阅读说明：本技术 多功能幂层电极材料及其制备方法 (Multifunctional power layer electrode material and preparation method thereof ) 是由 李衫衫 于庆河 米菁 郝雷 王树茂 蒋利军 刘皓 李世杰 于 2021-06-09 设计创作，主要内容包括：本发明提出一种多功能幂层电极材料,其包括基底、Ni-Mo电沉积层,该Ni-Mo电沉积层是由内、中、外三层复合而成,其中,内层颗粒尺寸小；中层为缓和层,颗粒尺寸适中；外层颗粒尺寸较大,表面凹凸不平。采用本发明设计的点沉积层解决了镀层与基底界面结合强度低的问题,能防止镀层脱落和提高耐腐性,以延长电极材料的使用寿命,降低了析氢过电位。此外,颗粒间较大的空隙也易于气体逃逸,解决了气体难以排出的难题。(The invention provides a multifunctional power layer electrode material, which comprises a substrate and a Ni-Mo electrodeposition layer, wherein the Ni-Mo electrodeposition layer is formed by compounding an inner layer, a middle layer and an outer layer, and the particle size of the inner layer is small; the middle layer is a moderation layer, and the particle size is moderate; the outer layer has larger particle size and uneven surface. The point deposition layer designed by the invention solves the problem of low bonding strength between the coating and the substrate interface, can prevent the coating from falling off and improve the corrosion resistance, so as to prolong the service life of the electrode material and reduce the hydrogen evolution overpotential. In addition, larger gaps among the particles are easy to escape, and the problem that the gas is difficult to discharge is solved.)

1. A multifunctional power layer electrode material, characterized in that: the Ni-Mo electrodeposited coating is formed by compounding an inner layer, a middle layer and an outer layer, wherein the inner layer is small in particle size; the middle layer is a moderation layer, and the particle size is moderate; the outer layer has larger particle size and uneven surface;

the electrodeposition process of the electrodeposition layer is that the current density is 0.1-5A/cm firstly²Performing electrodeposition for 10-60 min; then the current density is 5-10A/cm²Performing electrodeposition for 10-360 min; finally, the current density is 10-20A/cm²And then, carrying out electrodeposition for 10-180 min.

2. The multifunctional power layer electrode material of claim 1, wherein: the substrate may be foamed Ni, Ni mesh, Ni fiber felt.

3. The multifunctional power layer electrode material of claim 1 or 2, wherein: ni in the Ni-Mo electrodeposition layer: the mass percent of Mo is 30-90%: 10 to 70 percent.

4. A method for preparing the multifunctional power layer electrode material as claimed in any one of claims 1 to 3, comprising:

firstly, preparing a deposition solution;

secondly, pretreating a substrate;

thirdly, electrodeposition;

fourthly, post-processing;

and fifthly, performing heat treatment.

5. The method for preparing the multifunctional power layer electrode material of claim 4, wherein: the first step is to respectively prepare nickel sulfate with the concentration of 10-300 g/L, sodium molybdate with the concentration of 10-300 g/L, complexing agent with the concentration of 100-500 g/L, buffering agent with the concentration of 10-60 g/L, brightening agent with the concentration of 0.1-5 g/L, wetting agent with the concentration of 0.1-2 g/L and additive with the concentration of 0.1-2 g/L, mix and stir uniformly, adjust the pH of the solution to 3-14 by using dilute sulfuric acid or sodium hydroxide, and age for 1-3 hours.

6. The method for preparing the multifunctional power layer electrode material as claimed in claim 5, wherein: the molar ratio of the complexing agent to the sum of the metal nickel and the molybdenum ions is 1-1.5: 1.

7. The method for preparing the multifunctional power layer electrode material of claim 4, wherein: and the second step of substrate pretreatment is specifically to wash the substrate for 3-10 times respectively by using 0.1-30% dilute hydrochloric acid, deionized water and absolute ethyl alcohol, and place the substrate in a vacuum oven at 50-80 ℃ until the substrate is dried.

