Method for preparing nanocrystalline nickel foil through electro-deposition method and nanocrystalline nickel foil prepared through method

Abstract

According to the method for preparing the nanocrystalline nickel foil through the electro-deposition method and the nanocrystalline nickel foil prepared through the method, a nickel plate serves as an anode, a titanium plate serves as a cathode, the anode and the cathode are both placed in electrolyte, and the nanocrystalline nickel foil is prepared on the titanium plate through electro-deposition by adopting a pulse power source; the electrolyte comprises water and the following components by concentration: 300-500g / L of nickel sulfate; 5-15 g / L of nickel chloride; 0.01 to 0.2 g / L of a wetting agent; 20-60 g / L of a buffer agent; 0.05-2 g / L of a brightener; the pH value of the electrolyte is 2-4, and the electro-deposition temperature is 40-60 DEG C; the buffering agent is selected from one or two of citric acid and sodium citrate; and the brightener is selected from one or more of butynediol propoxide, butynediol ethoxylate, sodium sulfopropyne ether, propynol ethoxylate and glycerol monopropyne ether. Based on the method, the problem that in the prior art, the nickel foil prepared through an electro-deposition method is large in fine grain size is solved.

Description

Technical Field

[0001] The invention relates to the field of electrochemical deposition, and in particular to a method for preparing nanocrystalline nickel foil by electrochemical deposition and the prepared nanocrystalline nickel foil. Background Art

[0002] Nanomaterials exhibit many unique properties in chemistry, electromagnetism, optics, catalysis, etc., which give them a broad development and application prospect in the corresponding fields. In order to prepare nanomaterials with uniform grain size, stable structure, high purity and low porosity, research on their preparation methods has always attracted attention. At present, the synthesis and preparation methods of nanocrystalline metal materials are mainly divided into: precipitation method, sol-gel method, condensation method, amorphous initial crystallization method, gas evaporation method, electrodeposition, chemical plating, etc. Nickel foil is a raw material used in electronics, telecommunications, instrumentation and other industries. In recent years, the demand for thin nickel foil has increased day by day, and the scope of application has become wider and wider, but the nickel foil currently prepared by electrodeposition. The electrodeposition method makes nickel foil become material through electrodeposition in one time, with short process, high yield and low cost, which is particularly suitable for the production of thin foil. However, in the prior art, the nickel foil prepared by electrodeposition has a large fine grain size, and it is difficult to prepare nanocrystalline nickel foil with small grains and high density. Summary of the invention

[0003] The main purpose of the present invention is to provide a method for preparing nanocrystalline nickel foil by electrodeposition and the prepared nanocrystalline nickel foil, so as to solve the problem that the grain size of nickel foil prepared by electrodeposition in the prior art is too large.

[0004] In order to achieve the above object, the present invention provides a method for preparing nanocrystalline nickel foil by electrodeposition, wherein a nickel plate is used as an anode and a titanium plate is used as a cathode, the anode and the cathode are both placed in an electrolyte, and a pulse power supply is used to electrodeposit the nanocrystalline nickel foil on the titanium plate;

[0005] The electrolyte contains water and the following components in the following concentrations:

[0006] Nickel sulfate 300~500g / L;

[0007] Nickel chloride 5-15 g / L;

[0008] Wetting agent 0.01~0.2g / L;

[0009] Buffer 20~60g / L;

[0010] Brightener 0.05~2g / L;

[0011] The pH of the electrolyte is 2 to 4, and the temperature of electrodeposition is 40 to 60°C;

[0012] The buffer is selected from one or both of citric acid and sodium citrate;

[0013] The brightener is selected from one or more of propoxylated butynediol, ethoxylated butynediol, sulfopropargyl ether sodium salt, ethoxylated propargyl alcohol, and glycerol monopropargyl ether;

[0014] The wetting agent is selected from one or more of 2-ethylhexyl sodium sulfate, polyoxyethylene alkylphenol ether sulfate sodium salt, sulfosuccinate sodium salt, dipentyl sulfosuccinate sodium salt, and diethyl sulfosuccinate sodium salt.

[0015] Further, the wetting agent is selected from one or both of polyoxyethylene alkylphenol ether sodium sulfate and 2-ethylhexyl sodium sulfate;

[0016] Preferably, the concentration of the wetting agent is 0.03-0.1 g / L.

