taken out to obtain sintered sodium aluminate blocks.

[0066] ② Grind and sieve the sintered sodium aluminate blocks to obtain sodium aluminate microparticles;

[0067] The particle size of the sodium aluminate microparticles is 150 μm to 300 μm;

[0068] II. Ball milling and mixing:

[0069] Sodium aluminate microparticles and metal powder were ball-milled and mixed for 2 hours at a rotation speed of 300 r / min and a ball-to-material ratio of 2:1 to obtain a mixture.

[0070] The particle size of the metal powder is 10μm to 50μm; the volume ratio of sodium aluminate particles to metal powder is 1:1; the metal powder is TiNi alloy powder; the atomic ratio of Ti:Ni in the TiNi alloy powder is 1:1.

[0071] III. Preparation of porous TiNi-based alloys:

[0072] ① The mixture is placed in a graphite mold in a discharge plasma sintering furnace and pre-pressed for 5 minutes under a pressure of 30 MPa to obtain the pre-pressed mixture;

[0073] ② Under vacuum, the pre-compressed mixture is heated to 1200℃ at a heating rate of 120℃ / min, and held at 1200℃ for 10 min. Finally, it is cooled in the furnace to obtain TiNi-based alloy blocks.

[0074] ③ Use sandpaper to polish the TiNi-based alloy block until the metallic luster is exposed to obtain the precursor;

[0075] IV. Composite of the catalytic active layer:

[0076] ① The precursor was immersed in dilute hydrochloric acid and then placed in a high-frequency ultrasonic transducer. The reaction was carried out under the condition of 10kHz for 15 minutes to obtain a precursor with a surface covered with catalytically active material.

[0077] The concentration of the dilute hydrochloric acid is 0.1 mol / L;

[0078] ②The precursor covered with catalytic active material on the surface was cleaned sequentially with deionized water and ethanol, and then dried at a temperature of 60℃ to obtain a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode.

[0079] Figure 1The image shows the microstructure of the precursor prepared in step 3③ of Example 1. As can be seen from the image, the precursor surface has a pore structure with a pore size of about 200μm to 300μm. The pores contain sodium aluminate as a pore-forming agent, and the relatively flat morphology outside the pores is a TiNi alloy.

[0080] Figure 2 The image shows the microstructure of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1. As can be seen from the image, the catalyst layer on the electrode surface exhibits a bulk morphology without obvious nanoscale features. The electrode surface displays a porous structure because the sodium aluminate on the surface dissolves in the solution, exposing the pore structure of the TiNi alloy surface. The pore size is approximately 200 μm to 400 μm. This porous structure provides the electrode with a larger specific surface area, offering more active sites for the hydrogen evolution reaction (HER), thereby improving the catalytic performance of the HER. Furthermore, when the TiNi alloy and sodium aluminate composite material is placed in a dilute hydrochloric acid solution, the sodium aluminate in the pores dissolves in the solution and reacts with the TiNi alloy along with the hydrochloric acid, forming a catalyst layer on the surface. Since there is no large amount of TiNi element in the pores, the generated active material is less than that in the TiNi alloy planar portion. Therefore, the catalytically active material at the original pore location is less than that in the TiNi alloy planar portion, while still maintaining a certain porosity.

[0081] Figure 3 The image shows the X-ray diffraction pattern of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1. As can be seen from the image, the surface catalyst layer of the TiNi alloy-based porous composite electrocatalytic electrode consists of Ti4Ni2O... 0.3 Ti4Ni2O 0.6 It is composed of intermetallic compounds such as Ni3Ti, which all exhibit excellent electrical conductivity, providing a solid foundation for the electrode's outstanding hydrogen evolution catalytic activity.

[0082] In a three-electrode testing system using a carbon rod as the counter electrode and a 1 mol / L KOH solution as the electrolyte, the hydrogen evolution reaction (HER) was performed on the electrocatalytic electrode.

[0083] Figure 4 The figure shows the electrochemical active area of ​​the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 and a commercial TiNi alloy. As shown in the figure, the electrochemical active area of ​​the TiNi alloy-based porous composite electrocatalytic electrode is 15.37 mF / cm². 2 The electrochemically active surface area of ​​commercially available TiNi alloys is 0.11 mF / cm². 2 Due to the presence of the porous structure, the electrochemical active area of ​​the TiNi alloy-based porous composite electrocatalytic electrode is much higher than that of commercially available non-porous TiNi alloys.