8. The method for preparing the multifunctional power layer electrode material of claim 4, wherein: the third step of electrodepositing the coating further specifically comprises:

step 3.1, placing the prepared deposition solution in the first step into an electrodeposition tank;

3.2, placing the anode material and the substrate of the Ni-Mo alloy plate in an electrodeposition tank, and respectively connecting the anode and the cathode, wherein the distance between the cathode and the anode is controlled to be 5-30 cm;

3.3, inserting a heating rod into a groove of the electrodeposition tank, switching on a power supply, and controlling the temperature to be 20-80 ℃;

step 3.4, inserting a bubble remover on the electrodeposition tank, switching on a power supply, and removing bubbles for 5-30 min in advance to avoid the influence of bubbles in the deposition liquid on electrodeposition;

3.5, using a direct current power supply to switch on direct current, and firstly, controlling the current density to be 0.1-5A/cm²Performing electrodeposition for 10-60 min; then the current density is 5-10A/cm²Performing electrodeposition for 10-360 min; finally, the current density is 10-20A/cm²Down, electricityDepositing for 10-180 min.

9. The method for preparing the multifunctional power layer electrode material of claim 4, wherein: and the fourth step of post-treatment is further specifically that the substrate attached with the Ni-Mo electrodeposition layer is washed by deionized water and absolute ethyl alcohol respectively and sequentially for 3-10 times, and then the substrate is placed in a vacuum oven at 50-80 ℃ until the substrate is dried.

10. The method for preparing the multifunctional power layer electrode material of claim 4, wherein: and the fifth step of heat treatment is further specifically that the post-treated electrode material obtained in the fourth step is placed into a tubular furnace, heat treatment is carried out for 1-10 hours in the tubular furnace at 400-1000 ℃ at the heating rate of 2-15 ℃/min, and then the electrode material is naturally cooled to room temperature, so that the electrode material can be obtained.

Technical Field

The invention relates to the technical field of electrode materials, in particular to a multifunctional power layer electrode material and a preparation method thereof.

Background

With the decreasing of resources and energy sources, hydrogen energy is widely concerned as a green and ideal clean energy source. The current hydrogen production approach capable of realizing large-scale and low-cost hydrogen production is to electrolyze water to produce hydrogen. However, since the conventional electrode material has high hydrogen evolution overpotential, large cell pressure and large energy consumption, research and development of an electrode material having high catalytic activity is an important means for solving the above problems.

The Ni-Mo alloy is an electrode material with good hydrogen evolution activity in a binary alloy system, but the electrocatalytic activity and the service life of the Ni-Mo alloy still need to be further improved. Compared with other preparation methods, the sample prepared by electrodeposition has controllable grain size and compact and uniform coating, and the grain size and the roughness of the coating can be adjusted by regulating and controlling the current density and the electrodeposition time, so that the effects of increasing the specific surface area, improving the mechanical property and prolonging the service life of the material are achieved. The existing electrodeposition materials have single layer, two layers and multiple layers, but the problems of separation, bulging, falling off and the like of the plating layer and the substrate are caused in the electrochemical reaction and gas escape processes because the plating layer and the substrate have low bonding strength and weak bonding force.

Compared with the existing two-layer active multilayer Ni-Mo electrodeposited layer, the point-deposited layer designed by the invention solves the problem of low bonding strength between the coating and the substrate interface, can prevent the coating from falling off and improve the corrosion resistance, so as to prolong the service life of the electrode material and reduce the hydrogen evolution overpotential. In addition, larger gaps among the particles are easy to escape, and the problem that the gas is difficult to discharge is solved.

Disclosure of Invention

The invention aims to provide a multifunctional power layer electrode material, which solves the problem of low bonding strength between a plating layer and a substrate interface in the prior art, can prevent the plating layer from falling off and improve corrosion resistance, so as to prolong the service life of the electrode material and reduce hydrogen evolution overpotential. In addition, the multifunctional power layer electrode provided by the invention has the advantages that larger gaps among material particles are easy to escape, and the problem that gas is difficult to discharge is solved.