[0017] Furthermore, the brightener is selected from one or both of propoxylated butynediol and ethoxylated butynediol.

[0018] Preferably, the concentration of the brightener is 0.5-1 g / L.

[0019] Furthermore, the cathode current density is 1 to 4 A / dm 2 , the pulse period is 30ms~60ms, and the duty cycle is (1~3):1.

[0020] Furthermore, the pH of the electrolyte is adjusted by first mixing the components according to the formula, and then adding Na2CO3 powder and / or acidic aqueous solution to adjust the pH of the mixed system.

[0021] Furthermore, the acidic substances in the acidic aqueous solution are H2SO4 and HCl, and the molar ratio of H2SO4 and HCl is (6-8):1.

[0022] Furthermore, the distance between the anode and cathode is 5 to 20 mm;

[0023] Preferably, the distance between the two poles is 10-20 mm.

[0024] Further, the electrodeposition time is 1 to 5 h;

[0025] Preferably, the electrodeposition time is 2 to 3 hours;

[0026] Preferably, the titanium plate after electrodeposition is taken out from the electrolyte, and then washed and dried in sequence, and then the nickel metal layer formed after deposition is peeled off to obtain nanocrystalline nickel foil.

[0027] Furthermore, the nickel plate is in the form of a basket, including a metal basket and nickel metal waste filled in the metal basket.

[0028] According to another aspect of the present invention, there is provided a nanocrystalline nickel foil prepared by the above method for preparing the nanocrystalline nickel foil by electrodeposition.

[0029] Preferably, the average particle size of nanocrystals in the nanocrystalline nickel foil is 20 to 80 nm.

[0030] By applying the technical solution of the present invention, pulse electrodeposition and specific electrolyte components and concentrations are used, the grain size can be significantly refined, and small and uniform grains are generated. The prepared deposited layer has high purity and density, which is beneficial to improving the brightness and flatness of the nanocrystalline nickel foil, and can reduce the adsorption and precipitation of hydrogen during the deposition process, reduce the occurrence of hydrogen embrittlement, and make the nanocrystalline nickel foil have excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0032] Figure 1 The surface morphology of the nanocrystalline nickel foil prepared in Example 1 is shown;

[0033] Figure 2 The surface morphology of the nickel metal layer after electrolysis in Comparative Example 2 is shown;

[0034] Figure 3 The surface morphology of the nanocrystalline nickel foil prepared in Comparative Example 3 is shown;

[0035] Figure 4 The TEM image of the nanocrystalline nickel foil prepared in Example 4 is shown. DETAILED DESCRIPTION

[0036] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0037] The present invention provides a method for preparing nanocrystalline nickel foil by electrodeposition, wherein a nickel plate is used as an anode and a titanium plate is used as a cathode, the anode and the cathode are both placed in an electrolyte, and a pulse power supply is used to electrodeposit the nanocrystalline nickel foil on the titanium plate;

[0038] The electrolyte contains water and the following components in the following concentrations:

[0039] Nickel sulfate 300~500g / L;

[0040] Nickel chloride 5-15 g / L;

[0041] Wetting agent 0.01~0.2g / L;

[0042] Buffer 20~60g / L;

[0043] Brightener 0.05~2g / L;

[0044] The pH of the electrolyte is 2 to 4, and the temperature of electrodeposition is 40 to 60°C;

[0045] The buffer is selected from one or both of citric acid and sodium citrate;

[0046] The brightener is selected from one or more of propoxylated butynediol, ethoxylated butynediol, sulfopropargyl ether sodium salt, ethoxylated propargyl alcohol, and glycerol monopropargyl ether;

[0047] The wetting agent is selected from one or more of 2-ethylhexyl sodium sulfate, polyoxyethylene alkylphenol ether sulfate sodium salt, sulfosuccinate sodium salt, dipentyl sulfosuccinate sodium salt, and diethyl sulfosuccinate sodium salt.

[0048] By applying the technical solution of the present invention, pulse electrodeposition and specific electrolyte components and concentrations are used, the grain size can be significantly refined, and small and uniform grains are generated. The prepared deposited layer has high purity and density, which is beneficial to improving the brightness and flatness of the nanocrystalline nickel foil, and can reduce the adsorption and precipitation of hydrogen during the deposition process, reduce the occurrence of hydrogen embrittlement, and make the nanocrystalline nickel foil have excellent mechanical properties.