[0084] Figure 5 The figure shows the high-efficiency and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 and the HER polarization curves of a commercial 20% Pt / C electrode. As can be seen from the figure, the TiNi alloy-based porous composite electrocatalytic electrode can achieve 10 mA / cm² speed during the hydrogen evolution reaction (HER) with only a 72 mV overpotential. 2 The current density.

[0085] Figure 6 The constant current stability test of the highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode prepared in Example 1 was conducted in 1M KOH electrolyte. The catalyst exhibited excellent long-term service stability, with its HER overpotential increasing by only 7 mV within 200 h, and its performance showing almost no significant degradation.

Claims

1. A method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode, characterized in that... It is done in the following steps: I. Pretreatment with sodium aluminate pore-forming agent: ① The sodium aluminate powder is pressed into blocks, then sintered at high temperature in air atmosphere, and finally cooled in the furnace and taken out to obtain sodium aluminate sintered blocks. ② Grind and sieve the sintered sodium aluminate blocks to obtain sodium aluminate microparticles; II. Ball milling and mixing: Sodium aluminate particles and metal powder were ball-milled and mixed to obtain a mixture; The particle size of the metal powder is 10μm~50μm; The metal powder is a mixture of Ti powder, Ni powder and other element powders, and the atomic ratio of Ti:Ni:other elements in the mixture of Ti powder, Ni powder and other element powders is 1:1:(0~0.2). Alternatively, the metal powder may be TiNi alloy powder, wherein the atomic ratio of Ti to Ni in the TiNi alloy powder is 1:1; III. Preparation of porous TiNi-based alloys: ① The mixture is placed in a graphite mold in a discharge plasma sintering furnace and pre-pressed for 5 min to 15 min under a pressure of 30 MPa to 50 MPa to obtain the pre-pressed mixture; ② Under vacuum or protective atmosphere, the pre-compressed mixture is heated to 1100℃~1300℃ and held at 1100℃~1300℃ for 10min~20min. Finally, it is cooled with the furnace to obtain TiNi-based alloy blocks. ③ Polish the TiNi-based alloy block until the metallic luster is exposed to obtain the precursor; IV. Composite of the catalytic active layer: ① The precursor is immersed in dilute hydrochloric acid and then placed in a high-frequency ultrasonic transducer. Under the condition of 0.01kHz~20kHz, the reaction is oscillated for 5min~20min to obtain a precursor with a surface covered with catalytically active material. ② The precursor with catalytically active material on its surface is cleaned and dried, thus completing the preparation method of a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode.

2. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... Step 1 ① Under air atmosphere and temperature of 1000℃~1500℃, sinter at high temperature for 3h~4h.

3. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The particle size of the sodium aluminate microparticles mentioned in step 1② is 100μm~300μm.

4. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The volume ratio of sodium aluminate particles to metal powder in step two is (0.5~1.1):

1.

5. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The other elemental powders mentioned are one or a combination of Fe powder, Mo powder, Cr powder and Nb powder.

6. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The ball milling mixing described in step two is specifically carried out at a rotation speed of 300 r / min to 500 r / min and a ball-to-material ratio of (2 to 4):1 for 0.5 h to 6 h.

7. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The protective atmosphere mentioned in step 3② is a mixture of Ar and H2, or the protective atmosphere is one or a mixture of Ar, N2 and He.

8. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... In step 3②, under vacuum or a protective atmosphere, the pre-compressed mixture is heated to 1100℃~1300℃ at a heating rate of 100℃ / min~200℃ / min.

9. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... The concentration of the dilute hydrochloric acid mentioned in step 4① is 0.005 mol / L to 1 mol / L.

10. The method for preparing a highly efficient and stable TiNi alloy-based porous composite electrocatalytic electrode according to claim 1, characterized in that... Step 4②, the cleaning and drying process, is carried out in the following steps: cleaning with deionized water and ethanol in sequence, and then drying at a temperature of 25℃~80℃.

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