In order to solve the technical problems, the invention provides a multifunctional power layer electrode material which comprises a substrate and a Ni-Mo electrodeposition layer, wherein the Ni-Mo electrodeposition layer is formed by compounding an inner layer, a middle layer and an outer layer, and the particle size of the inner layer is small; the middle layer is a moderation layer, and the particle size is moderate; the outer layer has larger particle size and uneven surface;

the electrodeposition process of the electrodeposition layer is that the current density is 0.1-5A/cm firstly²Performing electrodeposition for 10-60 min; then the current density is 5-10A/cm²Performing electrodeposition for 10-360 min; finally, the current density is 10-20A/cm²And then, carrying out electrodeposition for 10-180 min.

Wherein, the substrate can be foamed Ni, Ni net, Ni fiber felt and the like.

Wherein, Ni in the Ni-Mo electrodeposition layer: the mass percent of Mo is 30-90%: 10 to 70 percent.

The invention also provides a preparation method of the multifunctional power layer electrode material, which comprises the following steps:

firstly, preparing a deposition solution;

secondly, pretreating a substrate;

thirdly, electrodeposition;

fourthly, post-processing;

and fifthly, performing heat treatment.

The first step is to respectively prepare nickel sulfate with the concentration of 10-300 g/L, sodium molybdate with the concentration of 10-300 g/L, complexing agent with the concentration of 100-500 g/L, buffering agent with the concentration of 10-60 g/L, brightener with the concentration of 0.1-5 g/L, wetting agent with the concentration of 0.1-2 g/L and additive with the concentration of 0.1-2 g/L, mix and stir uniformly, adjust the pH of the solution to 3-14 by using dilute sulfuric acid or sodium hydroxide, and age for 1-3 hours.

Wherein the molar ratio of the complexing agent to the sum of the metal nickel and the molybdenum ions is 1-1.5: 1.

And the second step of substrate pretreatment is to wash the substrate for 3-10 times by using 0.1-30% diluted hydrochloric acid, deionized water and absolute ethyl alcohol respectively, and place the substrate in a vacuum oven at 50-80 ℃ until the substrate is dried.

Wherein the third step of electrodepositing further comprises:

step 3.1, placing the prepared deposition solution in the first step into an electrodeposition tank;

3.2, placing the anode material and the substrate of the Ni-Mo alloy plate in an electrodeposition tank, and respectively connecting the anode and the cathode, wherein the distance between the cathode and the anode is controlled to be 5-30 cm;

3.3, inserting a heating rod into a groove of the electrodeposition tank, switching on a power supply, and controlling the temperature to be 20-80 ℃;

step 3.4, inserting a bubble remover on the electrodeposition tank, switching on a power supply, and removing bubbles for 5-30 min in advance to avoid the influence of bubbles in the deposition liquid on electrodeposition;

3.5, using a direct current power supply to switch on direct current, and firstly, controlling the current density to be 0.1-5A/cm²Performing electrodeposition for 10-60 min; then the current density is 5-10A/cm²Performing electrodeposition for 10-360 min; finally, the current density is 10-20A/cm²And then, carrying out electrodeposition for 10-180 min.

And the fourth step of post-treatment is further specifically that the substrate attached with the Ni-Mo electrodeposition layer is washed by deionized water and absolute ethyl alcohol for 3-10 times respectively, and then placed in a vacuum oven at 50-80 ℃ until being dried.

And the fifth step of heat treatment is further specifically that the post-treated electrode material obtained in the fourth step is placed into a tubular furnace, heat treatment is carried out for 1-10 hours in the tubular furnace at 400-1000 ℃ at the heating rate of 2-15 ℃/min, and then the electrode material is naturally cooled to room temperature, so that the electrode material can be obtained.

The invention has the advantages of

Compared with other alloy plating layers, the Ni-Mo electrodeposition layer in the electrode material has wear resistance, corrosion resistance and stability; the plating solution has low toxicity and low pollution degree to water source and atmosphere.