[0049] Nanocrystalline nickel foil is prepared by pulse electrodeposition technology. The current in the electrodeposition process is periodically changed, that is, in the "power-on" stage, metal ions are deposited on the cathode under the action of the electric field, and in the "power-off" stage, the metal ions in the electrolyte are allowed to diffuse and replenish near the cathode surface, thereby effectively reducing the concentration polarization phenomenon, promoting the growth of small and uniform grains, avoiding hydrogen embrittlement, and improving the purity and density of the deposited layer. The electrolyte formula uses 300-500g / L nickel sulfate as a nickel source to provide nickel ions required for electrodeposition. The exchange current density of nickel is small. When nickel is used as an anode, anode passivation is easy to occur at a higher current density. The electrolyte formula uses 5-15g / L nickel chloride, which can increase the activity of the nickel anode and promote its dissolution during the electrodeposition process. Specifically, chloride ions can react with the oxide layer formed on the surface of the nickel anode, destroy the stability of the oxide layer, accelerate the dissolution process of the anode, ensure the continuous supply of nickel ions in the electrolyte, increase the dissolution of the nickel anode during the electrodeposition process, ensure the continuous supply of nickel ions in the electrolyte, and use the above concentration of nickel chloride to facilitate continuous deposition to form a uniform deposition layer. The electrolyte formula uses 0.01-0.2g / L of the above wetting agent. The above concentration of wetting agent can improve the wettability of the electrode surface, promote the uniform precipitation of nickel ions on the cathode surface, reduce defects in deposition, such as pinholes and cracks, and improve the uniformity, density and overall quality of the deposition layer. The electrolyte formula uses 20-60g / L buffer, and the buffer uses citric acid and / or sodium citrate, which can effectively inhibit the rapid increase in pH caused by the precipitation of nickel near the cathode, ensure the stability of the electrodeposition process, and facilitate uniform metal deposition. The addition of the above-mentioned brightener can not only promote uniform metal deposition, improve the brightness and flatness of the coating, but also help to refine the grain size, form small and uniform grains, and reduce the adsorption and precipitation of hydrogen during the deposition process, which is conducive to avoiding hydrogen embrittlement, thereby improving the purity, density and mechanical properties of the deposited layer. In addition, the use of nickel plates as anodes basically does not consume electrolytes, and there is no need to replenish the electrolytes later. Only the nickel plates need to be replaced to continue electrolysis, which is simple in process and low in cost.

[0050] In some embodiments, the wetting agent is selected from one or two of polyoxyethylene alkylphenol ether sodium sulfate and 2-ethylhexyl sodium sulfate. Polyoxyethylene alkylphenol ether sodium sulfate increases its spreading ability on the interface due to its polyoxyethylene chain structure, thereby improving its wetting effect, which is beneficial to the uniform precipitation of nickel ions, reduces the generation of pinholes, has good biodegradability, and has less environmental impact; 2-ethylhexyl sodium sulfate has a good wetting effect, and also has emulsifying and dispersing effects, which is beneficial to the uniform precipitation of nickel ions, and has good chemical stability and is environmentally friendly; the use of the above wetting agent is beneficial to the uniform precipitation of nickel ions on the cathode surface, reduces the generation of pinholes, and has good compatibility when used in combination with brighteners such as propoxylated butynediol, which helps to refine the grain size, form fine and uniform grains, and improve its mechanical strength; the preferred concentration of the wetting agent is 0.03-0.1 g / L, which is beneficial to promote the uniform precipitation of nickel ions on the cathode surface and reduce costs.

[0051] In some embodiments, the brightener is selected from one or two of propoxylated butynediol and ethoxylated butynediol. The addition of brighteners such as propoxylated butynediol and ethoxylated butynediol can not only provide higher brightness, form a smoother and more uniform nickel foil surface, reduce surface defects and irregularities, and improve density and mechanical properties, but also effectively reduce the adhesion of bubbles on the electrode surface, making it easier for bubbles to detach from the electrode, thereby reducing resistance during electrolysis, improving the current efficiency of the electrolysis process, reducing energy consumption during the electrolysis process, and reducing production costs; preferably, the concentration of the brightener is 0.5-1 g / L, which is conducive to obtaining finer and more uniform grains and reducing costs.

[0052] In some embodiments, the cathode current density is 1 to 4 A / dm 2 , the pulse period is 30ms~60ms, and the duty cycle is (1~3):1. The current parameters in pulse electrodeposition affect grain growth and deposition quality. For example, the electrodeposition speed can be optimized by adjusting the current density, and the deposition conditions can be optimized by adjusting the pulse period and duty cycle, reducing impurity adsorption, and promoting grain refinement and uniform growth. The use of the above-mentioned cathode current density, pulse period and duty cycle is conducive to controlling the growth rate and size of the grains, thereby preparing nanocrystalline nickel foil with finer grains and more uniform structure. In addition, the use of the above-mentioned cathode current density, pulse period and duty cycle can better avoid concentration polarization and hydrogen embrittlement, and improve the purity and density of the material.

[0053] In some embodiments, the pH of the electrolyte is adjusted by: firstly mixing the components according to the formula, and then adding Na2CO3 powder and / or acidic aqueous solution to adjust the pH of the mixed system. Na2CO3 has weak alkalinity and can form a buffer system to resist the influence of external acidic and alkaline substances. It can accurately control the pH value and maintain the stability of the pH value of the solution. When reacting with acid, it mainly produces water and carbon dioxide without toxic byproducts. Preferably, the acidic substances in the acidic aqueous solution are H2SO4 and HCl, and the molar ratio of H2SO4 and HCl is (6 to 8): 1. The pH value affects the existence state and deposition efficiency of metal ions in the electrolyte. By adding Na2CO3 powder or acidic aqueous solution (wherein the molar ratio of H2SO4 and HCl is 6 to 8: 1), the pH value of the electrolyte is adjusted between 2 and 4, which is conducive to reducing the introduction of impurities and maintaining the stability of the initial ion concentrations in the electrolyte system and the stability of the electrolysis process.

[0054] In some embodiments, the distance between the anode and cathode electrodes is 5 to 20 mm. Adjustment of the electrode distance can improve the uniformity of current distribution in the electrolyte, facilitate uniform deposition of the deposition layer, and obtain nanocrystalline nickel foil with uniform grain distribution; preferably, the distance between the electrodes is 10 to 20 mm.

[0055] In some embodiments, the electrodeposition time is 1 to 5 hours, which is conducive to obtaining a bright, flat, complete, pinhole-free nanocrystalline nickel foil with high mechanical properties, and can reduce energy consumption and production cycle; preferably, the electrodeposition time is 2 to 3 hours; preferably, the titanium plate after electrodeposition is taken out from the electrolyte, and then cleaned and dried in sequence, and the nickel metal layer formed after deposition is stripped to obtain a nanocrystalline nickel foil, and the residual electrolyte on the surface is removed by cleaning, and the moisture is removed by drying, and finally an independent nanocrystalline nickel foil is stripped to facilitate further processing and application.

[0056] In some embodiments, the nickel plate is in the form of a basket, including a metal basket and nickel metal waste filled in the metal basket. The metal basket is generally made of an insoluble precious metal, such as platinum rhodium, rhodium iridium, or one of platinum rhodium iridium precious metals. Therefore, the waste or scraps of the nickel plate can be reused as an anode material for electrodeposition, which can not only continuously supply nickel ions in the electrolyte to ensure the continuous electrodeposition process, but also achieve the recycling of resources and effective control of costs.

[0057] According to another aspect of the present invention, a nanocrystalline nickel foil prepared by the method for preparing nanocrystalline nickel foil by electrodeposition as described above is provided; preferably, the average particle size of the nanocrystals in the nanocrystalline nickel foil is 20 to 80 nm. The above-mentioned nanocrystalline nickel foil with nano-sized grains has high purity, high density and good mechanical properties, and has broad application prospects.

[0058] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0059] Example 1

[0060] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using a nickel plate as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0061] The distance between the two electrodes is 10 mm, and the cathode current density is 3 A / dm 2 , the pulse period is 40ms and the duty cycle is 1.5:1;

[0062] The electrolyte includes water as a solvent and the following components in the following concentrations: 400 g / L nickel sulfate, 10 g / L nickel chloride, 0.05 g / L wetting agent 2-ethylhexyl sodium sulfate, 40 g / L buffer sodium citrate, and 0.5 g / L brightener propoxylated butynediol;

[0063] The pH of the electrolyte was 3, and the temperature of electrodeposition was 50°C;

[0064] The electrodeposition time is 3 hours. The titanium plate after electrodeposition is taken out from the electrolyte, cleaned, dried and peeled off in sequence to obtain a bright, smooth, complete and pinhole-free nanocrystalline nickel foil. Figure 1 shown.