In addition, the invention realizes that the Ni-Mo electro-deposition layer is composed of three electro-deposition layers through a special electro-deposition process, and the functions of the Ni-Mo electro-deposition layer are respectively as follows:

(1) under the condition of lower current density, the particle size of the electrodeposition layer is small, and the bonding force between the electrodeposition layer and the substrate is large, so that the problem of low bonding strength of the interface of the plating layer and the substrate is solved;

(2) under the medium current density, the electric deposition layer is used as an intermediate relaxation layer, which can prevent the coating from falling off and improve the corrosion resistance so as to prolong the service life of the electrode material;

(3) under higher current density, electrodeposition is carried out to increase the particle size and form an uneven surface so as to improve the specific surface area of the material and provide more catalytic active sites for the water electrolysis reaction, thereby reducing the hydrogen evolution overpotential. In addition, larger gaps among the particles are easy to escape, and the problem that the gas is difficult to discharge is solved.

Drawings

FIG. 1 is a schematic diagram of a foamed Ni-based electrodeposited Ni-Mo multifunctional power layer electrode material;

FIG. 2 is a schematic diagram of an electrode material of a Ni-Mo multifunctional power layer electrodeposited on a Ni net base;

FIG. 3 is a schematic diagram of an electrode material of a Ni-Mo multifunctional power layer electrodeposited on a Ni fiber felt base.

Detailed Description

In order to solve the technical problems, the invention provides a multifunctional power layer electrode material which comprises a substrate and a Ni-Mo electrodeposition layer, wherein the Ni-Mo electrodeposition layer is formed by compounding an inner layer, a middle layer and an outer layer, and the particle size of the inner layer is small; the middle layer is a moderation layer, and the particle size is moderate; the outer layer has larger particle size and uneven surface, and the specific surface area of the material is increased.

According to the invention, the electrodeposition layers with different particle sizes are prepared under low, medium and high current densities, so that the particle size of the inner layer is small and is 5-50 nm; the middle layer has moderate particle size of 50-100 nm; the outer layer has larger particle size of 100-500 nm and uneven surface.

The substrate may be foamed Ni, Ni mesh, Ni fiber felt, or the like.

The Ni-Mo electrodeposition layer is composed of three electrodeposition layers, wherein Ni: the mass percent of Mo is 30-90%: 10 to 70 percent.

The invention also provides a preparation method of the multifunctional power layer electrode material, which comprises the following steps:

firstly, preparing a deposition solution;

secondly, pretreating a substrate;

thirdly, electrodeposition;

fourthly, post-processing;

and fifthly, performing heat treatment.

The first step is to respectively prepare nickel sulfate with the concentration of 10-300 g/L, sodium molybdate with the concentration of 10-300 g/L, complexing agent with the concentration of 100-500 g/L, buffering agent with the concentration of 10-60 g/L, brightening agent with the concentration of 0.1-5 g/L, wetting agent with the concentration of 0.1-2 g/L and additive with the concentration of 0.1-2 g/L, mix and stir uniformly, adjust the pH of the solution to 3-14 by using dilute sulfuric acid or sodium hydroxide, and age for 1-3 hours.

Wherein the mol ratio of the complexing agent to the sum of the metal nickel and the molybdenum ions is preferably 1-1.5: 1.

The complexing agent may be citric acid or a citrate salt.

The buffer may be an ammonium salt or an acetate salt.

The brightener is preferably gelatin.

The wetting agent is preferably a lauryl sulfate or sulfonate.

The additive is preferably rare earth chloride or rare earth sulfate, has excellent physical properties such as photoelectromagnetism and the like, can form novel materials with different performances and various varieties with other materials after being added, improves the conductivity, and reduces the hydrogen evolution overpotential of the materials.

And the second step of substrate pretreatment is specifically to wash the substrate for 3-10 times respectively by using 0.1-30% dilute hydrochloric acid, deionized water and absolute ethyl alcohol, and place the substrate in a vacuum oven at 50-80 ℃ until the substrate is dried.

The third step of electrodepositing the coating further specifically comprises:

step 3.1, placing the prepared deposition solution in the first step into an electrodeposition tank;

3.2, placing the anode material and the substrate of the Ni-Mo alloy plate in an electrodeposition tank, and respectively connecting the anode and the cathode, wherein the distance between the cathode and the anode is controlled to be 5-30 cm;

3.3, inserting a heating rod into a groove of the electrodeposition tank, switching on a power supply, and controlling the temperature to be 20-80 ℃;

step 3.4, inserting a bubble remover on the electrodeposition tank, switching on a power supply, and removing bubbles for 5-30 min in advance to avoid the influence of bubbles in the deposition liquid on electrodeposition;

3.5, using a direct current power supply to switch on direct current, and firstly, controlling the current density to be 0.1-5A/cm²Performing electrodeposition for 10-60 min; then the current density is 5-10A/cm²Performing electrodeposition for 10-360 min; finally, the current density is 10-20A/cm²And then, carrying out electrodeposition for 10-180 min.

And the fourth step of post-treatment is further specifically that the substrate attached with the Ni-Mo electrodeposition layer is washed by deionized water and absolute ethyl alcohol respectively and sequentially for 3-10 times, and then the substrate is placed in a vacuum oven at 50-80 ℃ until the substrate is dried.

And the fifth step of heat treatment is further specifically that the post-treated electrode material obtained in the fourth step is placed into a tubular furnace, heat treatment is carried out for 1-10 hours in the tubular furnace at 400-1000 ℃ at the heating rate of 2-15 ℃/min, and then the electrode material is naturally cooled to room temperature, so that the electrode material can be obtained.

The following embodiments are described in detail to solve the technical problems by applying technical means to the present invention, and the implementation process of achieving the technical effects can be fully understood and implemented.

Example 1 preparation of foamed Ni-based electrodeposited Ni-Mo multifunctional power layer electrode Material

(1) Preparing nickel sulfate, sodium molybdate, complexing agent citric acid, buffering agent ammonium bicarbonate, brightening agent (gelatin), wetting agent sodium dodecyl sulfate and additive rare earth sodium chloride, wherein the concentrations of the complexing agent and the additive rare earth sodium chloride are respectively 120g/L, 40g/L, 300g/L, 15g/L, 2g/L, 1g/L and 1g/L, the mole fraction of the complexing agent and metal ions is controlled to be 1.3:1, the pH of the solution is adjusted to be 9 by using dilute sulfuric acid or sodium hydroxide, and aging is carried out for 2 hours;

(2) placing the prepared deposition solution in an electrodeposition tank;

(3) sequentially washing a substrate (foamed Ni, a Ni net and a Ni fiber felt) for 5 times by using 15% dilute hydrochloric acid, deionized water and absolute ethyl alcohol, and then placing the substrate in a vacuum oven at 60 ℃ until the substrate is dried;

(4) putting the cleaned substrate into the prepared deposition solution, then respectively connecting the substrate (foamed Ni, Ni net and Ni fiber felt) and a Ni-Mo (Ni: Mo 70%: 30%) alloy plate with a cathode electrode clamp and an anode electrode clamp, and controlling the distance between the cathode plate and the anode plate to be 8 cm;

(5) inserting a heating rod into a groove of the electro-deposition tank, switching on a power supply, and controlling the temperature to be 60 ℃;

(6) inserting a bubble remover on the electro-deposition tank, switching on a power supply, and removing bubbles for 10min in advance to avoid the influence of bubbles in the deposition liquid on electro-deposition;

(7) using a DC power supply to switch on DC power supply, and controlling the current density to be 1A/cm²Then, electrodepositing for 15 min; then the current density is 5A/cm²Performing electrodeposition for 30 min; finally, the current density is 12A/cm²Performing electrodeposition for 20 min;

(8) after the electrodeposition is finished, the substrate with the plating layer is washed for 5 times by deionized water and absolute ethyl alcohol respectively, and then is placed in a vacuum oven at 60 ℃ until being dried.

(9) And (3) carrying out heat treatment in a tube furnace at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the electrode material.