[0065] Example 2

[0066] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using a nickel plate as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0067] The distance between the two electrodes is 5 mm, and the cathode current density is 1 A / dm 2 , the pulse period is 30ms and the duty cycle is 1:1;

[0068] The electrolyte includes water as a solvent and the following components in the following concentrations: 300 g / L nickel sulfate, 10 g / L nickel chloride, 0.01 g / L sodium sulfosuccinate salt as a wetting agent, 20 g / L sodium citrate as a buffer, and 0.05 g / L ethoxylated butynediol as a brightener;

[0069] The pH of the electrolyte was 2, and the temperature of electrodeposition was 40°C;

[0070] The electroplating time is 3 hours. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and cleaned and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, smooth, complete and pinhole-free nanocrystalline nickel foil.

[0071] Example 3

[0072] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using a nickel plate as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0073] The distance between the two electrodes is 20 mm, and the cathode current density is 4 A / dm 2 , the pulse period is 60ms and the duty cycle is 3:1;

[0074] The electrolyte includes water as a solvent and the following components in the following concentrations: 300 g / L nickel sulfate, 5 g / L nickel chloride, 0.2 g / L diamyl sulfosuccinate sodium salt as a wetting agent, 60 g / L sodium citrate as a buffer, and 2 g / L ethoxylated propynyl alcohol as a brightener;

[0075] The pH of the electrolyte was 4, and the temperature of electrodeposition was 60°C;

[0076] The electroplating time is 3 hours. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and cleaned and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, smooth, complete and pinhole-free nanocrystalline nickel foil.

[0077] Example 4

[0078] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using a nickel plate as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0079] The distance between the two electrodes is 10 mm, and the cathode current density is 2 A / dm 2 , the pulse period is 40ms and the duty cycle is 1.5:1;

[0080] The electrolyte includes water as a solvent and the following components in the following concentrations: 300 g / L nickel sulfate, 10 g / L nickel chloride, 0.05 g / L wetting agent 2-ethylhexyl sodium sulfate, 40 g / L buffer sodium citrate, and 0.5 g / L brightener propoxylated butynediol;

[0081] The pH of the electrolyte was 2, and the temperature of electrodeposition was 60°C;

[0082] The electroplating time is 3 hours. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and cleaned and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, smooth, complete and pinhole-free nanocrystalline nickel foil.

[0083] Example 5

[0084] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using electrolytic nickel as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0085] The distance between the two electrodes is 10 mm, and the cathode current density is 2 A / dm 2 , the pulse period is 40ms and the duty cycle is 1.5:1;

[0086] The electrolyte includes water as a solvent and the following components in the following concentrations: 400 g / L nickel sulfate, 10 g / L nickel chloride, 0.05 g / L polyoxyethylene alkylphenol ether sulfate sodium salt as a wetting agent, 40 g / L sodium citrate as a buffer, and 1 g / L propoxylated butynediol as a brightener;

[0087] The pH of the electrolyte was 2, and the temperature of electrodeposition was 60°C;

[0088] The electroplating time is 3h. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and washed and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, flat, complete and pinhole-free nanocrystalline nickel foil.

[0089] Example 6

[0090] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using electrolytic nickel as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0091] The distance between the two electrodes is 10 mm, and the cathode current density is 4 A / dm 2 , the pulse period is 50ms and the duty cycle is 1:1;

[0092] The electrolyte includes water as a solvent and the following components in the following concentrations: 300 g / L nickel sulfate, 10 g / L nickel chloride, 0.05 g / L diamyl sulfosuccinate sodium salt as a wetting agent, 40 g / L citric acid as a buffer, and 1 g / L propoxylated butynediol as a brightener;

[0093] The pH of the electrolyte was 2, and the temperature of electrodeposition was 60°C;

[0094] The electroplating time is 3h. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and washed and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, flat, complete and pinhole-free nanocrystalline nickel foil.

[0095] Example 7

[0096] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using electrolytic nickel as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0097] The distance between the two electrodes is 10 mm, and the cathode current density is 2 A / dm 2 , the pulse period is 40ms and the duty cycle is 1.5:1;

[0098] The electrolyte includes water as a solvent and the following components in the following concentrations: nickel sulfate 500 g / L, nickel chloride 15 g / L, wetting agent 2-ethylhexyl sodium sulfate 0.05 g / L, buffer citric acid 50 g / L, brightener sulfopropargyl ether sodium salt 1 g / L;

[0099] The pH of the electrolyte was 2, and the temperature of electrodeposition was 60°C;

[0100] The electroplating time is 3h. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and washed and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, flat, complete and pinhole-free nanocrystalline nickel foil.

[0101] Example 8

[0102] A method for preparing nanocrystalline nickel foil by electrodeposition, the specific steps are as follows: using electrolytic nickel as an anode and a titanium plate as a cathode, placing both the anode and the cathode in an electrolyte, and using a pulse power supply to electrodeposit the nanocrystalline nickel foil on the titanium plate.

[0103] The distance between the two electrodes is 10 mm, and the cathode current density is 2 A / dm 2 , the pulse period is 40ms and the duty cycle is 1.5:1;

[0104] The electrolyte includes water as a solvent and the following components in the following concentrations: 300 g / L nickel sulfate, 10 g / L nickel chloride, 0.05 g / L dipentyl sulfosuccinate sodium salt as a wetting agent, 40 g / L sodium citrate as a buffer, and 1 g / L glycerol monopropynyl ether as a brightener;

[0105] The pH of the electrolyte was 3, and the temperature of electrodeposition was 40°C;

[0106] The electroplating time is 3h. The nickel metal layer titanium plate after the nickel metal layer electroplating is taken out from the nickel metal layer electrolyte and washed and dried in sequence. The nickel metal layer formed after the nickel metal layer deposition is peeled off to obtain a bright, flat, complete and pinhole-free nanocrystalline nickel foil.

[0107] Example 9

[0108] The only difference between the embodiment 1 and the embodiment 1 is that the wetting agent 2-ethylhexyl sodium sulfate is replaced by polyoxyethylene alkylphenol ether sodium sulfate.

[0109] Example 10

[0110] The only difference from Example 1 is that the wetting agent, sodium 2-ethylhexyl sulfate, is replaced by sodium diethyl sulfosuccinate.

[0111] Embodiment 11

[0112] The only difference between the above-mentioned embodiment and the embodiment 1 is that the brightener propoxylated butynediol is replaced by ethoxylated butynediol.

[0113] Example 12

[0114] The only difference between the above-mentioned embodiment and the embodiment 1 is that the brightener propoxylated butynediol is replaced by sulfopropargyl ether sodium salt.

[0115] Comparative Example 1

[0116] The only difference between the above method and Example 1 is that the sodium citrate in Example 1 is replaced by boric acid.

[0117] Comparative Example 2

[0118] The only difference from Example 1 is that no brightener propoxylated butynediol is added. Figure 2 As shown, after the electrolysis is completed, the nickel metal layer peels off and breaks, and has no shape.

[0119] Comparative Example 3

[0120] The only difference between this embodiment and Example 1 is that no wetting agent, 2-ethylhexyl sodium sulfate, is added. Figure 3 As shown, many pinholes appeared in the obtained nickel foil.

[0121] Nanocrystalline nickel foil performance test: The roughness of the nickel foil is measured using a roughness meter according to standard ISO8503; the thickness of the nickel foil is measured using a film thickness tester according to standard GB / T 36053-2018; the tensile strength and elongation of the nickel foil are tested using a tensile strength tester according to GB / T228; the nanocrystalline nickel foil is characterized by TEM, and then the grain size is statistically analyzed to obtain the average grain size. The TEM image of the nanocrystalline nickel foil prepared in Example 4 is as follows: Figure 4As shown in Table 1, small and uniform nanocrystals can be observed.

[0122] Table 1

[0123]

[0124] Note: “-” indicates that the relevant quantity was not measured.

[0125] It can be seen from Table 1 that, compared with Comparative Examples 1-3, the nanocrystalline nickel foil prepared in Examples 1-12 of the present invention generated fine grains and significantly refined the grain size. The prepared nanocrystalline nickel foil has low roughness, high tensile strength and high elongation.