Example 2 preparation of Ni mesh-based electrodeposited Ni-Mo multifunctional power layer electrode Material

(1) Preparing nickel sulfate, sodium molybdate, complexing agent citric acid, buffering agent ammonium bicarbonate, brightening agent gelatin, wetting agent sodium dodecyl sulfate and additive rare earth sodium chloride, wherein the concentrations of the complexing agent and the additive rare earth sodium chloride are respectively 120g/L, 40g/L, 300g/L, 15g/L, 2g/L, 1g/L and 1g/L, the mole fraction of the complexing agent and metal ions is controlled to be 1.3:1, the pH of the solution is adjusted to be 9 by using dilute sulfuric acid or sodium hydroxide, and aging is carried out for 2 hours;

(2) placing the prepared deposition solution in an electrodeposition tank;

(3) sequentially washing a substrate (foamed Ni, a Ni net and a Ni fiber felt) for 5 times by using 15% dilute hydrochloric acid, deionized water and absolute ethyl alcohol, and then placing the substrate in a vacuum oven at 60 ℃ until the substrate is dried;

(4) putting the cleaned substrate into the prepared deposition solution, then respectively connecting the substrate (foamed Ni, Ni net and Ni fiber felt) and a Ni-Mo (Ni: Mo 70%: 30%) alloy plate with a cathode electrode clamp and an anode electrode clamp, and controlling the distance between the cathode plate and the anode plate to be 8 cm;

(5) inserting a heating rod into a groove of the electro-deposition tank, switching on a power supply, and controlling the temperature to be 60 ℃;

(6) inserting a bubble remover on the electro-deposition tank, switching on a power supply, and removing bubbles for 10min in advance to avoid the influence of bubbles in the deposition liquid on electro-deposition;

(7) using a DC power supply to switch on DC power supply, and controlling the current density to be 1A/cm²Then, electrodepositing for 15 min; then the current density is 5A/cm²Performing electrodeposition for 30 min; finally, the current density is 12A/cm²Performing electrodeposition for 20 min;

(8) after the electrodeposition is finished, the substrate with the plating layer is washed for 5 times by deionized water and absolute ethyl alcohol respectively, and then is placed in a vacuum oven at 60 ℃ until being dried.

(9) And (3) carrying out heat treatment in a tube furnace at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the electrode material.

Example 3 preparation of Ni fiber felt-based electrodeposited Ni-Mo multifunctional power layer electrode material

(1) Preparing nickel sulfate, sodium molybdate, complexing agent citric acid, buffering agent ammonium bicarbonate, brightening agent gelatin, wetting agent sodium dodecyl sulfate and additive rare earth sodium chloride, wherein the concentrations of the complexing agent and the additive rare earth sodium chloride are respectively 120g/L, 40g/L, 300g/L, 15g/L, 2g/L, 1g/L and 1g/L, the mole fraction of the complexing agent and metal ions is controlled to be 1.3:1, the pH of the solution is adjusted to be 9 by using dilute sulfuric acid or sodium hydroxide, and aging is carried out for 2 hours;

(2) placing the prepared deposition solution in an electrodeposition tank;

(3) sequentially washing a substrate (foamed Ni, a Ni net and a Ni fiber felt) for 5 times by using 15% dilute hydrochloric acid, deionized water and absolute ethyl alcohol, and then placing the substrate in a vacuum oven at 60 ℃ until the substrate is dried;

(4) putting the cleaned substrate into a deposition tank filled with deposition liquid, and then respectively connecting the substrate (foamed Ni, Ni net and Ni fiber felt) and a Ni-Mo (Ni: Mo 70%: 30%) alloy plate with a cathode electrode clamp and an anode electrode clamp, and controlling the distance between the cathode plate and the anode plate to be 8 cm;

(5) inserting a heating rod into a groove of the deposition groove, switching on a power supply, and controlling the temperature to be 60 ℃;

(6) inserting a bubble remover on the electro-deposition tank, switching on a power supply, and removing bubbles for 10min in advance to avoid the influence of bubbles in the deposition liquid on electro-deposition;

(7) using a DC power supply to switch on DC power supply, and controlling the current density to be 1A/cm²Then, electrodepositing for 15 min; then the current density is 5A/cm²Performing electrodeposition for 30 min; finally, the current density is 12A/cm²Performing electrodeposition for 20 min;

(8) after the electrodeposition is finished, the substrate with the plating layer is washed for 5 times by deionized water and absolute ethyl alcohol respectively, and then is placed in a vacuum oven at 60 ℃ until being dried.

(9) And (3) carrying out heat treatment in a tube furnace at 500 ℃ for 2h at the heating rate of 5 ℃/min, and then naturally cooling to room temperature to obtain the electrode material.

All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.

The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.