[0126] In addition, it can be seen from the data in Examples 1 to 15 and Comparative Examples 1 to 6 that the addition of an appropriate amount of buffer and an appropriate amount of wetting agent in the electrolyte system can promote the uniform precipitation of nickel ions on the entire cathode plate, form a dense structure, and reduce the roughness of the nickel foil. Especially when sodium dihexyl sulfonate or sodium dipentyl sulfonate is used as a wetting agent (see Example 1, Examples 9-11), the roughness of the nickel foil is significantly reduced.

[0127] By comparing Example 1, Example 9, Example 10 and Comparative Example 3, it can be seen that the addition of a wetting agent, especially sodium polyoxyethylene alkylphenol ether sulfate and sodium 2-ethylhexyl sulfate, is beneficial to refining the grain size and uniform precipitation of nickel ions, avoiding the generation of pinholes, and obtaining a nanocrystalline nickel foil with high roughness, high tensile strength and high elongation.

[0128] From the comparison of Example 1, Example 1, Example 12 and Comparative Example 2, it can be seen that the addition of brightener, especially the addition of propoxylated butynediol and ethoxylated butynediol, is conducive to refining the grain size, forming a dense structure, and obtaining a nanocrystalline nickel foil with high roughness, high tensile strength and high elongation. From the comparison of Example 1 and Comparative Example 1, it can be seen that under the same addition amount, using citric acid as a buffer is more conducive to nanocrystalline nickel foil with fine grains, low roughness, high tensile strength and high elongation.

[0129] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing nanocrystalline nickel foil by electrodeposition, characterized in that: A nickel plate is used as an anode and a titanium plate is used as a cathode. The anode and the cathode are both placed in an electrolyte, and a pulse power source is used to electrodeposit the titanium plate to prepare a nanocrystalline nickel foil; The electrolyte comprises water and the following components: Nickel sulfate 300~500g / L; Nickel chloride 5-15 g / L; Wetting agent 0.01~0.2g / L; Buffer 20~60g / L; Brightener 0.05~2g / L; The pH of the electrolyte is 2 to 4, and the temperature of the electrodeposition is 40 to 60° C.; The buffer is selected from one or both of citric acid and sodium citrate; The brightener is selected from one or more of propoxylated butynediol, ethoxylated butynediol, sulfopropargyl ether sodium salt, ethoxylated propargyl alcohol, and glycerol monopropargyl ether; The wetting agent is selected from one or more of 2-ethylhexyl sodium sulfate, polyoxyethylene alkylphenol ether sulfate sodium salt, sulfosuccinate sodium salt, dipentyl sulfosuccinate sodium salt, and diethyl sulfosuccinate sodium salt.

2. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1, characterized in that: The wetting agent is selected from one or two of polyoxyethylene alkylphenol ether sodium sulfate and 2-ethylhexyl sodium sulfate; Preferably, the concentration of the wetting agent is 0.03-0.1 g / L.

3. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The brightener is selected from one or both of propoxylated butynediol and ethoxylated butynediol; Preferably, the concentration of the brightener is 0.5-1 g / L.

4. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: Cathode current density is 1~4A / dm 2 , the pulse period is 30ms~60ms, and the duty cycle is (1~3):

1.

5. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The pH of the electrolyte is adjusted by first mixing the components according to the formula, and then adding Na2CO3 powder and / or acidic aqueous solution to adjust the pH of the mixed system.

6. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The acidic substances in the acidic aqueous solution are H2SO4 and HCl, and the molar ratio of H2SO4 to HCl is (6-8):

1.

7. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The distance between the anode and the cathode is 5 to 20 mm; Preferably, the distance between the two poles is 10-20 mm.

8. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The electrodeposition time is 1 to 5 hours; Preferably, the electrodeposition time is 2 to 3 hours; Preferably, the titanium plate after the electrodeposition is taken out from the electrolyte, and then washed and dried in sequence, and then the nickel metal layer formed after the deposition is peeled off to obtain the nanocrystalline nickel foil.

9. The method for preparing nanocrystalline nickel foil by electrodeposition according to claim 1 or 2, characterized in that: The nickel plate is in the form of a basket, comprising a metal basket and nickel metal waste filled in the metal basket.

10. Nanocrystalline nickel foil prepared by the method for preparing nanocrystalline nickel foil by electrodeposition according to any one of claims 1 to 9; Preferably, the average particle size of nanocrystals in the nanocrystalline nickel foil is 20 to 80 nm.

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